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Sample records for heterogeneous fenton catalysts

  1. Magnetic minerals from volcanic Ultisols as heterogeneous Fenton catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Aravena, S., E-mail: susana.aq@gmail.com; Pizarro, C.; Rubio, M. A. [USACH, Facultad de Quimica y Biologia (Chile); Cavalcante, L. C. D. [Universidade Federal do Piaui, Centro de Ciencias da Natureza (Brazil); Garg, V. K. [Universidade de Brasilia, Instituto de Fisica (Brazil); Pereira, M. C.; Fabris, J. D. [ICEx-UFMG, Departamento de Quimica (Brazil)

    2010-01-15

    This study was devoted to the evaluation of the effectiveness of Fenton catalysts, based on magnetically-concentrated portions of iron oxide-rich sand fractions from two magnetic Ultisols, derived from volcanic materials of southern Chile. The samples were labeled according to the municipality where the sample sites are geographically located, namely Metrenco and Collipulli, and were characterized with Moessbauer spectroscopy at 298 K and saturation magnetization ({sigma}) measurements. Moessbauer data revealed a complex magnetic hyperfine structure for these magnetic portions from both soil-sand materials, suggesting relatively complex mineral assemblages. The monitored rate of H{sub 2}O{sub 2} decomposition via heterogeneous Fenton reaction revealed that materials from the Collipulli soil are more efficient Fenton catalyst than are those from the Metrenco soil. The reasons for these differences are from now on being explored on basis of a more detailed chemical investigation of these samples.

  2. Heterogeneous electro-Fenton catalyst for 1-butylpyridinium chloride degradation.

    Science.gov (United States)

    Meijide, Jessica; Pazos, Marta; Sanromán, Maria Ángeles

    2017-10-15

    The application of the electro-Fenton process for organic compound mineralisation has been widely reported over the past years. However, operational problems related to the use of soluble iron salt as a homogeneous catalyst involve the development of novel catalysts that are able to operate in a wide pH range. For this purpose, polyvinyl alcohol-alginate beads, containing goethite as iron, were synthesised and evaluated as heterogeneous electro-Fenton catalyst for 1-butylpyridinium chloride mineralisation. The influence of catalyst dosage and pH solution on ionic liquid degradation was analysed, achieving almost total oxidation after 60 min under optimal conditions (2 g/L catalyst concentration and pH 3). The results showed good catalyst stability and reusability, although its effectiveness decreases slightly after three successive cycles. Furthermore, a plausible mineralisation pathway was proposed based on the oxidation byproducts determined by chromatographic techniques. Finally, the Microtox® test revealed notable detoxification after treatment which demonstrates high catalyst ability for pyridinium-based ionic liquid degradation by the electro-Fenton process.

  3. Potential of Ceria-Based Catalysts for the Oxidation of Landfill Leachate by Heterogeneous Fenton Process

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    E. Aneggi

    2012-01-01

    Full Text Available In this study, ceria and ceria-zirconia solid solutions were tested as catalyst for the treatment of landfill leachate with a Fenton-like process. The catalysts considered in this work were pure ceria and ceria-zirconia solid solutions as well as iron-doped samples. All the catalysts were extensively characterized and applied in batch Fenton-like reactions by a close batch system, the COD (chemical oxygen demand and TOC (total organic carbon parameters were carried out before and after the treatments in order to assay oxidative abatement. Results show a measurable improvement of the TOC and COD abatement using ceria-based catalysts in Fenton-like process and the best result was achieved for iron-doped ceria-zirconia solid solution. Our outcomes point out that heterogeneous Fenton technique could be effectively used for the treatment of landfill leachate and it is worth to be the object of further investigations.

  4. Modified natural zeolite as heterogeneous Fenton catalyst in treatment of recalcitrants in industrial effluent

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    Milton M. Arimi

    2017-04-01

    Full Text Available Industrial effluents with high recalcitrants should undergo post-treatment after biological treatment. The aim of this study was to use cheap and abundantly available natural materials to develop heterogeneous Fenton catalysts for the removal of colored recalcitrants in molasses distillery wastewater (MDW. The pellets of zeolite, which is naturally available in many countries, were modified by pre-treatment with sulphuric acid, nitric acid and hydrochloric acid, before embedding on them the ferrous ions. The effects of pH and temperature on heterogeneous Fenton were studied using the modified catalysts. The sulphuric acid-ferrous modified catalysts showed the highest affectivity which achieved 90% color and 60% TOC (total organic carbon removal at 150 g/L pellet catalyst dosage, 2 g/L H2O2 and 25 °C. The heterogeneous Fenton with the same catalyst caused improvement in the biodegradability of anaerobic effluent from 0.07 to 0.55. The catalyst was also applied to pre-treat the raw MDW and increased it's biodegradability by 4%. The color of the resultant anaerobic effluent was also reduced. The kinetics of total TOC removal was found to depend on operation temperature. It was best described by simultaneous first and second order kinetics model for the initial reaction and second order model for the rest of the reaction.

  5. Simple Copper(II) Schiff Base Complex as Efficient Heterogeneous Photo-Fenton-like Catalyst

    National Research Council Canada - National Science Library

    Fei, Bao-Li; Wang, Jiang-Hong; Yan, Qing-Ling; Liu, Qing-Bo; Long, Jian-Ying; Li, Yang-Guang; Shao, Kui-Zhan; Su, Zhong-Min; Sun, Wei-Yin

    2014-01-01

    ...) as photo-Fenton-like catalysts. Both 1 and 2 exhibited excellent catalytic performance without an acidification process, and the mononuclear complex 2 functioned better than the dinuclear complex 1...

  6. Degradation of aniline by heterogeneous Fenton's reaction using a Ni-Fe oxalate complex catalyst.

    Science.gov (United States)

    Liu, Yucan; Zhang, Guangming; Fang, Shunyan; Chong, Shan; Zhu, Jia

    2016-11-01

    A Ni-Fe oxalate complex catalyst was synthesized and characterized by means of Brunauer-Emmet-Teller (BET) method, scanning electron microscope (SEM) and X-ray photo-electron spectroscopy (XPS). The catalyst showed good catalytic activity for aniline degradation by heterogeneous Fenton's reaction, in which the synergetic index was 9.3. The effects of reaction temperature, catalyst dosage, hydrogen peroxide concentration and initial pH were investigated. Under the optimum conditions (T = 293 K, catalyst dosage = 0.2 g/L, H2O2 concentration = 4 mmol/L and initial pH = 5.4), 100% aniline could be removed within 35 min, and approximately 88% deamination efficiency was achieved in 60 min. The aniline degradation process followed the pseudo-first-order kinetic (k = 0.177 min(-1)) with activation energy (Ea) of 49.4 kJ mol(-1). Aniline could be removed in a broad initial pH (3-8) due to the excellent pH-tolerance property of the catalyst. The detected ammonium ion indicated that deamination occurred during aniline degradation. It was proposed that deamination synchronized with aniline removal, and aniline was attacked by free radicals to generate benzoquinonimine and phenol. This system is promising for the removal of aniline from water. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Removal of methyl orange by heterogeneous Fenton catalysts prepared using glycerol as green reducing agent.

    Science.gov (United States)

    Trotte, Natália S F; Alzamora, M; Sánchez, D R; Carvalho, Nakédia M F

    2017-08-29

    This study aims to prepare environmentally friendly iron catalysts supported on silica, using glycerol as green reducing and stabilizing agent, for application in heterogeneous Fenton degradation of the pollutant dye methyl orange (MO). The catalysts were characterized by X-ray powder diffraction, atomic absorption spectroscopy, scanning electron microscopy, transmission electron microscopy, thermogravimetric analyses, Mössbauer and Fourier transform infrared spectroscopies, which revealed the formation of iron(II)/(III) oxalates from the oxidation of glycerol by the iron(III) nitrate precursor. Besides, iron oxihydroxide nanoparticles with superparamagnetic behavior were also formed. Iron catalysts prepared in the presence of nickel(II) or zinc(II) nitrates lead to the formation of the corresponding oxalates. The catalysts were able to degrade MO, efficiently in 180 min of reaction. Fe/SiO 2 furnished higher reaction rates, followed by Zn4Fe2/SiO 2 , which presented higher iron content as well as the smallest nanoparticles. Reaction parameters such as catalyst dosage, hydrogen peroxide concentration, pH and reaction temperature were investigated.

  8. Fast decolorization of azo methyl orange via heterogeneous Fenton and Fenton-like reactions using alginate-Fe2+/Fe3+films as catalysts.

    Science.gov (United States)

    Quadrado, Rafael F N; Fajardo, André R

    2017-12-01

    The efficiency of Fenton and Fenton-like processes can be seriously affected by the continuous loss of iron ions and by the formation of solid sludge. Here, alginate (Alg) films were synthesized to stabilize iron ions (Fe 2+ and Fe 3+ ) and to enhance their catalytic activities towards the decolorization of methyl orange via heterogeneous Fenton and Fenton-like processes. Iron ions were ionically bond to the Alg molecules resulting in a three-dimensional network with specific structural and morphological features according to the valence states of iron. Our results demonstrated that both Alg-Fe 2+ and Alg-Fe 3+ films show highlighted catalytic activity for the decolorization of MO and high decolorization rates. Reuse experiments demonstrated that both films could be employed in at least five consecutive decolorization processes without losing their catalytic efficiency or stability. Taken together, our findings reveal that the Alg-Fe 2+ and Alg-Fe 3+ films may be suitable low-cost catalysts in heterogeneous Fenton and Fenton-like processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. NiFe(C2O4)xas a heterogeneous Fenton catalyst for removal of methyl orange.

    Science.gov (United States)

    Liu, Yucan; Zhang, Guangming; Chong, Shan; Zhang, Nan; Chang, Huazhen; Huang, Ting; Fang, Shunyan

    2017-05-01

    This paper studies a heterogeneous Fenton catalyst NiFe(C 2 O 4 ) x , which showed better catalytic activity than Ni(C 2 O 4 ) x and better re-usability than Fe(C 2 O 4 ) x . The methyl orange removal efficiency was 98% in heterogeneous Fenton system using NiFe(C 2 O 4 ) x . The prepared NiFe(C 2 O 4 ) x had a laminated shape and the size was in the range of 2-4 μm, and Ni was doped into catalyst's structure successfully. The NiFe(C 2 O 4 ) x had a synergistic effect of catalyst of 24.7 for methyl orange removal, and the dope of Ni significantly reduced the leaching of Fe by 77%. The reaction factors and kinetics were investigated. Under the optimal conditions, 0.4 g/L of catalyst dose and 10 mmol/L of hydrogen peroxide concentration, 98% of methyl orange was removed within 20 min. Analysis showed that hydroxyl radicals and superoxide radicals participated in the reaction. With NiFe(C 2 O 4 ) x catalyst, the suitable pH range for heterogeneous Fenton system was wide from 3 to 10. The catalyst showed good efficiency after five times re-use. NiFe(C 2 O 4 ) x provided great potential in treatment of refractory wastewater with excellent property. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Residue-based iron oxide catalyst for the degradation of simulated petrochemical wastewater via heterogeneous photo-Fenton process.

    Science.gov (United States)

    Scaratti, Gidiane; Rauen, Thalita Grando; Baldissarelli, Vanessa Zanon; José, Humberto Jorge; Moreira, Regina De Fátima Peralta Muniz

    2017-08-10

    Iron oxide with a high degree of purity was recovered from waste and used as an environmentally friendly, low-cost catalyst in the application of the photo-Fenton process to simulated petrochemical wastewater (SPW). Iron oxide nanoparticles were characterized by X-ray powder diffraction, transmission electron microscopy, N2 adsorption/desorption isotherms, zeta potential, toxicity and atomic absorption spectrometry. The experiments were performed in a batch photochemical reactor, at 20 ± 2.0°C and pH 3.0. The SPW was efficiently mineralized and oxidized using a low catalyst dosage. The results showed that the organic compounds present in the wastewater were not adsorbed onto the solid surface. The solid was found to be stable with negligible leaching and low toxicity. The kTOC/kCOD ratios were calculated and varied according to the process: for a homogeneous reaction, the ratio obtained was 0.31 and for the heterogenous photo-Fenton process, it was closer to 1. The chemical oxygen demand and total organic carbon removal values were very close, indicating that the SPW is immediately mineralized, without producing partially oxidized compounds. The residue-based goethite studied represents a good alternative to commercially available catalysts in terms of sources and availability.

  11. Degradation of Amaranth azo dye in water by heterogeneous photo-Fenton process using FeWO4 catalyst prepared by microwave irradiation.

    Science.gov (United States)

    da Cruz Severo, Eric; Anchieta, Chayene Gonçalves; Foletto, Vitória Segabinazzi; Kuhn, Raquel Cristine; Collazzo, Gabriela Carvalho; Mazutti, Marcio Antonio; Foletto, Edson Luiz

    2016-01-01

    FeWO4 particles were synthesized by a simple, rapid and facile microwave technique and their catalytic properties in heterogeneous photo-Fenton reaction were evaluated. This material was employed in the degradation of Amaranth azo dye. Individual and interactive effects of operational parameters such as pH, dye concentration and H2O2 dosage on the decolorization efficiency of Amaranth dye were evaluated by 2(3) central composite design. According to characterization techniques, a porous material and a well-crystallized phase of FeWO4 oxide were obtained. Regarding the photo-Fenton reaction assays, up to 97% color and 58% organic carbon removal were achieved in the best experimental conditions. In addition, the photo-Fenton process maintained treatment efficiency over five catalyst reuse cycles to indicate the durability of the FeWO4 catalyst. In summary, the results reveal that the synthesized FeWO4 material is a promising catalyst for wastewater treatment by heterogeneous photo-Fenton process.

  12. Enhanced photo-Fenton degradation of rhodamine B using graphene oxide-amorphous FePO₄ as effective and stable heterogeneous catalyst.

    Science.gov (United States)

    Guo, Sheng; Zhang, Gaoke; Yu, Jimmy C

    2015-06-15

    A series of graphene oxide (GO)-FePO4 composites with different GO weight ratios (2.5%, 5%, 10%, w/w) were prepared using a simple precipitation process and were firstly used as heterogeneous photo-Fenton catalysts. FESEM images prove the loose structure of the 5GO-FePO4 composite. UV-vis analysis demonstrates that the introduction of GO could enhance solar energy utilization of the composites. Under visible light irradiation, the degradation rate of rhodamine B (RhB) by the 5GO-FePO4 composite was 2.87 times more than that by the pure FePO4 in the presence of hydrogen peroxide. The composite was highly effective for the degradation of RhB in a wide pH range of 2.18-10.40 with negligible iron leaching. Moreover, the composite still showed high catalytic activity after six cycles, which makes it a promising heterogeneous catalyst for wastewater treatment. The introduction of GO promotes the photo-Fenton reaction of GO-FePO4 via three roles: offering more active sites, increasing adsorption capacity and accelerating the Fe(3+)/Fe(2+) cycle by improving the utilization of solar energy. Our work may provide new insights for the development of new effective heterogeneous photo-Fenton catalyst. Copyright © 2015 Elsevier Inc. All rights reserved.

  13. Photo-Fenton oxidation of azo dye Reactive Black B using an immobilized iron oxide as heterogeneous catalyst.

    Science.gov (United States)

    Shih, Yu-Jen; Ho, Chien-Hung; Huang, Yao-Hui

    2013-04-01

    The heterogeneous oxidation of azo dye Reactive Black B (RBB) by the photo-Fenton system catalyzed with an immobilized iron oxide, B1 (supported with SiO2 grain), was investigated. Reactive Black B oxidation was carried out in an expended-bed reactor in which the effect of B1 dosage on the decolorization and degradation of RBB was examined. Through pseudo-first-order kinetic studies, decolorization was found to be faster than degradation with a fixed rate constant ratio. By determining the iron dissolution from B1, RBB oxidation was supposed to mainly occur on the B1 surface, which catalyzed the generation of hydroxyl radicals in the photo-Fenton reaction. Accordingly, the efficiency of photo-Fenton could reach 100% and 91.2% of decolorization and degradation, respectively, in 300 minutes.

  14. Heterogeneous Fenton-like discoloration of methyl orange using Fe3O4/MWCNTs as catalyst: combination mechanism and affecting parameters

    Science.gov (United States)

    Xu, Huan-Yan; Wang, Yuan; Shi, Tian-Nuo; Zhao, Hang; Tan, Qu; Zhao, Bo-Chao; He, Xiu-Lan; Qi, Shu-Yan

    2018-01-01

    Multi-walled carbon nanotubes (MWCNTs) can act not only as a support for Fe3O4 nanoparticles (NPs) but also as a coworker with synergistic effect, accordingly improving the heterogeneous Fenton-like efficiency of Fe3O4 NPs. In this study, Fe3O4 NPs were in situ anchored onto MWCNTs by a moderate co-precipitation method and the as-prepared Fe3O4/MWCNTs nanocomposites were employed as the highly efficient Fenton-like catalysts. The analyses of XRD, FTIR, Raman, FESEM, TEM and HRTEM results indicated the formation of Fe3O4 crystals in Fe3O4/MWCNTs nanocomposites prepared at different conditions and the interaction between Fe3O4 NPs and MWCNTs. Over a wide pH range, the surface of modified MWCNTs possessed negative charges. Based on these results, the possible combination mechanism between Fe3O4 NPs and MWCNTs was discussed and proposed. Moreover, the effects of preparation and catalytic conditions on the Fenton-like catalytic efficiency were investigated in order to gain further insight into the heterogeneous Fenton-like reaction catalyzed by Fe3O4/MWCNTs nanocomposites.

  15. Magnetic multi-metal co-doped magnesium ferrite nanoparticles: An efficient visible light-assisted heterogeneous Fenton-like catalyst synthesized from saprolite laterite ore.

    Science.gov (United States)

    Diao, Yifei; Yan, Zhikai; Guo, Min; Wang, Xidong

    2018-02-15

    Magnetic nanoparticles of multi-metal co-doped magnesium ferrite (MgFe 2 O 4 ) were synthesized from saprolite laterite ore by a hydrothermal method, and firstly proposed as a heterogeneous photon-Fenton-like catalyst for degradation of Rhodamine B (RhB). The factors that influence the degradation reaction including pH value, the concentration of H 2 O 2 and the amount of catalyst, were systematically investigated. The doped MgFe 2 O 4 exhibited a degradation efficiency up to 96.8%, and the chemical oxygen demand (COD) and total organic carbon (TOC) removal efficiencies about 85.6% and 68.3%, respectively, under visible light illumination for 180min. The high activity is mainly attributed to the high specific surface area of the catalyst and the synergistic interaction between photo-catalytic oxidation and Fenton-like oxidation. Moreover, the catalyst also showed good stability and recycling performance for degrading RhB. After five consecutive degradation cycles, the activity decayed no more than 10%. Compared to other catalysts prepared from pure chemical agents, the multi-metal co-doped MgFe 2 O 4 is more competitive due to its high activity, good stability, ease of recollection, and especially the use of saprolite laterite ore as precursor. This work may provide a new avenue to synthesize efficient ferrite catalysts for degrading organic pollutants in wastewater by using natural minerals. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Antimicrobial activities of hydrogen peroxide and its activation by a novel heterogeneous Fenton's-like modified PAN catalyst

    National Research Council Canada - National Science Library

    Boateng, M K; Price, S L; Huddersman, K D; Walsh, S E

    2011-01-01

    .... The antimicrobial properties of an iron-based novel heterogeneous polyacrylonitrile catalyst in combination with hydrogen peroxide were examined against Escherichia coli, Pseudomonas aeruginosa...

  17. Removal of Textile Dyes from Aqueous Solution by Heterogeneous Photo-Fenton Reaction Using Modified PAN Nanofiber Fe Complex as Catalyst

    Directory of Open Access Journals (Sweden)

    Xueting Zhao

    2013-01-01

    Full Text Available The modified PAN nanofiber Fe complex was prepared by the amidoximation and Fe coordination of PAN nanofiber was obtained using electrospinning technique and then used for the heterogeneous Fenton degradation of textile dyes as a novel catalyst. Some main factors affecting dye degradation such as Fe content of catalyst, irradiation intensity, H2O2 initial concentration, the solution pH as well as dye structure, and initial concentration were investigated. UV-Vis spectrum analysis and TOC measurement were also used to evaluate the dye degradation process. The results indicated that the modified PAN nanofiber Fe complex exhibited a much better catalytic activity for the heterogeneous Fenton degradation of textile dyes than the Fe complex prepared with conventional PAN yarns in the dark or under light irradiation. Increasing Fe content of catalyst or irradiation intensity would accelerate the dye degradation. And the highest degradation efficiency was obtained with 3.0 mmol L−1 H2O2 at pH 6. Moreover, this complex was proved to be a universal and efficient catalyst for degradation of three classes of textile dyes including azo dye, anthraquinone dye, and triphenylmethane dye. Additionally, the dye mineralization was also significantly enhanced in the presence of this complex.

  18. Heterogeneous photo-Fenton-like catalysts Cu2V2O7 and Cr2V4O13 for an efficient removal of azo dye in water

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    Sangeeta Kalal

    2016-12-01

    Full Text Available This work deals with the degradation of non-biodegradable azo-dye (Evans blue by the heterogeneous photo-Fenton-like process using copper pyrovanadate (Cu2V2O7 and chromium tetravanadate (Cr2V4O13 as catalysts, which have been prepared by wet chemical method. These catalysts were characterized by different techniques such as scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and Brunauer–Emmett–Teller surface area analysis. The effect of various parameters such as initial pH, concentration of dye, amount of catalyst, amount of H2O2, and light intensity on the reaction rate has also been studied. Photodegradation efficiency was found 77.78 and 79% for copper pyrovanadate (Cu2V2O7 and chromium tetravanadate (Cr2V4O13, respectively. A tentative mechanism involving ·OH radicals as an oxidant for the degradation of dye has also been proposed. The observations revealed that the rate of photo-Fenton-like degradation of dye follows pseudo-first-order kinetics.

  19. Extrusion of Fe2O3/SBA-15 mesoporous material for application as heterogeneous Fenton-like catalyst

    Directory of Open Access Journals (Sweden)

    María Isabel Pariente

    2015-03-01

    Full Text Available The aim of this work has been the extrusion of powder Fe2O3/SBA-15 catalyst in order to be successfully used in continuous catalytic fixed bed reactors as Fenton-like catalyst. The extrusion method was optimised using an amorphous silica material of similar properties than the Fe2O3/SBA-15 catalyst. The main studied variable was the composition of the extrusion paste using bentonite and methylcellulose as inorganic and organic binders, respectively. The organic content displayed a significant influence on the mechanical strength and specific surface area of the final extrudates. In contrast, the inorganic binder content hardly affected the final properties (in the studied range. The extruded Fe2O3/SBA-15 material showed a remarkable mechanical strength as well as the typical mesoporous structure of Fe2O3/SBA-15 with a relevant specific surface area (264 m2/g. The extruded catalyst achieved a high catalytic performance in the catalytic wet peroxide oxidation of phenol with a 60 % of total organic carbon reduction in both batch and continuous processes.

  20. Preservation of Fe complexes into layered double hydroxides improves the efficiency and the chemical stability of Fe complexes used as heterogeneous photo-Fenton catalysts

    Science.gov (United States)

    Huang, Zhujian; Wu, Pingxiao; Gong, Beini; Lu, Yonghong; Zhu, Nengwu; Hu, Zhixian

    2013-12-01

    Fe complexes ([Fe(Ox)3]3- and [Fe(Cit)2]3-) have been heterogenized through preservation into MgAl-layered double hydroxides (LDHs). The SEM images and N2 adsorption-desorption isotherm showed that the obtained products were mesoporous materials and the specific surface area of LDHs/Fe-complex composites were obviously greater than pristine LDHs, which is beneficial for the adsorption of organic pollutants. Measurement of adsorptive and heterogeneous photo-Fenton degradation of methylene blue (MB) suggested that the LDHs/Fe-complex composites had an excellent adsorption capacity at different pHs and the adsorption isotherm modeled well with the Langmuir equation. The enhancement of adsorption capacity may be attributed to the external hydroxyl groups of LDHs. MB was enriched on the surface of LDHs/Fe-complex composites, which favors MB degradation in situ. The obtained composites displayed an high photocatalytic activity in a pH range from 4.0 to 6.0 with dissolved Fe cation at a low concentration. Therefore, Fe complexes intercalated into LDHs can be an effective heterogeneous Fenton catalyst for oxidation of organic pollutants in a relatively wide pH range.

  1. Heterogeneous advanced photo-fenton oxidation of phenolic aqueous solutions over iron-containing SBA-15 catalyst

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    Bailiche Z.

    2013-09-01

    Full Text Available Iron-containing SBA15 catalysts have been prepared following different synthesisroutes, direct synthesis by adjusting pH at 3 and 6 and with post synthesis procedure. Activity and stability of these materials were assessed on the photo-Fenton degradation of phenolic aqueous solutions by H2O2 using near UV irradiation (254 nm at room temperature and initial neutral pH. Their catalytic performance was mentioned in terms of phenol and total organic carbon (TOC conversions. Several complementary techniques, including XRD, Nitrogen sorption isotherms, UV visible, were used to evaluate the final structural and textural properties of calcined Fe-SBA15 materials. These materials show a high activity and stability of iron species.

  2. Role of copper pyrovanadate as heterogeneous photo-Fenton like catalyst for the degradation of neutral red and azure-B: An eco-friendly approach

    Energy Technology Data Exchange (ETDEWEB)

    Kalal, Sangeeta; Ameta, Noopur; Kumar, Sudhish; Punjabi, Pinki Bala [M. L. Sukhadia University, Udaipur (India); Chauhan, Narendra Pal Singh [B. N. P. G. College, Udaipur (India); Ameta, Rakshit [PAHER University, Udaipur (India)

    2014-12-15

    The heterogeneous photo-Fenton like process is a green chemical pathway.. It has an edge over conventional Fenton and photo-Fenton processes as it does not require the removal of ferrous/ferric ions in the form of sludge. We prepared copper pyrovanadate or Volborthite (Cu{sub 3}V{sub 2}(OH){sub 2}O{sub 7}·2H{sub 2}O) composite photocatalyst by wet chemical method. The photocatalyst was characterized by SEM, XRD, IR, TGA/DSC, EDX and BET. Experiments demonstrated that catalyst could effectively catalyze degradation of neutral red and azure-B in presence of H{sub 2}O{sub 2} in visible light. Moreover, the photo-Fenton-like catalytic activity of Cu{sub 3}V{sub 2}(OH){sub 2}O{sub 7}·2H{sub 2}O was much higher than CuO and V{sub 2}O{sub 5}, when used alone as photocatalyst. The effect of variation of different parameters, i.e., pH, amount of photocatalyst, concentration of dye, amount of H{sub 2}O{sub 2} and light intensity was also investigated. The degradation was well fitted under pseudo-first-order reaction with a rate constant of 2.081x10{sup −4} sec{sup −1} and 3.876x10{sup −4} sec{sup −1} for neutral red and azure-B, respectively. Quality parameters of dye solutions before and after photo-Fenton degradation were also determined. A tentative mechanism involving •OH radical as an oxidant has been proposed. The high catalytic activity may be due to the Cu{sub 3}V{sub 2}(OH){sub 2}O{sub 7}·2H{sub 2}O shell, which not only increased the surface hydroxyl groups, but also enhanced the interfacial electron transfer.. The catalyst has been found to possess good recyclability.

  3. NATURAL IRON OXIDE AS A HETEROGENEOUS PHOTO-FENTON-LIKE CATALYST FOR THE DEGRADATION OF 1-NAPHTHOL UNDER ARTIFICIAL AND SOLAR LIGHT

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    L MAMMERI

    2014-07-01

    Full Text Available A heterogeneous photo-Fenton-like degradation process of 1-naphthol (1-NP promoted by natural iron oxide (NIO in the presence of H2O2 was studied under artificial (365 nm and solar irradiation. This is an important reaction for the environment since both H2O2 and iron oxides are common constituents of natural waters. Furthermore, iron oxides function as catalysts in chemical oxidation processes used with H2O2 for treatment of contaminated waters. The NIO used in this study was characterized by X-ray diffraction (XRD, X-ray fluorescence and Brunauer–Emmett–Teller (BET methods. The results show that the NIO is a composite material that contains predominantly crystalline hematite particales (Fe2O3. The Fe2O3 in NIO was able to initiate the Fenton-like and photo-Fenton-like reactions. The effects of initial pH, catalyst dosage, H2O2 concentration and the wavelength of the light source (UV and solar on the photodegradation of 1-NP were investigated. The optimal content of the NIO was 1 g L-1 and the optimal H2O2 concentration was 10 mM. The degradation could occur efficiently over a wide pH range of 3-8.3. Furthermore, an important effect of light was observed. The photo-oxidation of 1-NP in NIO-H2O2 system under solar light was significantly accelerated in comparison with artificial irradiation at 365 nm.

  4. Preparative treatment with NaOH to selectively concentrate iron oxides of a Chilean volcanic soil material to produce effective heterogeneous Fenton catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Manzo, Valentina; Pizarro, Carmen, E-mail: carmen.pizarro@usach.cl; Rubio, Maria Angelica [USACH, Facultad de Quimica y Biologia (Chile); Cavalcante, Luis Carlos Duarte [UFMG, Departamento de Quimica-ICEx (Brazil); Garg, Vijayendra Kumar [Universidade de Brasilia, Instituto de Fisica (Brazil); Fabris, Jose Domingos [UFMG, Departamento de Quimica-ICEx (Brazil)

    2011-11-15

    A Chilean volcanic Ultisol material was first size-fractionated so as to obtain the fraction with mean particle sizes {phi} < 53 {mu}m. This sample was then sequentially treated three or five times with 5 mol L{sup - 1} NaOH, in an attempt to evaluate the effectiveness of the selective chemical dissolution to concentrate iron oxides, as a preparation procedure before using the materials as heterogeneous Fenton catalysts. The effects of those treatments on the iron oxides mineralogy were monitored with Moessbauer spectroscopy. The NaOH-treated samples were tested as catalysts towards the H{sub 2}O{sub 2} decomposition. Three or five sequential NaOH treatments were found to be comparably effective, by concentrating nearly the same proportion of iron oxides in the remaining solid phase (25.1 {+-} 0.4 and 23.3 {+-} 0.2 mass%, respectively). 298 K-Moessbauer patterns were similar for both samples, with a central (super)paramagnetic Fe{sup 3 + } doublet and a broad sextet, assignable to several closely coexisting magnetically ordered forms of iron oxides. Despite of this nearly similar effect of the two treatments, the Ultisol material treated three times with NaOH presents higher heterogeneous catalytic efficiency and is more suitable to decompose H{sub 2}O{sub 2} than that with five treatments.

  5. One-step preparation of nanostructured martite catalyst and graphite electrode by glow discharge plasma for heterogeneous electro-Fenton like process.

    Science.gov (United States)

    Khataee, Alireza; Sajjadi, Saeed; Hasanzadeh, Aliyeh; Vahid, Behrouz; Joo, Sang Woo

    2017-09-01

    Natural Martite ore particles and graphite were modified by alternating current (AC) glow discharge plasma to form nanostructured catalyst and cathode electrode for using in the heterogeneous-electro Fenton-like (Het-EF-like) process. The performance of the plasma-treated martite (PTM) and graphite electrode (PTGE) was studied for the treatment of paraquat herbicide in a batch system. 85.78% degradation efficiency for 20 mg L -1 paraquat was achieved in the modified process under desired operational conditions (i.e. current intensity of 300 mA, catalyst amount of 1 g L -1 , pH = 6, and background electrolyte (Na 2 SO 4 ) concentration of 0.05 mol L -1 ) which was higher than the 41.03% for the unmodified one after 150 min of treatment. The ecofriendly modification of the martite particles and the graphite electrode, no chemical needed, low leached iron and milder operational pH were the main privileges of plasma utilization. Moreover, the degradation efficiency through the process was not declined after five repeated cycles at the optimized conditions, which proved the stability of the nanostructured PTM and PTGE in the long-term usage. The archived results exhibit this method is the first example of high efficient, cost-effective, and environment-friendly method for generation of nanostructured samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Nanocasted synthesis of magnetic mesoporous iron cerium bimetal oxides (MMIC) as an efficient heterogeneous Fenton-like catalyst for oxidation of arsenite.

    Science.gov (United States)

    Wen, Zhipan; Zhang, Yalei; Dai, Chaomeng; Sun, Zhen

    2015-04-28

    Magnetic mesoporous iron cerium bimetal oxides (MMIC) with large surface area and pore volume was synthesized via the hard template approach. This obtained MMIC was easily separated from aqueous solution with an external magnetic field and was proposed as a heterogeneous Fenton-like catalyst for oxidation of As(III). The MMIC presented excellent catalytic activity for the oxidation of As(III), achieving almost complete oxidation of 1000ppb As(III) after 60min and complete removal of arsenic species after 180min with reaction conditions of 0.4g/L catalyst, pH of 3.0 and 0.4mM H2O2. Kinetics analysis showed that arsenic removal followed the pseudo-first order, and the pseudo-first-order rate constants increased from 0.0014min(-1) to 0.0548min(-1) as the H2O2 concentration increased from 0.04mM to 0.4mM. On the basis of the effects of XPS analysis and reactive oxidizing species, As(III) in aqueous solution was mainly oxidized by OH radicals, including the surface-bound OHads generated on the MMIC surface which were involved in Fe(2+) and Ce(3+), and free OHfree generation by soluble iron ions which were released from the MMIC into the bulk solution, and the generated As(V) was finally removed by MMIC through adsorption. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Renovation and Reuse of Reactive Dyeing Effluent by a Novel Heterogeneous Fenton System Based on Metal Modified PTFE Fibrous Catalyst/H2O2

    Directory of Open Access Journals (Sweden)

    Bing Li

    2013-01-01

    Full Text Available Cu-Fe bimetallic grafted polytetrafluoroethylene (PTFE fiber complexes were prepared and optimized as the novel heterogeneous Fenton catalysts for the degradation of reactive dyes under UV irradiation. Cotton fabrics were dyed with three reactive dyes, namely, Reactive Red 195, Reactive Yellow 145, and Reactive Blue 222, in tap fresh water using exhaustion process. The spent dyeing effluents were then collected and degraded with the optimized Cu-Fe bimetallic grafted PTFE fiber complex/H2O2 system. The treated dyeing effluents were characterized and reused for the dyeing of cotton fabrics through the same process. The effect of reuse process number on quality of the dyed cotton fabrics was examined. The results indicated that the Cu-Fe bimetallic modified PTFE fiber complex with a Cu/Fe molar ratio of 2.87 was found to be the most effective fibrous catalyst, which enhanced complete decolorization of the treated dyeing effluents with H2O2 in 4 h. However, the TOC removal for the treated dyeing effluents was below 80%. The dyeing quality was not affected for three successive cycles. The increase in residual TOC value influences fourth dyeing cycle. Further TOC reduction of the treated effluents is needed for its repeated reuse in more than three dyeing cycles.

  8. Photocatalytic degradation of Maxilon C.I. basic dye using CS/CoFe{sub 2}O{sub 4}/GONCs as a heterogeneous photo-Fenton catalyst prepared by gamma irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Al-Kahtani, Abdullah A. [Chemistry Department, College of Science, King Saud University, P. O. Box 2455, Riyadh 11451 (Saudi Arabia); Pharmaceutical Chemistry Department, College of Pharmacy, Prince Sattam Bin Abdulaziz University, P. O. Box 173, Alkharj 11942 (Saudi Arabia); Abou Taleb, Manal F., E-mail: abutalib_m@yahoo.com [Chemistry Department, College of Science and Humanities, Prince Sattam Bin Abdulaziz University, P. O. Box 173, Alkharj 11942 (Saudi Arabia); Polymer Department National Center for Radiation Research and Technology, Nasr city, Cairo (Egypt)

    2016-05-15

    Highlights: • CS/CF/GONCs were synthesized via γ-irradiation and used as a heterogeneous photo-Fenton catalyst. • It can degrade Maxilon C.I. basic dye under sunlight irradiation. • A possible degradation pathway of Maxilon C.I. Basic was proposed. • The degradation of Maxilon follows pseudo-first-order kinetics. • The catalyst can be separated by an external magnetic field. • Cyclic degradation tests show the catalyst is highly active, stable and recoverable. - Abstract: CS/CF/GONCs were synthesized via gamma irradiation cross-linking method with the aid of sonication. The nanocomposites exhibited a photo-Fenton catalytic feature for the degradation of Maxilon C.I. basic dye in aqueous medium using sunlight. The effects of pH, H{sub 2}O{sub 2} concentration, and dosage of the catalyst, on the degradation rates of the dyes were examined. The optimal degradation rate was reached with 10 mM H{sub 2}O{sub 2} at pH 9.5. It was verified that the Maxilon C.I. basic dye degradation rate fits a pseudo-first-order kinetics for different initial concentrations of Maxilon C.I. dye. Fourth cyclic tests for Maxilon C.I. degradation showed that the magnetic catalyst was very stable, recoverable, highly active, and easy to separate using an external magnet. Hence, this magnetic catalyst has potential use in organic pollutant removal.

  9. Synergistic Enhancement in Catalytic Performance of Superparamagnetic Fe3O4@Bacilus subtilis as Recyclable Fenton-Like Catalyst

    National Research Council Canada - National Science Library

    Pei Zheng; Zhe Pan; Jun Zhang

    2017-01-01

    Novel well-defined superparamagnetic Fe3O4@Bacilus subtilis composite (Fe3O4@B. subtilis SPMC) was synthesized through a facile electrostatic attraction method and used as a recyclable heterogeneous Fenton-like catalyst...

  10. Degradation of bisphenol A in water by the heterogeneous photo-Fenton.

    Science.gov (United States)

    Jiang, Chuanrui; Xu, Zhencheng; Guo, Qingwei; Zhuo, Qiongfang

    2014-01-01

    Bisphenol A (BPA) is a kind of a controversial endocrine disruptor, and is ubiquitous in environment. The degradation of BPA with the heterogeneous photo-Fenton system was demonstrated in this study. The Fe-Y molecular sieve catalyst was prepared with the ion exchange method, and it was characterized by X-ray radiation diffraction (XRD). The effects ofpH, initial concentration of H2O2, initial BPA concentration, and irradiation intensity on the degradation of BPA were investigated. The service life and iron solubility of catalyst were also tested. XRD test shows that the major phase of the Fe-Y catalyst was Fe2O3. The method of heterogeneous photo-Fenton with Fe-Y catalyst was superior to photolysis, photo-oxidation with only hydrogen, heterogeneous Fenton, and homogeneous photo-Fenton approaches. pH value had no obvious effects on BPA degradation over the range of 2.2-7.2. The initial concentration of H2O2 had an optimal value of 20 x 10(-4) mol/L. The decrease in initial concentration of BPA was favourable for degradation. The intensity of ultraviolet irradiation has no obvious effect on the BPA removal. The stability tests indicated that the Fe-Y catalyst can be reused and iron solubility concentration ranged from NA to 0.0062 mg/L. Based on the results, the heterogeneous photo-Fenton treatment is the available method for the degradation of BPA.

  11. Modified Fe{sub 3}O{sub 4}- hydroxyapatite nanocomposites as heterogeneous catalysts in three UV, Vis and Fenton like degradation systems

    Energy Technology Data Exchange (ETDEWEB)

    Valizadeh, S., E-mail: valizadehsolmaz@yahoo.com; Rasoulifard, M.H., E-mail: m_h_rasoulifard@znu.ac.ir; Dorraji, M.S. Seyed, E-mail: dorraji@znu.ac.ir

    2014-11-15

    Graphical abstract: - Highlights: • Photocatalytic degradation of dye by Ag modified HAP under visible light. • Study of Fenton like degradation of dye by transition metal ions modified HAP. • Comparison of catalytic systems according to Langmuir-Hinshelwood kinetic expression. - Abstract: The magnetite-hydroxyapatite (M-HAP) nanocomposites were prepared by a chemical co- precipitation procedure and characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and diffuse reflectance spectra (DRS). The ability of the synthesized catalyst for photocatalytic degradation of Acid Blue 25 (AB25), as an organic dye, under UV irradiation was studied. The catalyst was modified employing transition metals (Mn, Fe, Co, Ni, Cu and Zn) trying to improve the catalytic performance of HAP in absence of UV irradiation and in the presence of hydrogen peroxide i.e. a Fenton like reaction. The best results obtained for Cu and Co modified M-HAPs and the effect of operational parameters such pH, amount of catalyst and hydrogen peroxide concentration was studied. In order to investigate the performance of HAP based photocatalyst in visible light region, M-HAP was modified with silver ions. At the end, Langmuir-Hinshelwood kinetic expression used to evaluate and compare the catalytic systems. The strongest degradation activity was observed for Ag-M-HAP/Vis system because of Ag{sub 3}PO{sub 4} formation. Apparent reaction rate constant (K{sub app}) by Ag-M-HAP/Vis was 63, 36 and 19 times faster than Cu-M-HAP(II)/H{sub 2}O{sub 2}, Co-M-HAP(II)/H{sub 2}O{sub 2} and M-HAP (I)/UV systems, respectively.

  12. New Porphyrin/Fe-Loaded TiO2 Composites as Heterogeneous Photo-Fenton Catalysts for the Efficient Degradation of 4-Nitrophenol

    Directory of Open Access Journals (Sweden)

    Giuseppe Mele

    2013-01-01

    Full Text Available A new class of porphyrin(Pp/Fe co-loaded TiO2 composites opportunely prepared by impregnation of [5,10,15,20-tetra(4-tert-butylphenyl] porphyrin (H2Pp or Cu(II[5,10,15,20-tetra(4-tert-butylphenyl] porphyrin (CuPp onto Fe-loaded TiO2 particles showed high activities by carrying out the degradation of 4-nitrophenol (4-NP as probe reaction in aqueous suspension under heterogeneous photo-Fenton-like reactions by using UV-visible light. The combination of porphyrin-Fe-TiO2 in the presence of H2O2 showed to be more efficient than the simple bare TiO2 or Fe-TiO2.

  13. Effects of Solvent Diols on the Synthesis of ZnFe2O4 Particles and Their Use as Heterogeneous Photo-Fenton Catalysts

    Directory of Open Access Journals (Sweden)

    Chayene Gonçalves Anchieta

    2014-09-01

    Full Text Available A solvothermal method was used to prepare zinc ferrite spinel oxide (ZnFe2O4 using ethylene glycol and 1,4 butanediol as solvent diols, and the influence of diols on the physical properties of ZnFe2O4 particles was investigated. The produced particles were characterized by X-ray powder diffraction (XRD, atomic force microscopy (AFM, Fourier transform infrared spectroscopy (FTIR and nitrogen adsorption isotherms, and the catalytic activity for the organic pollutant decomposition by heterogeneous photo-Fenton reaction was investigated. Both solvents produced particles with cubic spinel structure. Microporous and mesoporous structures were obtained when ethylene glycol and 1,4 butanediol were used as diols, respectively. A higher pore volume and surface area, as well as a higher catalytic activity for the pollutant degradation were found when 1,4 butanediol was used as solvent.

  14. Visible light-degradation of azo dye methyl orange using TiO2/β-FeOOH as a heterogeneous photo-Fenton-like catalyst.

    Science.gov (United States)

    Xu, Zhihui; Zhang, Ming; Wu, Jingyu; Liang, Jianru; Zhou, Lixiang; L, Bo

    2013-01-01

    In this study, a novel TiO2/β-FeOOH composite photocatalyst was synthesized by a hydrothermal method. X-ray diffraction, Fourier transform infrared spectrum, UV-vis diffuse reflectance spectra and scanning electron microscopy (SEM) were used to characterize the composite photocatalyst. The photocatalytic activity of the prepared composite photocatalyst was evaluated in a heterogeneous photo-Fenton-like process using methyl orange (MO) as target pollutant. The TiO2/β-FeOOH composites exhibited higher photocatalytic activity than pure β-FeOOH and TiO2 under visible-light irradiation. The enhanced photocatalytic activity can be ascribed to the formation of TiO2/β-FeOOH heterostructure, which plays an important role in expanding the photoactivity to the visible light region and in effectively prolonging the lifetime of photoinduced electrons and holes. Further investigation revealed that the 25TiO2/β-FeOOH composite synthesized with the TiO2/Fe(3+) in a mole ratio of 25:75 showed the highest catalytic activity.

  15. Sono-photo-Fenton oxidation of bisphenol-A over a LaFeO3perovskite catalyst.

    Science.gov (United States)

    Dükkancı, Meral

    2018-01-01

    In this study, oxidation of bisphenol-A (IUPAC name - 2,2-(4,4-dihydroxyphenyl, BPA), which is an endocrine disrupting phenolic compound used in the polycarbonate plastic and epoxy resin industry, was investigated using sono-photo-Fenton process under visible light irradiation in the presence of an iron containing perovskite catalyst, LaFeO 3 . The catalyst prepared by sol-gel method, calcined at 500°C showed a catalytic activity in BPA oxidation using sono-photo-Fenton process with a degradation degree and a chemical oxygen demand (COD) reduction of 21.8% and 11.2%, respectively. Degradation of BPA was studied by using individual and combined advanced oxidation techniques including sonication, heterogeneous Fenton reaction and photo oxidation over this catalyst to understand the effect of each process on degradation of BPA. It was seen, the role of sonication was very important in hybrid sono-photo-Fenton process due to the pyrolysis and sonoluminescence effects caused by ultrasonic irradiation. The prepared LaFeO 3 perovskite catalyst was a good sonocatalyst rather than a photocatalyst. Sonication was not only the effective process to degrade BPA but also it was the cost effective process in terms of energy consumption. The studies show that the energy consumption is lower in the sono-Fenton process than those in the photo-Fenton and sono-photo- Fenton processes. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Heterogeneous chromium catalysts

    OpenAIRE

    2005-01-01

    The present invention relates to a heterogeneous chromium catalyst system for the polymerisation of ethylene and/or alpha olefins prepared by the steps of: (a) providing a silica-containing support, (b) treating the silica-containing support with a chromium compound to form a chromium-based silica-containing support, (c) activating the chromium-based silica-containing support, (d) chemically reducing the activated chromium-based silica-containing support to produce a precursor catalyst, (e) r...

  17. Heterogeneous chromium catalysts

    NARCIS (Netherlands)

    2005-01-01

    The present invention relates to a heterogeneous chromium catalyst system for the polymerisation of ethylene and/or alpha olefins prepared by the steps of: (a) providing a silica-containing support, (b) treating the silica-containing support with a chromium compound to form a chromium-based

  18. Magnetite/Fe-Al-montmorillonite as a Fenton catalyst with efficient degradation of phenol.

    Science.gov (United States)

    Wei, Xipeng; Wu, Honghai; Sun, Feng

    2017-10-15

    A Fe-Al-MPM material assembled from nanosized magnetite and Fe-Al-pillared montmorillonite (Fe-Al-Mt) was characterized by XRD, XPS, BET, SEM and TEM. Fe-Al-Mt was proven to be capable of facilitating the dispersion of magnetite nanoparticles and inhibiting their aggregation. The coupling of Fe-Al-Mt with magnetite in Fe-Al-MPM improved its Fenton catalytic activity. Complete conversion of phenol within 80min with a high TOC removal rate (>78%) was achieved using Fe-Al-MPM as a heterogeneous Fenton catalyst under optimized conditions. The Fenton process first underwent a slow induction reaction, followed by the rapid oxidative decomposition of phenol. The existence of the induction reaction period was attributed to the need for activation of the iron species on the catalyst surfaces, and the duration depended on the solution temperature, pH and catalyst's nature. More importantly, Fe-Al-MPM showed high stability, with a low iron-release even after it was recycled 5 times. The minimal iron-leaching from Fe-Al-MPM was ascribed to the competitive adsorption of the incorporated aluminum and all the iron species for the residual (low ecotoxicity) organic ligands. These organic acids were among the main products that remained at the end of the Fenton process. Also important was the ease of separation of Fe-Al-MPM under a magnetic field. Copyright © 2017 Elsevier Inc. All rights reserved.

  19. Heterogeneous photo-Fenton oxidation with natural clays for phenol and tyrosol remediation

    Directory of Open Access Journals (Sweden)

    Djeffal L.

    2013-09-01

    Full Text Available Due to their excellent properties, clays have been widely used in several applications, particularly in catalysis. In this paper, three clays were used as heterogeneous photo-Fenton catalysts for phenol and tyrosol oxidations. Particular attention was given to the effect of the main operating conditions on the process performance. A total conversion was obtained for both organic pollutants with studied catalysts in 20 minutes reaction. For phenol, a total organic carbon (TOC conversion of 93% was obtained using sieved and calcined smectite clay. The TOC conversion was 60% for tyrosol with the same catalyst. Clays were characterized by chemical analysis, BET, XRD, TPR and SEM.

  20. Heterogeneous Photo-Fenton Reaction Catalyzed by Nanosized Iron Oxides for Water Treatment

    Directory of Open Access Journals (Sweden)

    Chuan Wang

    2012-01-01

    Full Text Available Great efforts have been exerted in overcoming the drawbacks of the Fenton reaction for water treatment applications. The drawbacks include pH confinement, handling of iron sludge, slow regeneration of Fe(II, and so forth. This paper highlights the recent developments in the heterogeneous photo-Fenton reaction which utilizes nanosized iron oxides as catalyst for maximizing the activity due to the enhanced physical or chemical properties brought about by the unique structures. This paper also summarizes the fundamentals of the Fenton reaction, which determine the inherent drawbacks and associated advances, to address the advantages of iron oxides and nanosized iron oxides. Tips for applying this method in water treatment are also provided. Given that the environmental effect of nanosized iron oxides is not yet well established, rapid research growth may occur in the near future to advance this promising technology toward water treatment once it is smartly coupled with conventional technologies.

  1. Immobilizing LaFeO3 nanoparticles on carbon spheres for enhanced heterogeneous photo-Fenton like performance

    Science.gov (United States)

    Wang, Kaixuan; Niu, Helin; Chen, Jingshuai; Song, Jiming; Mao, Changjie; Zhang, Shengyi; Gao, Yuanhao

    2017-05-01

    LaFeO3 nanoparticles immobilized on the surface of monodisperse carbon spheres have been obtained through a facile and environmentally friendly ultrasonic assisted surface ions adsorption method. The LaFeO3/C nanocomposite was evaluated as photo-Fenton like catalyst for the degradation of Rhodamine B (RhB) under visible light irradiation (λ > 420 nm). The LaFeO3/C nanocomposite possesses high specific surface area compared with pure LaFeO3 and significantly enhanced photo-Fenton like catalytic performance. The possible formation process of the LaFeO3/C nanocomposite and the mechanism for photo-Fenton like reaction were discussed. The superior property was attributed to the synergistic effects from the photo-Fenton like process and the presence of carbon spheres. In addition, the heterogeneous process led to better recyclability of this type of catalyst.

  2. Microwave-assisted preparation of flower-like cobalt phosphate and its application as a new heterogeneous Fenton-like catalyst

    Science.gov (United States)

    Hu, Xiaoxia; Li, Rong; Zhao, Shuyu; Xing, Yanjun

    2017-02-01

    A novel flower-like 3D hierarchical cobalt phosphate Co3(PO4)2·8H2O (fCoP), and a plate-like cobalt phosphate (pCoP) were successfully synthesized via a microwave-assisted method at low temperature under atmospheric pressure using hexamethylene tetramine (HMTA) or urea as a template. All CoPs were characterized using XRD, FESEM, TEM, DRS and surface photovoltage spectra (SPS). The performance of the photocatalytic degradation of Rhodamine B (RhB) via a Fenton-like process on CoPs was evaluated both in the dark and under illumination. The results showed that the morphology and composition of the CoPs affected the RhB degradation. The flower-like hierarchical fCoP favored the photo degradation of RhB. fCoP was also confirmed to have the merits of easy recycling and good stability based on successive degradation experiments. The active species trapping experiments showed that the superoxide radical (rad O2-) was the dominant active species in the Fenton-like process. The catalytic activation was confirmed to be related to both the Co(II) on the surface and the fCoP framework.

  3. Ferrocene-functionalized graphitic carbon nitride as an enhanced heterogeneous catalyst of Fenton reaction for degradation of Rhodamine B under visible light irradiation.

    Science.gov (United States)

    Lin, Kun-Yi Andrew; Lin, Jyun-Ting

    2017-09-01

    To enhance degradation of Rhodamine B (RhB), a toxic xanthene dye, an iron-doped graphitic carbon nitride (CN) is prepared by establishing a covalent bond (-CN-) bridging ferrocene (Fc) and CN via a Schiff base reaction. The π-conjugation between the aromatic Fc and CN can be much enhanced by the covalent bond, thereby facilitating the bulk-to-surface charge transfer and separation as well as reversible photo-redox reactions during photocatalytic reactions. Thus, the resulting Fc-CN exhibits a much higher catalytic activity than CN to activate hydrogen peroxide (HP) for RhB degradation, because the photocatalytically generated electrons from CN can activate HP and effectively maintain the bivalence state of Fe in Fc, which also induces the activation of HP. The RhB degradation by the Fc-CN activated HP process (Fc-CN-HP) is validated to involve OH(•) by examining the effect of radical probe agent as well as electron paramagnetic resonance (EPR) spectroscopic analysis. Fc-CN is also proven to activate HP for RhB degradation over multiple times without loss of catalytic activity. Through determining the degradation intermediates, RhB is indeed fully decomposed by Fc-CN-HP into much lower-molecular-weight organic compounds. These features indicate that Fc-functionalization can be an advantageous technique to enhance the catalytic activity of CN for activating HP. The results obtained in this study are essential to further design and utilize Fc-functionalized CN for Fenton-like reactions. The findings shown here, especially the degradation mechanism and pathway, are also quite important for treating xanthene dyes in wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Immobilizing LaFeO{sub 3} nanoparticles on carbon spheres for enhanced heterogeneous photo-Fenton like performance

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Kaixuan [School of Chemistry and Chemical Engineering, Anhui University, Hefei 230601 (China); Niu, Helin, E-mail: niuhelin@ahu.edu.cn [School of Chemistry and Chemical Engineering, Anhui University, Hefei 230601 (China); Chen, Jingshuai; Song, Jiming; Mao, Changjie; Zhang, Shengyi [School of Chemistry and Chemical Engineering, Anhui University, Hefei 230601 (China); Gao, Yuanhao [Institute of Surface Micro and Nano Materials, Xuchang University, Henan 461000 (China)

    2017-05-15

    Highlights: • LaFeO{sub 3} nanoparticles sub–10 nm were successfully immobilized on monodisperse carbon spheres for the first time through a facile and environmental friendly ultrasonic assisted surface ions adsorption method. • LaFeO{sub 3}/C nanocomposite exhibits much higher photo-Fenton like catalytic activity than LaFeO{sub 3}. • The superior property was attributed to the synergistic effects from the photo-Fenton like process and the presence of monodisperse carbon spheres. - Abstract: LaFeO{sub 3} nanoparticles immobilized on the surface of monodisperse carbon spheres have been obtained through a facile and environmentally friendly ultrasonic assisted surface ions adsorption method. The LaFeO{sub 3}/C nanocomposite was evaluated as photo-Fenton like catalyst for the degradation of Rhodamine B (RhB) under visible light irradiation (λ > 420 nm). The LaFeO{sub 3}/C nanocomposite possesses high specific surface area compared with pure LaFeO{sub 3} and significantly enhanced photo-Fenton like catalytic performance. The possible formation process of the LaFeO{sub 3}/C nanocomposite and the mechanism for photo-Fenton like reaction were discussed. The superior property was attributed to the synergistic effects from the photo-Fenton like process and the presence of carbon spheres. In addition, the heterogeneous process led to better recyclability of this type of catalyst.

  5. [Biosynthetic schwertmannite as catalyst in Fenton-like reactions for degradation of methyl orange].

    Science.gov (United States)

    Wang, Kuai-Bing; Fang, Di; Xu, Zhi-Hui; Shi, Ying; Zheng, Guan-Yu; Zhou, Li-Xiang

    2015-03-01

    Biosynthesized schwertmannite was used as catalyst in photo-Fenton-like reaction to facilitate the degradation of methyl orange (MO). Schwertmannite was synthesized through the oxidation of FeSO4 by Acidithiobacillus ferrooxidans LX5 cell suspension at an initial pH 2.5 and 28 degress C for 3 days and characterized using X-ray diffraction spectroscopy and scanning electron microscope. The oxidative degradation of MO in the photo-Fenton-like reaction was studied at different initial pH values of suspension, concentrations of H2O2 and dosages of catalyst. The results suggested that the biosynthetic schwertmannite showed a good catalytic activity in the MO degradation via *OH radical mechanism. Considerable degradation efficiency of MO was still obtained in approximately neutral condition or in the presence of high concentrations of chloride, sulfate and nitrate. This work demonstrated that the heterogeneous photo-Fenton-like reaction catalyzed by the biosynthetic schwertmannite is a promising advanced oxidation technology for the treatment of wastewater containing MO.

  6. Design of heterogeneous catalysts

    DEFF Research Database (Denmark)

    Frey, Anne Mette

    was inspired by a computational screening, suggesting that alloys such as Ni-Fe, Co-Ni, and Co-Fe should show superior activity to the industrially used nickel catalyst. Especially the Ni-Fe system was considered to be interesting, since such alloy catalysts should be both more active and cheaper than the Ni....... Previously it has been shown that calcination of cobalt catalyst in a NO/He mixture resulted in improved catalytic activity compared to standard air calcined samples, since more homogenous cobalt particles with a narrow particle size distribution were formed. Unfortunately the C5+ selectivity decreased...... well, and the best catalyst prepared had a C5+ yield almost a factor of two higher than a standard air calcined Co catalyst. In the NH3-SCR reaction it is desirable to develop an active and stable catalyst for NOx removal in automotive applications, since the traditionally used vanadium-based catalyst...

  7. Effect of alkali cations on heterogeneous photo-Fenton process mediated by Prussian blue colloids

    Energy Technology Data Exchange (ETDEWEB)

    Liu Shouqing, E-mail: shouqing_liu@hotmail.com [Provincial Key Laboratory of Environmental Science and Engineering, College of Chemistry and Bioengineering, Suzhou University of Science and Technology, Suzhou 215009 (China); Cheng Shi; Feng Lianrong; Wang Xiaomei; Chen Zhigang [Provincial Key Laboratory of Environmental Science and Engineering, College of Chemistry and Bioengineering, Suzhou University of Science and Technology, Suzhou 215009 (China)

    2010-10-15

    This article evaluates Prussian blue (iron hexacyanoferrate) colloids as a heterogeneous photo-Fenton catalyst for the degradation of Rhodamine B. The emphasis is laid on the effects of alkali metal cations on the photo-Fenton process. The facts show that alkali cations strongly affect the degradation rate of organic species. The degradation rates of Rhodamine B, Malachite Green, and Methyl Orange in the presence of KCl, KNO{sub 3}, and K{sub 2}SO{sub 4}, respectively, are faster than their degradation rates in the presence of the corresponding sodium salts. The average degradation rates of Rhodamine B in 0.2 M KCl, NaCl, RbCl, and CsCl solution, decline in sequence, and the rate in KCl solution is greater than that without any salt added deliberately. Thus, potassium ions accelerate the degradation rate, but sodium, rubidium, and cesium ions slow the rate. The order of the rates is R{sub K} > R > R{sub Na} > R{sub Rb} > R{sub Cs}, which is consistent with that of the voltammetric oxidation currents of Prussian blue in the corresponding cation solutions. This phenomenon is attributed to the molecular recognition of the microstructure in Prussian blue nanoparticles to the alkali cations. The reaction mechanism of the photo-Fenton process has also been explored.

  8. In-situ characterization of heterogeneous catalysts

    CERN Document Server

    Rodriguez, Jose A; Chupas, Peter J

    2013-01-01

    Helps researchers develop new catalysts for sustainable fuel and chemical production Reviewing the latest developments in the field, this book explores the in-situ characterization of heterogeneous catalysts, enabling readers to take full advantage of the sophisticated techniques used to study heterogeneous catalysts and reaction mechanisms. In using these techniques, readers can learn to improve the selectivity and the performance of catalysts and how to prepare catalysts as efficiently as possible, with minimum waste. In-situ Characterization of Heterogeneous Catalysts feat

  9. Heterogenization of alkene epoxidation catalysts

    Directory of Open Access Journals (Sweden)

    Buffon Regina

    2003-01-01

    Full Text Available This account describes our efforts to heterogenize epoxidation catalysts. Anchored and sol-gel entrapped molybdenum were shown to be very selective, but had a strongly reduced activity. On the other hand, molybdenum silicates were very active and stable as long as no diols were present in the reaction mixture. Heterogenized rhenium catalysts were less active but allowed the use of anhydrous hydrogen peroxide as oxidant. However, the high cost and difficult regeneration prevents the industrial use of these catalysts. During these investigations, we found that alumina alone is active in the epoxidation with anhydrous hydrogen peroxide, giving good conversions to epoxides with high selectivity. More research is needed in order to clarify the nature of the hydroxyl groups responsible for its catalytic activity and thus to produce an appropriate material which would allow the obtention of epoxides with high selectivity under industrial conditions.

  10. Heterogeneous Fenton-like oxidation of monochlorobenzene using green synthesis of iron nanoparticles.

    Science.gov (United States)

    Kuang, Ye; Wang, Qingping; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravendra

    2013-11-15

    Iron nanoparticles (Fe NPs) were synthesized using tea extracts as a catalyst for the Fenton-like oxidation of monochlorobenzene (MCB), where 69%, 53%, and 39% of MCB were, respectively, degraded by Fe NPs synthesized using green tea extracts, oolong tea extracts, and black tea extracts. Fe NPs synthesized using green tea extracts (GT-Fe NPs) demonstrated the best degradation since green tea contains a high concentration of caffeine/polyphenols used as both reducing and capping agents in the synthesis of Fe NPs. This was confirmed by SEM image, EDS, and XRD pattern of GT-Fe NPs. In addition, batch experiments show that the oxidation of MCB and the removal of chemical oxygen demand (COD) using GT-Fe NPs were 81% and 31%, respectively, at optimal conditions, where dosages were 0.6g/L GT-Fe NPs, 0.045 mol/L H2O2, and initial pH of 3.0. Compared to homogeneous Fenton oxidation of MCB, GT-Fe NPs as a heterogeneous catalyst indicate that Fe(2+) and Fe(3+) leached from GT-Fe NPs nanoparticles and consequently reduced the formation of iron sludge. Finally, GT-Fe NPs were successful in removing MCB from wastewaters, and the possible Fenton-like oxidative mechanism of MCB was proposed. The proposition was based on adsorption of MCB on the surface of GT-Fe NPs, decomposition of H2O2, generation of hydroxyl radicals, and oxidation of MCB. Copyright © 2013 Elsevier Inc. All rights reserved.

  11. Heterogeneous fenton degradation of azo dyes catalyzed by modified polyacrylonitrile fiber fe complexes: QSPR (quantitative structure peorperty relationship) study.

    Science.gov (United States)

    Li, Bing; Dong, Yongchun; Ding, Zhizhong

    2013-07-01

    The amidoximated polyacrylonitrile (PAN) fiber Fe complexes were prepared and used as the heterogeneous Fenton catalysts for the degradation of 28 anionic water soluble azo dyes in water under visible irradiation. The multiple linear regression (MLR) method was employed to develop the quantitative structure property relationship (QSPR) model equations for the decoloration and mineralization of azo dyes. Moreover, the predictive ability of the QSPR model equations was assessed using Leave-one-out (LOO) and cross-validation (CV) methods. Additionally, the effect of Fe content of catalyst and the sodium chloride in water on QSPR model equations were also investigated. The results indicated that the heterogeneous photo-Fenton degradation of the azo dyes with different structures was conducted in the presence of the amidoximated PAN fiber Fe complex. The QSPR model equations for the dye decoloration and mineralization were successfully developed using MLR technique. MW/S (molecular weight divided by the number of sulphonate groups) and NN=N (the number of azo linkage) are considered as the most important determining factor for the dye degradation and mineralization, and there is a significant negative correlation between MW/S or NN=N and degradation percentage or total organic carbon (TOC) removal. Moreover, LOO and CV analysis suggested that the obtained QSPR model equations have the better prediction ability. The variation in Fe content of catalyst and the addition of sodium chloride did not alter the nature of the QSPR model equations.

  12. Fosetyl-Al photo-Fenton degradation and its endogenous catalyst inhibition.

    Science.gov (United States)

    Micó, María M; Zapata, Ana; Maldonado, Manuel I; Bacardit, Jordi; Malfeito, Jorge; Sans, Carme

    2014-01-30

    Interferences from many sources can affect photo-Fenton reaction performance. Among them, catalyst inhibition can be caused by the complexation and/or precipitation of iron species by the organic matter and salts present in the reaction media. This is the case of the oxidation of effluents containing organophosphorous fosetyl-Al. The degradation of this fungicide generates phosphate anions that scavenge iron and hinder Fe(II) availability. Experimental design was applied to artificially enlighten photo-Fenton reaction, in order to evaluate fosetyl-Al degradation. The performed experiments suggested how iron inhibition takes place. The monitoring of photo-Fenton reaction over a mixture of fosetyl-Al with other two pesticides also showed the interferences caused by the presence of the fungicide on other species degradation. Solar empowered photo-Fenton was also essayed for comparison purposes. Artificial and solar light photo-Fenton reactions were revealed as effective treatments for the elimination of tested fungicide. However, the phosphate ions generated during fosetyl oxidation decreased iron availability, what hampered organic matter degradation. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Removal of polyvinylamine sulfonate anthrapyridone dye by application of heterogeneous electro-Fenton process.

    Science.gov (United States)

    Bouzayani, Bakhta; Meijide, Jessica; Pazos, Marta; Elaoud, Sourour Chaâbane; Sanroman, Maria Angeles

    2017-08-01

    Diversity and rapidly multiplication of the pollutants incite as to improve the conventional treatments wastewater methods. One of the bottlenecks often faced is the presence into wastewater of organic pollutants with complex structures that requests the design of efficient processes. Thus, this work investigates the removal of polyvinylamine sulfonate anthrapyridone (PSA) dye which complex structure makes difficult its degradation by conventional technologies. For that, a heterogeneous oxidative process using pyrite as sustainable catalyst was designed. Initially, the performance of the system BBD-carbon felt as anode and cathode, respectively for the production of H2O2 was determined in comparison with system boron-doped diamond nickel foam. The carbon felt electrode provided the highest oxidant production, and it was selected for the treatment of the polymeric dye. Several oxidative processes were evaluated, and the best degradation levels were obtained by application of electro-Fenton-pyrite process. In addition, it was determined that dye removal followed a kinetic model of pseudo-first-order achieving the highest efficiency by operation at optimum dosage of pyrite 2 g/L and 200 mA of current intensity. Depending on the optimal experimental conditions, these values lead to a nearly complete mineralization (total organic carbon removal of 95%) after 6 h. Furthermore, the reusability of pyrite was evaluated, by removal of PSA in four cycles.

  14. Electrochemical dissolution of steel as a typical catalyst for electro-Fenton oxidation.

    Science.gov (United States)

    Kočanová, Veronika; Dušek, Libor

    Although traditional Fenton reaction is known for a long time, it is still a perspective method for removal of pollution from wastewater. Applications of electro-Fenton oxidation are commonly used in wastewater treatment. These methods are classified into groups-electrochemical advanced oxidation processes. Typical catalysts for these technologies are Fe(2+) ions. Comparison between two material types of steel was investigated in this paper. Alloy steel Cr-Ni and non-alloy steel were used as a source of Fe(2+) ions as catalyst for electro-Fenton oxidation. Electrochemical dissolution was chosen as a method of catalyst dosage. Various parameters were tested depending on the type of material of alloy and non-alloy steel at a time. Corrosion properties were also experimentally tested of both materials of steel anodes. Electrochemically dissolved Fe(2+) and Fe(3+) sludge could be very well removed from treated water by the sedimentation process. At first the solutions were adjusted, then loosely precipitated, and at the end sedimented. Residual concentrations of iron in the solutions determined by UV/VIS spectrophotometry were in compliance with the threshold limits stated by the government regulation.

  15. Heterogeneous photo-Fenton decolorization of Orange II over Al-pillared Fe-smectite: response surface approach, degradation pathway, and toxicity evaluation.

    Science.gov (United States)

    Li, Huiyuan; Li, Yanli; Xiang, Luojing; Huang, Qianqian; Qiu, Juanjuan; Zhang, Hui; Sivaiah, Matte Venkata; Baron, Fabien; Barrault, Joel; Petit, Sabine; Valange, Sabine

    2015-04-28

    A ferric smectite clay material was synthesized and further intercalated with Al2O3 pillars for the first time with the aim of evaluating its ability to be used as heterogeneous catalyst for the photo-Fenton decolorization of azo dye Orange II. UV irradiation was found to enhance the activity of the catalyst in the heterogeneous photo-Fenton process. Catalyst loading of 0.5g/L and hydrogen peroxide concentration of 13.5mM yielded a remarkable color removal, accompanied by excellent catalyst stability. The decolorization of Orange II followed the pseudo-first-order kinetics for initial dye concentrations from 20 to 160mg/L. The central composite design (CCD) based on the response surface methodology (RSM) was applied to evaluate the effects of several operating parameters, namely initial pH, catalyst loading and hydrogen peroxide concentration, on the decolorization efficiency. The RSM model was derived and the response surface plots were developed based on the results. Moreover, the main intermediate products were separated and identified using gas chromatography-mass spectrometry (GC-MS) and a possible degradation pathway was proposed accordingly. The acute toxicity experiments illustrated that the Daphniamagna immobilization rate continuously decreased during 150min reaction, indicating that the effluent was suitable for sequential biological treatment. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Heterogeneous photo-Fenton decolorization of Orange II over Al-pillared Fe-smectite: Response surface approach, degradation pathway, and toxicity evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Huiyuan; Li, Yanli [Department of Environmental Engineering, Wuhan University, Wuhan 430079 (China); Xiang, Luojing [Department of Environmental Engineering, Wuhan University, Wuhan 430079 (China); Université de Poitiers, UMR CNRS 7285, IC2MP, ENSIP, B1, 1 rue Marcel Doré, TSA 41105, Poitiers 86073 Cedex 9 (France); Huang, Qianqian; Qiu, Juanjuan [Department of Environmental Engineering, Wuhan University, Wuhan 430079 (China); Zhang, Hui, E-mail: eeng@whu.edu.cn [Department of Environmental Engineering, Wuhan University, Wuhan 430079 (China); Sivaiah, Matte Venkata; Baron, Fabien; Barrault, Joel; Petit, Sabine [Université de Poitiers, UMR CNRS 7285, IC2MP, ENSIP, B1, 1 rue Marcel Doré, TSA 41105, Poitiers 86073 Cedex 9 (France); Valange, Sabine, E-mail: sabine.valange@univ-poitiers.fr [Université de Poitiers, UMR CNRS 7285, IC2MP, ENSIP, B1, 1 rue Marcel Doré, TSA 41105, Poitiers 86073 Cedex 9 (France)

    2015-04-28

    Highlights: • Al-pillared Fe-smectite was synthesized and used as the photo-Fenton catalyst. • Response surface methodology was used to study the effects of reaction parameters. • The main intermediate products were identified by GC–MS technique. • A possible degradation pathway of Orange II was proposed. • All the generated products of Orange II were less toxic than the original dye. - Abstract: A ferric smectite clay material was synthesized and further intercalated with Al{sub 2}O{sub 3} pillars for the first time with the aim of evaluating its ability to be used as heterogeneous catalyst for the photo-Fenton decolorization of azo dye Orange II. UV irradiation was found to enhance the activity of the catalyst in the heterogeneous photo-Fenton process. Catalyst loading of 0.5 g/L and hydrogen peroxide concentration of 13.5 mM yielded a remarkable color removal, accompanied by excellent catalyst stability. The decolorization of Orange II followed the pseudo-first-order kinetics for initial dye concentrations from 20 to 160 mg/L. The central composite design (CCD) based on the response surface methodology (RSM) was applied to evaluate the effects of several operating parameters, namely initial pH, catalyst loading and hydrogen peroxide concentration, on the decolorization efficiency. The RSM model was derived and the response surface plots were developed based on the results. Moreover, the main intermediate products were separated and identified using gas chromatography–mass spectrometry (GC–MS) and a possible degradation pathway was proposed accordingly. The acute toxicity experiments illustrated that the Daphniamagna immobilization rate continuously decreased during 150 min reaction, indicating that the effluent was suitable for sequential biological treatment.

  17. Heterogeneous Metal Catalysts for Oxidation Reactions

    Directory of Open Access Journals (Sweden)

    Md. Eaqub Ali

    2014-01-01

    Full Text Available Oxidation reactions may be considered as the heart of chemical synthesis. However, the indiscriminate uses of harsh and corrosive chemicals in this endeavor are threating to the ecosystems, public health, and terrestrial, aquatic, and aerial flora and fauna. Heterogeneous catalysts with various supports are brought to the spotlight because of their excellent capabilities to accelerate the rate of chemical reactions with low cost. They also minimize the use of chemicals in industries and thus are friendly and green to the environment. However, heterogeneous oxidation catalysis are not comprehensively presented in literature. In this short review, we clearly depicted the current state of catalytic oxidation reactions in chemical industries with specific emphasis on heterogeneous catalysts. We outlined here both the synthesis and applications of important oxidation catalysts. We believe it would serve as a reference guide for the selection of oxidation catalysts for both industries and academics.

  18. Microwave-Assisted Synthesis of Fe3O4Nanocrystals with Predominantly Exposed Facets and Their Heterogeneous UVA/Fenton Catalytic Activity.

    Science.gov (United States)

    Zhong, Yuanhong; Yu, Lin; Chen, Zhi-Feng; He, Hongping; Ye, Fei; Cheng, Gao; Zhang, Qianxin

    2017-08-30

    Fe 3 O 4 nanocrystals with five different morphologies (i.e., nanospheres, nanorods, nanocubes, nano-octahedrons, and nanoplates) were acquired using a simple, efficient, and economic microwave-assisted oxidation technique. The microstructure, morphology, predominant exposed facets, and iron atom local environment of Fe 3 O 4 were revealed by powder X-ray diffraction (PXRD), scanning transmission electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectrometer (XPS), and Mössbauer spectrum. We demonstrated that the heterogeneous UVA/Fenton catalytic activities of Fe 3 O 4 nanocrystals are morphology/facets dependent. Under UVA irradiation, the catalytic activity of the as-prepared Fe 3 O 4 was in the sequence of nanospheres > nanoplates > nano-octahedrons ≈ nanocubes > nanorods > nano-octahedrons (by coprecipitation). The dominating factor for the catalytic performance was the particle size and BET specific surface area; moreover, the exposed {111} facets, which contained more Fe 2+ species, on the nanocrystal surface led to a stronger UVA/Fenton catalytic activity. Both • OH and O 2 •- radicals participated in the UVA/Fenton degradation process, and • OH played the dominant role. These morphology-controlled nanomagnetites showed great potential in applications as heterogeneous UVA/Fenton catalysts for effectively treating nonbiodegradable organic pollutants.

  19. Selective Oxidations using Nanostructured Heterogeneous Catalysts

    DEFF Research Database (Denmark)

    Mielby, Jerrik Jørgen

    and because they produce H2O as the only by-product. Chapter 1 gives a short introduction to basic concepts in heterogeneous catalysis and green chemistry. Furthermore, the chapter gives an overview of the most important strategies to synthesise functional nanostructured materials and highlights how detailed......The aim of this thesis is to investigate and develop new efficient methods to oxidise alcohols and amines using heterogeneous catalysts and either O2 or H2O2 as oxidants. From an economic and environmental point of view, these oxidants are ideal, because they are cheap and readily available...... understanding of size, shape and structure can help in the development of new and more efficient heterogeneous catalysts. The chapter is not intended to give a complete survey, but rather to introduce some of the recent developments in the synthesis of nanostructured heterogeneous catalysts. Finally...

  20. Optimization of the heterogeneous Fenton-oxidation of the model pollutant 2,4-xylidine using the optimal experimental design methodology

    Energy Technology Data Exchange (ETDEWEB)

    Rios-Enriquez, M. [Universidad Nacional Autonoma de Mexico (Mexico). Facultad de Quimica; Karlsruhe Univ. (Germany). Engler-Bunte-Inst.; Shahin, N.; Lang, J.; Oliveros, E.; Bossmann, S.H.; Braun, A. [Karlsruhe Univ. (Germany). Engler-Bunte-Inst.; Duran-de-Bazua, C. [Universidad Nacional Autonoma de Mexico (Mexico). Facultad de Quimica

    2004-11-01

    Among advanced oxidation processes (AOP), the photochemically enhanced Fenton reaction (photo-Fenton) may be particularly effective for the treatment of industrial waste water, and the possibility to use solar light is an additional advantage of this process. In the present work, a Fe{sup 3+}exchanged zeolite Y was tested as a heterogeneous photo-Fenton catalyst for the degradation of the model organic pollutant, 2,4-xylidine. The performance of the catalyst was investigated using a bench photochemical reactor as well as solar reactors. The incident solar radiant powers (determined by ferrioxalate actinometry) showed linear correlations with the outputs of a Si-photodiode and a bolometer mounted on the solar unit, and could therefore be easily estimated from the on-line observation of the sensor outputs. The experimental design methodology was used for planning the experiments under normalized conditions and for modeling the rates of 2,4-xylidine oxidation as a function of the concentrations of the additives (Fe{sup 3+}exchanged zeolite catalyst and hydrogen peroxide). Although a direct quantitative comparison between both reactors is difficult (different geometries and volumes, different spectral distribution of the radiation sources), the performance of the solar reactor appears to compare favorably with that of the bench photochemical reactor. (Author)

  1. Winery wastewater treatment by heterogeneous Photo-Fenton process and activated sludges; Depuracion de efluentes vinicolas ediante tratamientos Foto-Fenton en fase heterogenea y lodos activos

    Energy Technology Data Exchange (ETDEWEB)

    Mosteo, R.; Lalinde, N.; Ormad, Maria O. M.; Ovelleiro, J. L.

    2007-07-01

    The system composed by heterogeneous Photon-Fenton assisted by solar light and biological treatment based on activated sludge process treats adequately real winery wastewaters. the previous stage based on heterogeneous Photo-Fenton process produces a partial degradation of winery wastewaters and achieves a yield of degradation of organic matter (measured as TOC) close to 50%. The activated sludge process in simple stage doesn't present any operation problems (bulking phenomenon) and achieves a yield of degradation of organic matter of 90%. (Author) 16 refs.

  2. Hydrothermal synthesis of bismuth ferrite Fenton-like catalysts and their properties

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Min; Li, Wenjuan, E-mail: liwenjuan2801@163.com; Du, Yong; Kong, Defen; Wang, Ze; Meng, Yi; Sun, Xiaolan; Yan, Tingjiang; Kong, Desheng; You, Jinmao [Qufu Normal University, Shandong Province Key Laboratory of Life-Organic Analysis (China)

    2016-11-15

    Bismuth ferrite, Fenton-like catalysts have been successfully synthesized via simple hydrothermal methods without any templates. Through changing the molar ratio of Bi/Fe, the two main phases BiFeO{sub 3} and Bi{sub 25}FeO{sub 40} can be synthesized under different temperatures. Furthermore, different morphologies of the BiFeO{sub 3} phase can be adjusted by changing different concentrations of HNO{sub 3} and NaOH which were used to dissolve the reactants and adjust the pH values in the prepared process. When the concentration of HNO{sub 3}/NaOH was 8/12 M, some uniform cylindrical bodies with equal height (1 μm) and width (0.6 μm) were obtained, which have not been reported before. The uniform structures exhibited better activities in the photoassisted Fenton-like oxidation process for the degradation of rhodamine B (RhB) under visible light irradiation (420 nm < λ < 800 nm). Through the detection of the degradation mechanism, it showed that the concerted effect of the catalysts and H{sub 2}O{sub 2} can increase the generation of the charge carriers and accelerate the photogenerated charge transfer between the catalysts and dyes. The BiFeO{sub 3} samples also showed magnetic properties at room temperature, which may have potential applications in multiferroic or magnetoelectric sensors and devices.

  3. Preparation of immobilized coating Fenton-like catalyst for high efficient degradation of phenol.

    Science.gov (United States)

    Wang, Jiankang; Yao, Zhongping; Wang, Yajing; Xia, Qixing; Chu, Huiya; Jiang, Zhaohua

    2017-05-01

    In this study, solid acid amorphous Fe 3 O 4 /SiO 2 ceramic coating decorated with sulfur on Q235 carbon steel as Fenton-like catalyst for phenol degradation was successfully prepared by plasma electrolytic oxidation (PEO) in silicate electrolyte containing Na 2 S 2 O 8 as sulfur source. The surface morphology and phase composition were characterized by SEM, EDS, XRD and XPS analyses. NH 3 -TPD was used to evaluate surface acidity of PEO coating. The results indicated that sulfur decorated amorphous Fe 3 O 4 /SiO 2 ceramic coatings with porous structure and higher acid strength had the similar pore size and the surface became more and more uneven with the increase of Na 2 S 2 O 8 in the silicate electrolyte. The Fenton-like catalytic activity of sulfur decorated PEO coatings was also evaluated. In contrast to negligible catalytic activity of sulfur undecorated PEO coating, catalytic activity of sulfur decorated PEO coating was excellent and PEO coating prepared with 3.0 g Na 2 S 2 O 8 had the highest catalytic activity which could degrade 99% of phenol within 8 min under circumneutral pH. The outstanding performance of sulfur decorated PEO coating was attributed to strong acidic microenvironment and more Fe 2+ on the surface. The strong acid sites played a key factor in determining catalytic activity of catalyst. In conclusion, rapid phenol removal under circumneutral pH and easier separation endowed it potential application in wastewater treatment. In addition, this strategy of preparing immobilized solid acid coating could provide guidance for designing Fenton-like catalyst with excellent catalytic activity and easier separation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Heterogeneous Catalyst Deactivation and Regeneration: A Review

    Directory of Open Access Journals (Sweden)

    Morris D. Argyle

    2015-02-01

    Full Text Available Deactivation of heterogeneous catalysts is a ubiquitous problem that causes loss of catalytic rate with time. This review on deactivation and regeneration of heterogeneous catalysts classifies deactivation by type (chemical, thermal, and mechanical and by mechanism (poisoning, fouling, thermal degradation, vapor formation, vapor-solid and solid-solid reactions, and attrition/crushing. The key features and considerations for each of these deactivation types is reviewed in detail with reference to the latest literature reports in these areas. Two case studies on the deactivation mechanisms of catalysts used for cobalt Fischer-Tropsch and selective catalytic reduction are considered to provide additional depth in the topics of sintering, coking, poisoning, and fouling. Regeneration considerations and options are also briefly discussed for each deactivation mechanism.

  5. Enhanced heterogeneous photo-Fenton process modified by magnetite and EDDS: BPA degradation.

    Science.gov (United States)

    Huang, Wenyu; Luo, Mengqi; Wei, Chaoshuai; Wang, Yinghui; Hanna, Khalil; Mailhot, Gilles

    2017-04-01

    In this research, magnetite and ethylenediamine-N,N'-disuccinic acid (EDDS) are used in a heterogeneous photo-Fenton system in order to find a new way to remove organic contaminants from water. Influence of different parameters including magnetite dosage, EDDS concentration, H2O2 concentration, and pH value were evaluated. The effect of different radical species including HO· and HO2·/O2·- was investigated by addition of different scavengers into the system. The addition of EDDS improved the heterogeneous photo-Fenton degradation of bisphenol A (BPA) through the formation of photochemically efficient Fe-EDDS complex. This effect is dependent on the H2O2 and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O2·- to generate Fe(II) from Fe(III) species reduction. GC-MS analysis suggested that the cleavage of the two benzene rings is the first degradation step followed by oxidation leading to the formation of the benzene derivatives. Then, the benzene ring was opened due to the attack of HO· radicals producing short-chain organic compounds of low molecular weight like glycerol and ethylene glycol. These findings regarding the capability of EDDS/magnetite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.

  6. Using iron-loaded sepiolite obtained by adsorption as a catalyst in the electro-Fenton oxidation of Reactive Black 5.

    Science.gov (United States)

    Iglesias, O; Fernández de Dios, M A; Pazos, M; Sanromán, M A

    2013-09-01

    This study explores the possibility of using iron-loaded sepiolite, obtained by recovering iron from polluted water, as a catalyst in the electro-Fenton oxidation of organic pollutants in textile effluents. The removal of iron ions from aqueous solution by adsorption on sepiolite was studied in batch tests at iron concentrations between 100 and 1,000 ppm. Electro-Fenton experiments were carried out in an electrochemical cell with a working volume of 0.15 L, an air flow of 1 L/min, and 3 g of iron-loaded sepiolite. An electric field was applied using a boron-doped diamond anode and a graphite sheet cathode connected to a direct current power supply with a constant potential drop. Reactive Black 5 (100 mg/L) was selected as the model dye. The adsorption isotherms proved the ability of the used adsorbent. The removal of the iron ion by adsorption on sepiolite was in the range of 80-100 % for the studied concentration range. The Langmuir and Freundlich isotherms were found to be applicable in terms of the relatively high regression values. Iron-loaded sepiolite could be used as an effective heterogeneous catalyst for the degradation of organic dyes in the electro-Fenton process. Successive batch processes were performed at optimal working conditions (5 V and pH 2). The results indicate the suitability of the proposed combined process, adsorption to iron remediation followed by the application of the obtained iron-loaded sepiolite to the electro-Fenton technique, to oxidize polluted effluents.

  7. Homogeneous and heterogenized iridium water oxidation catalysts

    Science.gov (United States)

    Macchioni, Alceo

    2014-10-01

    The development of an efficient catalyst for the oxidative splitting of water into molecular oxygen, protons and electrons is of key importance for producing solar fuels through artificial photosynthesis. We are facing the problem by means of a rational approach aimed at understanding how catalytic performance may be optimized by the knowledge of the reaction mechanism of water oxidation and the fate of the catalytic site under the inevitably harsh oxidative conditions. For the purposes of our study we selected iridium water oxidation catalysts, exhibiting remarkable performance (TOF > 5 s-1 and TON > 20000). In particular, we recently focused our attention on [Cp*Ir(N,O)X] (N,O = 2-pyridincarboxylate; X = Cl or NO3) and [IrCl(Hedta)]Na water oxidation catalysts. The former exhibited a remarkable TOF whereas the latter showed a very high TON. Furthermore, [IrCl(Hedta)]Na was heterogenized onto TiO2 taking advantage of the presence of a dandling -COOH functionality. The heterogenized catalyst maintained approximately the same catalytic activity of the homogeneous analogous with the advantage that could be reused many times. Mechanistic studies were performed in order to shed some light on the rate-determining step and the transformation of catalysts when exposed to "oxidative stress". It was found that the last oxidative step, preceding oxygen liberation, is the rate-determining step when a small excess of sacrificial oxidant is used. In addition, several intermediates of the oxidative transformation of the catalyst were intercepted and characterized by NMR, X-Ray diffractometry and ESI-MS.

  8. Integrated heterogeneous sono-photo Fenton processes for the degradation of phenolic aqueous solutions.

    Science.gov (United States)

    Segura, Y; Molina, R; Martínez, F; Melero, J A

    2009-03-01

    The removal of organic compounds from aqueous solutions has been tackled by a novel integrated heterogeneous system. The efficacy of the different systems has been assessed using Fenton-like processes (H2O2/Fe2O3-SBA-15) and phenol as model pollutant. Sono- and photo-Fenton processes separately applied as well as combined systems were studied in order to evaluate of possible beneficial effects on the use of coupled systems. The sequential system evidences an enhancement in terms of phenol and TOC conversions compared to the ultrasound or UV-light irradiation processes. A total phenol degradation and ca. 90% TOC reduction are achieved by sequentially ultrasound followed by UV-visible light irradiation. These effects are ascribed cavitation effect of ultrasound producing a reduction of particle size that provides a higher amount of available active sites due to an increased surface area for the subsequent photo-Fenton system. These encouraging results open new paths for the existing oxidation technologies for potable water and wastewater treatment.

  9. Oxidative Degradation of Chlorophenolic Compounds with Modified-Fenton Process Using Pyrite as the Catalyst

    Science.gov (United States)

    Kantar, Cetin; Urken, Ozge; Oral, Ozlem; Kaplan, Iremsu; Ayman Oz, Nilgun

    2017-04-01

    Oxidative dehalogenation has been shown to be a viable and cost effective process for dealing with a particularly persistent class of contaminants (e.g., chlorophenolic compounds (CP)) often found in contaminated soil and ground water. Here, the degradation of various chlorophenolic compounds (e.g., 2-CP, 4-CP, 2,3-di CP, 2,4-di CP, 2,4,6-tri CP, 2,3,4,6-Tetra CP) was investigated by modified Fenton process using pyrite as source of Fe2+ (catalyst) . The effects of different parameters such as chlorophenol type, pH and chlorophenol, pyrite and H2O2 concentrations on the degradation kinetics of chlorophenols were studied in batch reactors. Our results show that while the rate of chloropehenol degradation increased with decreasing solution pH, no direct correlation was observed between H2O2 concentration and chlorophenol degradation, indicating a complex mechanism involved in CP degradation by modified Fenton process. The batch results also show that the CP degradation was highly dependent on CP type, the number and location of chloride ions in the structure. Overall, the results of this study suggest that pyrite can be effectively used in reactive treatment barriers for in-situ treatment of subsurface systems contaminated with chlorophenols.

  10. Rapid and facile preparation of zinc ferrite (ZnFe{sub 2}O{sub 4}) oxide by microwave-solvothermal technique and its catalytic activity in heterogeneous photo-Fenton reaction

    Energy Technology Data Exchange (ETDEWEB)

    Anchieta, Chayene G.; Severo, Eric C.; Rigo, Caroline; Mazutti, Marcio A. [Department of Chemical Engineering, Federal University of Santa Maria, 97105-900, Santa Maria (Brazil); Kuhn, Raquel C., E-mail: raquelckuhn@yahoo.com.br [Department of Chemical Engineering, Federal University of Santa Maria, 97105-900, Santa Maria (Brazil); Muller, Edson I.; Flores, Erico M.M. [Department of Chemistry, Federal University of Santa Maria, 97105-900, Santa Maria (Brazil); Moreira, Regina F.P.M. [Department of Chemical Engineering and Food Engineering, Federal University of Santa Catarina, 88040-970, Florianópolis (Brazil); Foletto, Edson L. [Department of Chemical Engineering, Federal University of Santa Maria, 97105-900, Santa Maria (Brazil)

    2015-06-15

    In this work zinc ferrite (ZnFe{sub 2}O{sub 4}) oxide was rapidly and easily prepared by microwave-solvothermal route and its catalytic property in photo-Fenton reaction was evaluated. The effects of microwave heating time and power on the properties of produced particles were investigated. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM) and nitrogen adsorption–desorption isotherms were the techniques used for characterizing the solid products. The synthesized material was tested as a catalyst in the degradation of the textile dye molecule by the heterogeneous photo-Fenton process. Characterization results showed that the microwave heating time and power have significant influences on the formation of the phase spinel as well as on its physical properties. The reaction results showed that the ZnFe{sub 2}O{sub 4} oxide has good photocatalytic activity, which can be attributed to high surface area and pore volume, and large pore size. The ZnFe{sub 2}O{sub 4} oxide produced by the microwave irradiation exhibited promising photocatalytic activity for the removal of textile dye, reaching nearly 100% of decolorization at 40 min and 60% of mineralization at 240 min. Therefore, ZnFe{sub 2}O{sub 4} particles rapidly prepared by the microwave route have the potential for use in treatment of textile wastewater by the heterogeneous photo-Fenton process. - Highlights: • ZnFe{sub 2}O{sub 4} was synthesized by microwave-solvothermal method. • ZnFe{sub 2}O{sub 4} was prepared by different microwave heating times and powers. • ZnFe{sub 2}O{sub 4} was used as heterogeneous photo-Fenton catalyst. • Degradation of Procion red dye using heterogeneous photo-Fenton process. • ZnFe{sub 2}O{sub 4} was highly efficient to degrade textile dye under visible light.

  11. Evaluation of MnO2-templated iron oxide-coated diatomites for their catalytic performance in heterogeneous photo Fenton-like system.

    Science.gov (United States)

    He, Yi; Jiang, De Bin; Jiang, De Yi; Chen, Jie; Zhang, Yu Xin

    2018-02-15

    Herein, iron oxide-coated diatomites were prepared through hydrothermal synthesis and sacrificial template redox etching reaction. The microstructure characterization results revealed that the Fe2O3 nanorods were uniformly distributed on the surface of diatomite. The effects of diverse synthetic parameters on morphology of as-synthesized Fe2O3@diatomite were investigated. When the reaction time was prolonged from 12h to 24h, the morphology of FeOOH would change from nanorods into nanoflowers. Two different crystal phases of Fe2O3@diatomite were obtained from the FeOOH@diatomite samples calcined under different atmospheres. The catalytic activity of α-Fe2O3@diatomite was evaluated by the heterogeneous photo Fenton-like system through degradation of methylene blue (MB, 10 - 40mgL-1) in the presence of hydrogen peroxide (H2O2, 9mM - 120mM) under UV light irradiation. It was found that α-Fe2O3@diatomite composites showed very excellent degradation efficiency, which was about 99% within 120min under UV irradiation. This catalyst extended the range of pH values of homogeneous Fenton reaction, in which the MB removal rate was maintained over 80.8%. Moreover, the α-Fe2O3@diatomite catalyst still showed sound reusability after 5 rounds of degradation of MB dye. In principles, a possible photo-catalytic mechanism was proposed to testify metal oxides composites for heterogeneous photo Fenton-like reaction. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Electroplating sludge derived zinc-ferrite catalyst for the efficient photo-Fenton degradation of dye.

    Science.gov (United States)

    Cao, Zhenbang; Zhang, Jia; Zhou, Jizhi; Ruan, Xiuxiu; Chen, Dan; Liu, Jianyong; Liu, Qiang; Qian, Guangren

    2017-05-15

    A zinc-dominant ferrite catalyst for efficient degradation of organic dye was prepared by the calcination of electroplating sludge (ES). Characterizations indicated that zinc ferrite (ZnFe2O4) coexisted with Fe2O3 structure was the predominant phase in the calcined electroplating sludge (CES). CES displayed a high decolorization ratio (88.3%) of methylene blue (MB) in the presence of H2O2 combined with UV irradiation. The high efficiency could be ascribed to the photocatalytic process induced by ZnFe2O4 and the photo-Fenton dye degradation by ferrous content, and a small amount of Al and Mg in the sludge might also contribute to the catalysis. Moreover, the degradation capability of dye by CES was supported by the synthetic ZnFe2O4 with different Zn to Fe molar ratio (n(Zn): n(Fe)), as 84.81%-86.83% of dye was removed with n(Zn): n(Fe) ranged from 1:0.5 to 1:3. All synthetic ferrite samples in the simulation achieved adjacent equilibrium decolorization ratio, the flexible proportioning of divalent metal ions (M2+) to trivalent metal ions (M3+) applied in the synthesis indicated that the catalyst has a high availability. Therefore, an efficacious catalyst for the degradation of dye can potentially be derived from heavy metal-containing ES, it's a novel approach for the reutilization of ES. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Preparation of a Modified PTFE Fibrous Photo-Fenton Catalyst and Its Optimization towards the Degradation of Organic Dye

    Directory of Open Access Journals (Sweden)

    Zhizhong Ding

    2012-01-01

    Full Text Available Polytetrafluoroethylene (PTFE fiber was grafted with acrylic acid to impart the carboxyl groups onto the fiber surface, which were used to coordinate with both transition metal ions Fe(III and Cu(II and a rare metal ion Ce(III to prepare the metal grafted PTFE fiber complexes as the novel heterogeneous Fenton catalysts for the degradation of the azo dye in water under visible irradiation. Some factors affecting the preparation process, such as nature and concentration of metal ions in the coordination solution, grafting degree of PTFE and reaction temperature were optimized with respect to the content and strength of metal fixation on the fiber and dye degradation efficiency. The results indicated that increasing metal ion concentrations in solution and grafting degree of PTFE fiber as well as higher coordination temperature led to a significant increase in metal content, especially Fe(III and Cu(II content of the complexes. Fe(III ions fixed on the fiber showed the better catalytic performance than Cu(II and Ce(III ions fixed when three different complexes with similar metal content being employed, respectively. Moreover, Increasing Fe content or incorporation of Cu(II ions could significantly improve the catalytic activity of the complexes.

  14. Heterogeneous fenton process using the mineral hematite for the discolouration of a reactive dye solution

    Directory of Open Access Journals (Sweden)

    F. V. F. Araujo

    2011-12-01

    Full Text Available This work reports a study on the heterogeneous Fenton reaction using hematite powder (Fe2O3 in suspension for the discolouration of the reactive dye Drimarene Red X-6BN in aqueous solutions. The efficiency of the process was studied as a function of the experimental conditions: initial pH; H2O2 dose; and hematite powder concentration; all of which showed a strong effect on the reaction kinetics. Under the best experimental conditions: pH = 2.5; H2O2 dose = 800 mg/L; and [Hematite] = 20 g/L, it was possible to remove about 99% of the initial colour in 120 minutes in a batch reaction at 25ºC. The analysis of the kinetic results suggests that the reaction is initiated by heterogeneous generation of free radicals on the hematite surface, but as soluble iron (III and iron (II species are released into the solution during the course of the reaction, a simultaneous homogeneous Fenton reaction step propagates and contributes to the overall reaction.

  15. Rape oil transesterification over heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Encinar, J.M.; Martinez, G. [Dpto. Ingenieria Quimica y Quimica Fisica, UEX, Avda. Elvas s/n, 06071-Badajoz (Spain); Gonzalez, J.F. [Dpto. Fisica Aplicada, UEX, Avda Elvas s/n, 06071-Badajoz (Spain); Pardal, A. [Dpto. Ciencias do Ambiente, ESAB, IPBeja, Rua Pedro Soares s/n, 7800-Beja (Portugal)

    2010-11-15

    This work studies the application of KNO{sub 3}/CaO catalyst in the transesterification reaction of triglycerides with methanol. The objective of the work was characterizing the methyl esters for its use as biodiesel in compression ignition motors. The variables affecting the methyl ester yield during the transesterification reaction, such as, amount of KNO{sub 3} impregnated in CaO, the total catalyst content, reaction temperature, agitation rate, and the methanol/oil molar ratio, were investigated to optimize the reaction conditions. The evolution of the process was followed by gas chromatography, determining the concentration of the methyl esters at different reaction times. The biodiesel was characterized by its density, viscosity, cetane index, saponification value, iodine value, acidity index, CFPP (cold filter plugging point), flash point and combustion point, according to ISO norms. The results showed that calcium oxide, impregnated with KNO{sub 3}, have a strong basicity and high catalytic activity as a heterogeneous solid base catalyst. The biodiesel with the best properties was obtained using an amount of KNO{sub 3} of 10% impregnated in CaO, a methanol/oil molar ratio of 6:1, a reaction temperature of 65 C, a reaction time of 3.0 h, and a catalyst total content of 1.0%. In these conditions, the oil conversion was 98% and the final product obtained had very similar characteristics to a no. 2 diesel, and therefore, these methyl esters might be used as an alternative to fossil fuels. (author)

  16. Hydroxyl radical production by a heterogeneous Fenton reaction supported in insoluble tannin from bark of Pinus radiata.

    Science.gov (United States)

    Romero, Romina; Contreras, David; Segura, Cristina; Schwederski, Brigitte; Kaim, Wolfgang

    2017-03-01

    Fenton reactions driven by dihydroxybenzenes (DHBs) have been used for pollutant removal via advanced oxidation processes (AOPs), but such systems have the disadvantage of DHB release into the aqueous phase. In this work, insoluble tannins from bark can be used to drive Fenton reactions and as a heterogeneous support. This avoids the release of DHBs into the aqueous phase and can be used for AOPs. The production of ·OH was investigated using a spin-trapping electron paramagnetic resonance technique (5-dimethyl-1-pyrroline-N-oxide/·OH) in the first minute of the reaction and a high-performance liquid chromatography-fluorescence technique (coumarin/7-hydroxycoumarin) for 20 min. The ·OH yield achieved using insoluble tannins from Pinus radiata bark was higher than that achieved using catechin to drive the Fenton reaction. The Fenton-like system driven by insoluble tannins achieved 92.6 ± 0.3 % degradation of atrazine in 30 min. The degradation kinetics of atrazine was linearly correlated with ·OH production. The increased reactivity in ·OH production and insolubility of the ligand are promising for the development of a new technique for degradation of pollutants in wastewater using heterogeneous Fenton systems.

  17. Determination of phthalate esters in airborne particulates by heterogeneous photo-Fenton catalyzed aromatic hydroxylation fluorimetry.

    Science.gov (United States)

    Zeng, He-Hua; Li, Xue-Qin; Hao, Wen-Li; Zhang, Li-Zhong; Wei, Ting; Zhao, Xiu-Feng; Liu, Yu-Yan; Li, Jian-Hui

    2017-02-15

    The environmental contaminants phthalic acid esters (PAEs) were determined by aromatic hydroxylation fluorimetry combined with heterogeneous photo-Fenton process in the presence of vermiculite supported BiFeO3 (VMT-BiFeO3). In strong alkaline solution, PAEs were hydrolyzed into phthalates with no fluorescence, which then reacted with hydroxyl free radicals produced in photo-Fenton process catalyzed by VMT-BiFeO3 to form the fluorescent hydroxyl phthalates. The fluorescence intensity was proportional to the concentration of PAEs with the maximum excitation and emission wavelength of 300nm and 417nm, respectively. A good linear relationship can be obtained in the range of 3.8×10-7 to 4.8×10-5molL-1 for DEP with correlation coefficient of 0.9997, and the sensitivity of the method was high with detection limit of 5.43×10-8molL-1. The method has been successfully applied to determine total PAEs in airborne particulates with satisfactory results. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Degradation of industrial azo dye in aqueous solution by heterogeneous Fenton process (fly ash/H2O2

    Directory of Open Access Journals (Sweden)

    Bečelić-Tomin Milena R.

    2012-01-01

    Full Text Available The aim of this study was to investigate the possibilities and efficiency of heterogeneous Fenton process with the use of fly ash from thermal power plants Kolubara, Serbia, as the catalyst in the degradation of industrial azo dye Zetanyl Rosso B-NG. The effects of various experimental parameters such as pH, temperature, concentration of fly ash, the initial concentration of H2O2 and initial concentration of dye on the kinetics and efficiency of decolorization were investigated. Simultaneous leaching of iron from fly ash was monitored. The optimum conditions had been determined, and it was found that decolorization efficiency obtained after 150 min of reaction, was about 98.9%. The optimal parameters were: initial pH = 3; [H2O2]0 = 6 mM; dosage of fly ash = 0.1g/l (for dye concentration of 100 mg/l; temperature = 22 °C. The effectiveness of the applied treatment for mineralization of dye solution was investigated, under optimal conditions determined by the examination of various factors influencing the decolorization process at the specified contact time. The maximum achieved reduction of total organic carbon content was 96.5%. The results indicate that the reuse of fly ash as the catalyst support in •OH production in this process achieves significant efficiency in terms of decolorization, 94.4% and mineralization, 89.6%. Futhermore, fly ash showed adequate stability during the reaction (low iron leaching, concentrations under optimal reaction condition were about 2 mg/l.

  19. Enhancement of Treatment Efficiency of Recalcitrant Wastewater Containing Textile Dyes Using a Newly Developed Iron Zeolite Socony Mobil-5 Heterogeneous Catalyst.

    Science.gov (United States)

    Ahmad, Mushtaq; Asghar, Anam; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

    2015-01-01

    Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption.

  20. Rapid degradation of methylene blue in a novel heterogeneous Fe3O4 @rGO@TiO2-catalyzed photo-Fenton system

    Science.gov (United States)

    Yang, Xiaoling; Chen, Wei; Huang, Jianfei; Zhou, Ying; Zhu, Yihua; Li, Chunzhong

    2015-05-01

    Herein, a ternary nanocomposite with TiO2 nanoparticles anchored on reduced graphene oxide (rGO)-encapsulated Fe3O4 spheres (Fe3O4@rGO@TiO2) is presented as a high efficient heterogeneous catalyst for photo-Fenton degradation of recalcitrant pollutants under neutral pH. Fe3O4@rGO@TiO2 was synthesized by depositing TiO2 nanoparticles on the surface of the Fe3O4 spheres wrapped by graphene oxide (GO) which was obtained by an electrostatic layer-by-layer method. This as-prepared catalyst reflected good ferromagnetism and superior stability which makes it convenient to be separated and recycled. Due to the synergic effects between the different components composed the catalyst, swift reduction of Fe3+ can be achieved to regenerate Fe2+. Fe3O4@rGO@TiO2 exhibited enhancing catalytic activity for the degradation of azo-dyes compared with Fe3O4, Fe3O4@SiO2@TiO2 or SiO2@rGO@TiO2, further conforming the rapid redox reaction between Fe2+ and Fe3+. All these merits indicate that the composite catalyst possesses great potential for visible-light driven destruction of organic compounds.

  1. Degradation of polyvinyl alcohol (PVA) by homogeneous and heterogeneous photocatalysis applied to the photochemically enhanced Fenton reaction.

    Science.gov (United States)

    Bossmann, S H; Oliveros, E; Göb, S; Kantor, M; Göppert, A; Lei, L; Yue, P L; Braun, A M

    2001-01-01

    The reaction mechanism of the oxidative degradation of polyvinyl alcohol (PVA) by the photochemically enhanced Fenton reaction was studied using a homogeneous (Fe2+(aq) + H2O2) and a heterogeneous reaction system (iron(III)-exchanged zeolite Y+ H2O2). In the homogeneous Fenton system, efficient degradation was observed in a batch reactor, equipped with a medium pressure mercury arc in a Pyrex envelope and employing 80% of the stoichiometric amount of H2O2 required for the total oxidation of PVA and a concentration ratio as low as I mole of iron(II) sulfate per 20 moles of PVA sub-units (C2H40). Model PVA polymers of three different molecular weights (15,000, 49,000 and 100,000 g mol(-1)) were found to follow identical degradation patterns. Strong experimental evidence supports the formation of supermacromolecules (MW: 1-5 x 10(6) g/mol) consisting of oxidized PVA and trapped iron(III) at an early reaction stage. Low molecular weight intermediates, such as oxalic acid, formic acid or formaldehyde were not found during PVA degradation in the homogeneous Fenton system, and we may deduce that the manifold of degradation reactions is mainly taking place within the super-macromolecules from which CO2 is directly released. However, in the heterogeneous Fenton system, the reaction behavior was found to be distinctly different: a decrease of the molecular weights of all three tested monodisperse PVA samples was observed by the broadening of the GPC-traces during irradiation, and oxalic acid was formed. The results lead to the mechanistic hypothesis that during the heterogeneous Fenton process, the cleavage of the PVA-chains may occur at random positions, the reactive centres being located inside the iron(III)-doped zeolite Y photocatalysts.

  2. Heterogeneous photo-Fenton degradation of acid red B over Fe2O3 supported on activated carbon fiber.

    Science.gov (United States)

    Lan, Huachun; Wang, Aiming; Liu, Ruiping; Liu, Huijuan; Qu, Jiuhui

    2015-03-21

    Fe2O3 supported on activated carbon fiber (Fe2O3/ACF) was prepared via an impregnation method and characterized by X-ray diffraction, scanning electron microscopy and BET analysis. The results indicated that Fe2O3 with small particle size was highly dispersed on the surface of the ACF and the introduction of Fe2O3 did not change the ACF pore structure. Fe2O3/ACF exhibited a higher Fenton efficiency for the degradation of acid red B (ARB), especially under simulated solar irradiation. Complete decoloration of the ARB solution and 43% removal of TOC could be achieved within 200 min under optimal conditions. It was verified that more ˙OH radicals were generated in the photo-assisted Fenton process and involved as active species in ARB degradation. FTIR analysis indicated that the degradation of ARB was initiated through the cleavage of -N=N-, followed by hydroxylation and opening of phenyl rings to form aliphatic acids, and further oxidation of aliphatic acids would produce CO2 and H2O. Moreover, Fe2O3/ACF maintained its activity after being reused 4 times and the release of iron from the catalyst was found to be insignificant during the Fenton and photo-Fenton processes, indicating that Fe2O3/ACF had good long-term stability. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Preparation of Heterogeneous CaO Catalysts for Biodiesel Production

    Science.gov (United States)

    Widayat, W.; Darmawan, T.; Hadiyanto, H.; Rosyid, R. Ar

    2017-07-01

    The objective of this research was to develop heterogeneous catalysts from three CaO sources for biodiesel synthesis. The CaO catalyst were prepared from limestone, calcium hydroxide and calciun carbonate with thermal processing in a muffle furnace at 900°C.. The results showed that CaO catalyst from limestone has better characteristic than catalyst from Calcium Hydroxide and Calcium Carbonate. From morphology testing, the CaO catalyst derived from limestone formed a crystal, while The X-ray difraction analysis showed that the amount of CaO contained in limestone was the highest among the others. The yield of biodiesel obtained from the experiment was 89.98% for the catalyst from limestone; 85.15% for the catalyst Ca (OH)2; and 78.71% for CaCO3 catalyst.

  4. Preparation of a new Fenton-like catalyst from red mud using molasses wastewater as partial acidifying agent.

    Science.gov (United States)

    Wei, Guangtao; Shao, Luhua; Mo, Jihua; Li, Zhongmin; Zhang, Linye

    2017-06-01

    Using molasses wastewater as partial acidifying agent, a new Fenton-like catalyst (ACRM sm ) was prepared through a simple process of acidification and calcination using red mud as main material. With molasses wastewater, both the free alkali and the chemically bonded alkali in red mud were effectively removed under the action of H2SO4 and molasses wastewater, and the prepared ACRM sm was a near-neutral catalyst. The ACRM sm preparation conditions were as follows: for 3 g of red mud, 9 mL of 0.7 mol/L H2SO4 plus 2 g of molasses wastewater as the acidifying agent, calcination temperature 573 K, and calcination time 1 h. Iron phase of ACRM sm was mainly α-Fe2O3 and trace amount of carbon existed in ACRM sm . The addition of molasses wastewater not only effectively reduced the consumption of H2SO4 in acidification of red mud but also resulted in the generation of carbon and significantly improved the distribution of macropore in prepared ACRM sm . It was found that near-neutral pH of catalyst, generated carbon, and wide distribution of macropore were the main reasons for the high catalytic activity of ACRM sm . The generated carbon and wide distribution of macropore were entirely due to the molasses wastewater added. In degradation of orange II, ACRM sm retained most of its catalytic stability and activity after five recycling times, indicating ACRM sm had an excellent long-term stability in the Fenton-like process. Furthermore, the performance test of settling showed ACRM sm had an excellent settleability. ACRMsm was a safe and green catalytic material used in Fenton-like oxidation for wastewater treatment.

  5. Magnetically separable core-shell structural γ-Fe2O3@Cu/Al-MCM-41 nanocomposite and its performance in heterogeneous Fenton catalysis.

    Science.gov (United States)

    Ling, Yuhan; Long, Mingce; Hu, Peidong; Chen, Ya; Huang, Juwei

    2014-01-15

    To target the low catalytic activity and the inconvenient separation of copper loading nanocatalysts in heterogeneous Fenton-like reaction, a core-shell structural magnetically separable catalyst, with γ-Fe2O3 nanoparticles as the core layer and the copper and aluminum containing MCM-41 as the shell layer, has been fabricated. The role of aluminum has been discussed by comparing the copper containing mesoporous silica with various Cu contents. Their physiochemical properties have been characterized by XRD, UV-vis, FT-IR, TEM, nitrogen physisorption and magnetite susceptibility measurements. Double content Cu incorporation results in an improved catalytic activity for phenol degradation at the given condition (40°C, initial pH=4), but leads to a declined BET surface area and less ordered mesophase structure. Aluminum incorporation helps to retain the high BET surface area (785.2m(2)/g) and the regular hexagonal mesoporous structure of MCM-41, which make the catalyst possess a lower copper content and even a higher catalytic activity than that with the double copper content in the absence of aluminum. The catalysts can be facilely separated by an external magnetic field for recycle usage. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Reduced Graphene Oxide as a Metal-Free Catalyst for the Light-Assisted Fenton-Like Reaction

    OpenAIRE

    Espinosa López, Juan Carlos; Navalón Oltra, Sergio; Alvaro Rodríguez, Maria Mercedes; García Gómez, Hermenegildo

    2016-01-01

    Natural Sunlight irradiation increases the catalytic activity of reduced graphene oxide (rGO) as metal-free Fenton-like catalyst for phenol degradation. Intermediacy of hydroxyl radicals was proved by electron paramagnetic resonance spectroscopy using a spin trapping agent. Spanish Ministry of Economy and Competitiveness CTQ-2014-53292-R CTQ-2015-69153-CO2-1 Generalidad Valenciana 2013/014 Espinosa López, JC.; Navalón Oltra, S.; Alvaro Rodríguez, MM.; García Gómez, H. (2016). Re...

  7. Functionalized magnetic nanoparticles: A novel heterogeneous catalyst support

    Science.gov (United States)

    Functionalized magnetic nanoparticles have emerged as viable alternatives to conventional materials, as robust, high-surface-area heterogeneous catalyst supports. Post-synthetic surface modification protocol for magnetic nanoparticles has been developed that imparts desirable che...

  8. Comparison of heterogeneous fenton process and adsorption process on magnetic nanocomposite for ciprofloxacin removal from aqueous solutions

    Directory of Open Access Journals (Sweden)

    MT. Samadi

    2016-04-01

    Full Text Available Background: Continuous input of antibiotics to the environment can cause many potential problems such as antibiotic resistance in pathogens. Objective: The aim of this study was to compare heterogeneous fenton process and adsorption process on magnetic nanocomposite for ciprofloxacin removal from aqueous solutions. Methods: This experimental study was conducted at the Hamadan University of Medical Science in 2014. The efficiency of magnetic nanocomposite for ciprofloxacin removal was assessed in a batch system considering 15-300 min reaction time, pH 4-10, 30-200 mg/L initial ciprofloxacin concentration, 1-3 g/L adsorbent and 5-25 mmol/L HR2ROR2R. Physical and structural characteristics of the synthesized adsorbent were analyzed using Fourier Transform Infrared Spectra (FTIR techniques. Findings: The maximum efficiency of heterogeneous fenton process and adsorption process was obtained at pH 4 and 7 in which the efficiency of ciprofloxacin removal was 95% and 87%, respectively. The equilibrium adsorption data was well fitted with Langmuir isotherm. The reaction rate had the best compatibility with pseudo-second-order kinetic model. Conclusion: With regards to the results, magnetic nanocomposite (Fe3O4/MWCNTs can be considered as an acceptable adsorbent in heterogeneous fenton procces for ciprofloxacin removal from aqueous solutions.

  9. Titanium dioxide as a catalyst support in heterogeneous catalysis.

    Science.gov (United States)

    Bagheri, Samira; Muhd Julkapli, Nurhidayatullaili; Bee Abd Hamid, Sharifah

    2014-01-01

    The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications.

  10. Titanium Dioxide as a Catalyst Support in Heterogeneous Catalysis

    Science.gov (United States)

    Bagheri, Samira; Muhd Julkapli, Nurhidayatullaili; Bee Abd Hamid, Sharifah

    2014-01-01

    The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications. PMID:25383380

  11. Preparation of biodiesel from soybean oil by using heterogeneous catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Ferdous, Kaniz; Rakib Uddin, M.; Islam, M.A. [Department of Chemical Engineering and Polymer Science, Shah Jalal University of Science and Technology, Sylhet 3114 (Bangladesh); Khan, Maksudur R. [Department of Chemical Engineering and Polymer Science, Shah Jalal University of Science and Technology, Sylhet 3114 (Bangladesh); Faculty of Chemical and Natural Resources Engineering, University Malaysia Pahang, 26300 Gambang, Kuantan, Pahang (Malaysia)

    2013-07-01

    The predicted shortage of fossil fuels and related environmental concerns has recently attracted significant attention to search alternative fuel. Biodiesel is one of the alternatives to fossil fuel. Now-a-days, most biodiesel is produced by the transesterification of oils using methanol and a homogeneous base catalyst. The use of homogeneous catalysts is normally limited to batch mode processing followed by a catalyst separation step. The immiscible glycerol phase, which accumulates during the course of the reaction, solubilizes the homogeneous base catalyst and therefore, withdraws from the reaction medium. Moreover, other difficulties of using homogeneous base catalysts relate to their sensitivity to free fatty acid (FFA) and water and resulting saponification phenomenon. High energy consumption and costly separation of the catalyst from the reaction mixture have inspired the use of heterogeneous catalyst. The use of heterogeneous catalysts does not lead to the formation of soaps through neutralization of FFA and saponification of oil. In the present paper, biodiesel was prepared from crude (soybean) oil by transesterification reaction using heterogeneous base catalyst name calcium oxide (CaO). Various reaction parameters were optimized and the biodiesel properties were evaluated.

  12. Facile preparation of magnetic mesoporous Fe3O4/C/Cu composites as high performance Fenton-like catalysts

    Science.gov (United States)

    Li, Keyan; Zhao, Yongqin; Janik, Michael J.; Song, Chunshan; Guo, Xinwen

    2017-02-01

    Fe-Cu composites with different compositions and morphologies were synthesized by a hydrothermal method combined with precursor thermal transformation. γ-Fe2O3/CuO and α-Fe2O3/CuO were obtained by calcining the Fe and Cu tartrates under air atmosphere at 350 °C and 500 °C, respectively, while Fe3O4/C/Cu was obtained by calcining the tartrate precursor under N2 atmosphere at 500 °C. The Fe3O4/C/Cu composite possessed mesoporous structure and large surface area up to 133 m2 g-1. The Fenton catalytic performance of Fe3O4/C/Cu composite was closely related to the Fe/Cu molar ratio, and only proper amounts of Fe and Cu exhibited a synergistic enhancement in Fenton catalytic activity. Cu inclusion reduced Fe3+ to Fe2+, which accelerated the Fe3+/Fe2+ cycles and favored H2O2 decomposition to produce more hydroxyl radicals for methylene blue (MB) oxidation. Due to the photo-reduction of Fe3+ and Cu2+, the Fenton catalytic performance was greatly improved when amending with visible light irradiation in the Fe3O4/C/Cu-H2O2 system, and MB (100 mg L-1) was nearly removed within 60 min. The Fe3O4/C/Cu composite showed good recyclability and could be conveniently separated by an applied magnetic field. Compared with conventional methods for mesoporous composite construction, the thermolysis method using mixed metal tartrates as precursors has the advantages of easy preparation and low cost. This strategy provides a facile, cheap and green method for the synthesis of mesoporous composites as excellent Fenton-like catalysts, without any additional reductants or organic surfactants.

  13. Coupling of acrylic dyeing wastewater treatment by heterogeneous Fenton oxidation in a continuous stirred tank reactor with biological degradation in a sequential batch reactor.

    Science.gov (United States)

    Esteves, Bruno M; Rodrigues, Carmen S D; Boaventura, Rui A R; Maldonado-Hódar, F J; Madeira, Luís M

    2016-01-15

    This work deals with the treatment of a recalcitrant effluent, from the dyeing stage of acrylic fibres, by combination of the heterogeneous Fenton's process in a continuous stirred tank reactor (CSTR) with biological degradation in a sequential batch reactor (SBR). Three different catalysts (a commercial Fe/ZSM-5 zeolite and two distinct Fe-containing activated carbons - ACs - prepared by wet impregnation of iron acetate and iron nitrate) were employed on the Fenton's process, and afterwards a parametric study was carried out to determine the effect of the main operating conditions, namely the hydrogen peroxide feed concentration, temperature and contact time. Under the best operating conditions found, using the activated carbon impregnated with iron nitrate, 62.7% of discolouration and 39.9% of total organic carbon (TOC) reduction were achieved, at steady-state. Furthermore, a considerable increase in the effluent's biodegradability was attained (BOD5:COD ratio increased from <0.001 to 0.27 and SOUR - specific oxygen uptake rate - from <0.2 to 11.1 mg O2/(gVSS·h)), alongside a major decrease in its toxicity (from 92.1 to 94.0% of Vibrio fischeri inhibition down to 6.9-9.9%). This allowed the application of the subsequent biological degradation stage. The combination of the two processes provided a treated effluent that clearly complies with the legislated discharge limits. It was also found that the iron leaching from the three catalysts tested was very small in all runs, a crucial factor for the stability and long-term use of such materials. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Decolorization of azo dyes Orange G using hydrodynamic cavitation coupled with heterogeneous Fenton process.

    Science.gov (United States)

    Cai, Meiqiang; Su, Jie; Zhu, Yizu; Wei, Xiaoqing; Jin, Micong; Zhang, Haojie; Dong, Chunying; Wei, Zongsu

    2016-01-01

    The present work demonstrates the application of the combination of hydrodynamic cavitation (HC) and the heterogeneous Fenton process (HF, Fe(0)/H2O2) for the decolorization of azo dye Orange G (OG). The effects of main affecting operation conditions such as the inlet fluid pressure, initial concentration of OG, H2O2 and zero valent iron (ZVI), the fixed position of ZVI, and medium pH on decolorization efficiency were discussed with guidelines for selection of optimum parameters. The results revealed that the acidic conditions are preferred for OG decolorizaiton. The decolorization rate increased with increasing H2O2 and ZVI concentration and decreased with increasing OG initial concentration. Besides, the decolorization rate was strongly dependent on the fixed position of ZVI. The analysis results of degradation products using liquid chromatography-ESI-TOF mass spectrometry revealed that the degradation mechanism of OG proceeds mainly via reductive cleavage of the azo linkage due to the attack of hydroxyl radical. The present work has conclusively established that the combination of HC and HF can be more energy efficient and gives higher decolorization rate of OG as compared with HC and HF alone. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Preparation of transition metal composite graphite felt cathode for efficient heterogeneous electro-Fenton process.

    Science.gov (United States)

    Liang, Liang; Yu, Fangke; An, Yiran; Liu, Mengmeng; Zhou, Minghua

    2017-01-01

    A composite graphite felt (GF) modified with transition metal was fabricated and used as cathode in heterogeneous electro-Fenton (EF) for methyl orange (MO) degradation. Characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), the morphology and surface physicochemical properties of the cathodes after modification were observed considerably changed. After loading metals, the current response became higher, the accumulation of H2O2 and the degradation efficiency of MO were improved. Under the same conditions, GF-Co had the highest catalytic activity for electro-reduction of O2 to H2O2 and MO degradation. At pH 3, 99 % of MO degradation efficiency was obtained using GF-Co after 120 min treatment and even at initial pH 9, 82 % of that was obtained. TOC removal efficiency reached 93.8 % using GF-Co at pH 3 after 120 min treatment while that was 12.3 % using GF. After ten-time runs, the mineralization ratio of the GF-Co was still 89.5 %, suggesting that GF-Co was very promising for wastewater treatment. The addition of isopropanol proved that (·)OH played an important role in degradation of MO.

  16. Visible-light photo-Fenton oxidation of phenol with rGO-α-FeOOH supported on Al-doped mesoporous silica (MCM-41) at neutral pH: Performance and optimization of the catalyst.

    Science.gov (United States)

    Wang, Ying; Liang, Mingxing; Fang, Jiasheng; Fu, Jun; Chen, Xiaochun

    2017-09-01

    In this study, α-FeOOH on reduced graphene oxide (rGO-α-FeOOH) supported on an Al-doped MCM-41 catalyst (RFAM) was optimized for the visible-light photo-Fenton oxidation of phenol at neutral pH. The stability of the catalysts, effect of bubbling aeration, and degradation intermediates were investigated. Results indicated that RFAM with a large Brunauer-Emmett-Teller (BET) area and mesoporous structure displayed excellent catalytic activity for the visible-light-driven (VLD) photo-Fenton process. Phenol degradation was well described by a pseudo-first-order reaction kinetics model. Raman analysis demonstrated that an rGO-α-FeOOH (RF) composite is formed during the ferrous-ion-induced self-assembly process. Al-MCM-41 could uniformly disperse RF nanosheets and promote the mobility and diffusion of matter. The activity of the main catalyst α-FeOOH was enhanced after the incorporation of rGO nanosheets. The α-FeOOH crystal in RFAM showed catalytic activity superior to those of Fe3O4 and Fe2O3. The RFAM catalyst, with an optimal GO-Fe(2+)mass ratio of 2.33, exhibited a larger BET area, pore size, and pore volume, and thus exhibited high performance and energy utilization efficiency in the VLD photo-Fenton reaction with remarkable stability. Bubbling N2 inhibited catalytic performance, while bubbling O2 or air only slightly accelerated the phenol degradation. Visible light played an important role in accelerating the formation of reactive oxygen species (·OH) for the highly efficient phenol degradation. Analysis of degradation intermediates indicated a high phenol mineralization level and the formation of low-molecular-weight organic acids. This work would be helpful in providing an insight into a new type of catalyst assembly and a possible route to a promising heterogeneous catalyst applicable in the visible light photo-Fenton process for effective wastewater remediation at neutral pH. Copyright © 2017. Published by Elsevier Ltd.

  17. Hydrogenation of artemisinin to dihydroartemisinin over heterogeneous metal catalysts

    Science.gov (United States)

    Kristiani, Anis; Pertiwi, Ralentri; Adilina, Indri Badria

    2017-01-01

    A series of heterogeneous metal catalysts of Ni, Pd, and Pt, both of synthesized and commercial catalysts were used for hydrogenation of artemisinin to dihydroartemisinin. Their catalytic properties were determsined by Surface Area Analyzer and Thermogravimetry Analyzer. The catalytic properties in various reaction conditions in terms of temperature, pressure, reaction time and reactant/catalyst ratio were also studied. The results catalytic activity tests showed that synthesized catalysts of Ni/zeolite, Ni-Sn/zeolite, Ni/bentonite and Ni-Sn/bentonite were not able to produced dihydroartemisinin and deoxyartemisinin was mainly formed. Meanwhile, commercial catalysts of Ni skeletal, Pd/activated charcoal and Pt/activated charcoal yielded the desired dihydroartemisinin product. Ni skeletal commercial catalyst gave the best performance of hydrogenation artemisinin to dihydroartemisinin in room temperature and low H2 pressure.

  18. Hydrogenation of citral into its derivatives using heterogeneous catalyst

    Science.gov (United States)

    Sudiyarmanto, Hidayati, Luthfiana Nurul; Kristiani, Anis; Aulia, Fauzan

    2017-11-01

    Citral as known as a monoterpene can be found in plants and citrus fruits. The hydrogenation of citral into its derivatives become interesting area for scientist. This compound and its derivatives can be used for many application in pharmaceuticals and food areas. The development of heterogeneous catalysts become an important aspect in catalytic hydrogenation citral process. Nickel supported catalysts are well known as hydrogenation catalyst. These heterogeneous catalysts were tested their catalytic activity in hydrogenation of citral. The effect of various operation conditions, in term of feed concentration, catalyst loading, temperature, and reaction time were also studied. The liquid products produced were analyzed by using Gas Chromatography-Mass Spectroscopy (GC-MS). The result of catalytic activity tests showed nickel skeletal catalyst exhibits best catalytic activity in hydrogenation of citral. The optimum of operation condition was achieved in citral concentration 0.1 M with nickel skeletal catalyst loading of 10% (w/w) at 80 °C and 20 bar for 2 hours produced the highest conversion as of 64.20% and the dominant product resulted was citronellal as of 56.48%.

  19. Selective Fenton-like oxidation of methylene blue on modified Fe-zeolites prepared via molecular imprinting technique.

    Science.gov (United States)

    Zhang, Yuanyuan; Shang, Jiaobo; Song, Yanqun; Rong, Chuan; Wang, Yinghui; Huang, Wenyu; Yu, Kefu

    2017-02-01

    A facile strategy to increase the selectivity of heterogeneous Fenton oxidation is investigated. The increase was reached by increasing selective adsorption of heterogeneous Fenton catalyst to a target pollutant. The heterogeneous Fenton catalyst was prepared by a two-step process. First, zeolite particles were imprinted by the target pollutant, methylene blue (MB), in their aggregations, and second, iron ions were loaded on the zeolite aggregations to form the molecule imprinted Fe-zeolites (MI-FZ) Fenton catalyst. Its adsorption amount for MB reached as high as 44.6 mg g(-1) while the adsorption amount of un-imprinted Fe-zeolites (FZ) is only 15.6 mg g(-1). Fenton removal efficiency of MI-FZ for MB was 87.7%, being 33.9% higher than that of FZ. The selective Fenton oxidation of MI-FZ for MB was further confirmed by its removal performance for the mixed MB and bisphenol A (BPA) in solution. The removal efficiency of MB was 44.7% while that of BPA was only 14.9%. This fact shows that molecular imprinting is suitable to prepare the Fe-zeolites (FZ)-based Fenton catalyst with high selectivity for removal of target pollutants, at least MB.

  20. Treatment of Actual Chemical Wastewater by a Heterogeneous Fenton Process Using Natural Pyrite

    National Research Council Canada - National Science Library

    Sun, Liang; Li, Yan; Li, Aimin

    2015-01-01

    .... Excessive amounts of pyrite and H₂O₂ did not negatively affect the pyrite Fenton system. The amount of aniline generated indicated that nitrobenzene reduction by pyrite was promoted using a low initial concentration of H₂O₂ (<5 mmol/L...

  1. Treatment of Actual Chemical Wastewater by a Heterogeneous Fenton Process Using Natural Pyrite.

    Science.gov (United States)

    Sun, Liang; Li, Yan; Li, Aimin

    2015-10-28

    Wastewater from chemical plants has remarkable antibiotic effects on the microorganisms in traditional biological treatment processes. An enhanced Fenton system catalyzed by natural pyrite was developed to degrade this kind of wastewater. Approximately 30% chemical oxygen demand (COD) was removed within 120 min when 50 mmol/L H₂O₂ and 10 g/L natural pyrite were used at initial pH from 1.8 to 7. A BOD₅/COD enhancement efficiency of 210% and an acute biotoxicity removal efficiency of 84% were achieved. The COD removal efficiency was less sensitive to initial pH than was the classic Fenton process. Excessive amounts of pyrite and H₂O₂ did not negatively affect the pyrite Fenton system. The amount of aniline generated indicated that nitrobenzene reduction by pyrite was promoted using a low initial concentration of H₂O₂ (reduction by natural pyrite of organic molecules containing an electron-withdrawing group to electron-donating group. Thus, the Fenton-like process catalyzed by pyrite can remediate wastewater containing organic pollutants under mild reaction conditions and provide an alternative environmentally friendly method by which to reuse natural pyrite.

  2. Treatment of Actual Chemical Wastewater by a Heterogeneous Fenton Process Using Natural Pyrite

    Directory of Open Access Journals (Sweden)

    Liang Sun

    2015-10-01

    Full Text Available Wastewater from chemical plants has remarkable antibiotic effects on the microorganisms in traditional biological treatment processes. An enhanced Fenton system catalyzed by natural pyrite was developed to degrade this kind of wastewater. Approximately 30% chemical oxygen demand (COD was removed within 120 min when 50 mmol/L H2O2 and 10 g/L natural pyrite were used at initial pH from 1.8 to 7. A BOD5/COD enhancement efficiency of 210% and an acute biotoxicity removal efficiency of 84% were achieved. The COD removal efficiency was less sensitive to initial pH than was the classic Fenton process. Excessive amounts of pyrite and H2O2 did not negatively affect the pyrite Fenton system. The amount of aniline generated indicated that nitrobenzene reduction by pyrite was promoted using a low initial concentration of H2O2 (<5 mmol/L. Fluorescence excitation emission matrix analyses illustrated that H2O2 facilitated the reduction by natural pyrite of organic molecules containing an electron-withdrawing group to electron-donating group. Thus, the Fenton-like process catalyzed by pyrite can remediate wastewater containing organic pollutants under mild reaction conditions and provide an alternative environmentally friendly method by which to reuse natural pyrite.

  3. Nano-catalysts: Bridging the gap between homogeneous and heterogeneous catalysis

    Science.gov (United States)

    Functionalized nanoparticles have emerged as sustainable alternatives to conventional materials, as robust, high-surface-area heterogeneous catalyst supports. We envisioned a catalyst system, which can bridge the homogenous and heterogeneous system. Postsynthetic surface modifica...

  4. Novel RGO/α-FeOOH supported catalyst for Fenton oxidation of phenol at a wide pH range using solar-light-driven irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ying, E-mail: yingwang@bnu.edu.cn [The Key Laboratory of Water and Sediment Sciences, Ministry of Education, School of Environment, Beijing Normal University, Beijing 100875 (China); Fang, Jiasheng, E-mail: fangfangcanfly@163.com [The Key Laboratory of Water and Sediment Sciences, Ministry of Education, School of Environment, Beijing Normal University, Beijing 100875 (China); School of Chemistry and Chemical Engineering, Southeast University, Jiangsu Optoelectronic Functional Materials and Engineering Laboratory, Nanjing 211189 (China); Crittenden, John C., E-mail: John.Crittenden@ce.gatech.edu [School of Civil and Environmental Engineering and the Brook Byers Institute for Sustainable Systems, Georgia Institute of Technology, Atlanta, GA 30332-0595 (United States); Shen, Chanchan [The Key Laboratory of Water and Sediment Sciences, Ministry of Education, School of Environment, Beijing Normal University, Beijing 100875 (China)

    2017-05-05

    Graphical abstract: Schematic of the preparation of RF supported catalysts and the reaction mechanism for SLD Fenton catalytic degradation of aqueous phenol. - Highlights: • Novel SLD Fenton catalyst was synthesized via in-situ induced self-assembly process. • RGO improved light-harvesting capacity and enhanced electro-transport performance. • Visible light irradiation accelerated reaction and extended operating pHs (4.0–8.0). • H{sub 2}O{sub 2} reduction and H{sub 2}O oxidation yielded ·OH in Fe{sup Ⅱ}/Fe{sup Ⅲ} and Fe{sup Ⅲ}/Fe{sup Ⅳ} cycling process. - Abstract: A novel solar-light-driven (SLD) Fenton catalyst was developed by reducing the ferrous-ion onto graphene oxide (GO) and forming reduced graphene oxide/α-FeOOH composites (RF) via in-situ induced self-assembly process. The RF was supported on several mesoporous supports (i.e., Al-MCM-41, MCM-41 and γ-Al{sub 2}O{sub 3}). The activity, stability and energy use for phenol oxidation were systematically studied for a wide pH range. Furthermore, the catalytic mechanism at acid and alkaline aqueous conditions was also elucidated. The results showed that Fe(II) was reduced onto GO nanosheets and α-FeOOH crystals were formed during the self-assembly process. Compared with Fenton reaction without SLD irradiation, the visible light irradiation not only dramatically accelerated the rate of Fenton-based reactions, but also extended the operating pH for the Fenton reaction (from 4.0 to 8.0). The phenol oxidation on RF supported catalysts was fitting well with the pseudo-first-order kinetics, and needed low initiating energy, insensitive to the reacting temperature changes (273–318 K). The Al-MCM-41 supported RF was a more highly energy-efficient catalyst with the prominent catalytic activity at wide operating pHs. During the reaction, ·OH radicals were generated by the SLD irradiation from H{sub 2}O{sub 2} reduction and H{sub 2}O oxidation in the Fe{sup Ⅱ}/Fe{sup Ⅲ} and Fe{sup Ⅲ}/Fe{sup

  5. Mechanistic insight into sonochemical biodiesel synthesis using heterogeneous base catalyst.

    Science.gov (United States)

    Choudhury, Hanif A; Chakma, Sankar; Moholkar, Vijayanand S

    2014-01-01

    The beneficial effect of ultrasound on transesterification reaction is well known. Heterogeneous (or solid) catalysts for biodiesel synthesis have merit that they do not contaminate the byproduct of glycerol. In this paper, we have attempted to identify the mechanistic features of ultrasound-enhanced biodiesel synthesis with the base-catalyst of CaO. A statistical design of experiments (Box-Behnken) was used to identify the influence of temperature, alcohol to oil molar ratio and catalyst loading on transesterification yield. The optimum values of these parameters for the highest yield were identified through Response Surface Method (with a quadratic model) and ANOVA. These values are: temperature=62 °C, molar ratio=10:1 and catalyst loading=6 wt.%. The activation energy was determined as 82.3 kJ/mol, which is higher than that for homogeneous catalyzed system (for both acidic and basic catalyst). The experimental results have been analyzed vis-à-vis simulations of cavitation bubble dynamics. Due to 3-phase heterogeneity of the system, the yield was dominated by intrinsic kinetics, and the optimum temperature for the highest yield was close to boiling point of methanol. At this temperature, the influence of cavitation bubbles (in terms of both sonochemical and sonophysical effect) is negligible, and ultrasonic micro-streaming provided necessary convection in the system. The influence of all parameters on the reaction system was found to be strongly inter-dependent. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Salicylic acid degradation by advanced oxidation processes. Coupling of solar photoelectro-Fenton and solar heterogeneous photocatalysis.

    Science.gov (United States)

    Garza-Campos, Benjamin; Brillas, Enric; Hernández-Ramírez, Aracely; El-Ghenymy, Abdellatif; Guzmán-Mar, Jorge Luis; Ruiz-Ruiz, Edgar J

    2016-12-05

    A 3.0 L solar flow plant with a Pt/air-diffusion (anode/cathode) cell, a solar photoreactor and a photocatalytic photoreactor filled with TiO2-coated glass spheres has been utilized to couple solar photoelectro-Fenton (SPEF) and solar heterogeneous photocatalysis (SPC) for treating a 165mgL(-1) salicylic acid solution of pH 3.0. Organics were destroyed by OH radicals formed on the TiO2 photocatalyst and at the Pt anode during water oxidation and in the bulk from Fenton's reaction between added Fe(2+) and cathodically generated H2O2, along with the photolytic action of sunlight. Poor salicylic acid removal and mineralization were attained using SPC, anodic oxidation with electrogenerated H2O2 (AO-H2O2) and coupled AO-H2O2-SPC. The electro-Fenton process accelerated the substrate decay, but with low mineralization by the formation of byproducts that are hardly destroyed by OH. The mineralization was strongly increased by SPEF due to the photolysis of products by sunlight, being enhanced by coupled SPEF-SPC due to the additional oxidation by OH at the TiO2 surface. The effect of current density on the performance of both processes was examined. The most potent SPEF-SPC process at 150mAcm(-2) yielded 87% mineralization and 13% current efficiency after consuming 6.0AhL(-1). Maleic, fumaric and oxalic acids detected as final carboxylic acids were completely removed by SPEF and SPEF-SPC. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. The modification of ion exchange heterogeneous catalysts for biodiesel synthesis

    Science.gov (United States)

    Hartono, R.; Mulia, B.; Sahlan, M.; Utami, T. S.; Wijanarko, Anondho; Hermansyah, Heri

    2017-03-01

    Conventionally, biodiesel is produced by using the homogeneous catalyst which has difficulty in high cost of the separation process. The heterogeneous catalysts ion exchange resin by its Solid phase can make an easier separation process, able to be reactivated and used repeatedly. In this research, the heterogeneous catalyst from various source such as Lewatit macro porous resin, Amberlite gel resin and natural zeolite bayah was investigated their performance to produced biodiesel from used cooking oil. Initially, the preparation of the ion exchange process with variations in time, temperature, the concentration of HCl and NaOH solution was investigated. Then, the activity of heterogeneous catalyst to produced biodiesel under the variation of stirring rate, zeolite particle size, and comparison of different ion exchange catalysts were also investigated. Finally, the stability test and regeneration treatment were also investigated. The optimum operating conditions of biodiesel synthesis process is at the temperature of 60 °C for 2 h with a stirring speed of 700 rpm. Natural zeolite Bayah with 6 M of NaOH solution produced 16.19%, Amberlite gel with 6 M HCL produced 65.22% of biodiesel yield and material Lewatit macro porous with 6 M of NaOH solution produced 85.94% as the maximum result. As the best result, Material Lewatit macro porous selected as the material which was used in the variation of stirring speed, temperature, and reaction time, the concentration of base and stability test. According to the results of analysis, calculations yield methyl oleic HPLC produced by Lewatit macro porous with 6 M NaOH at 62.95%.

  8. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Grass, Michael Edward [Univ. of California, Berkeley, CA (United States)

    2008-09-01

    Model heterogeneous catalysts have been synthesized and studied to better understand how the surface structure of noble metal nanoparticles affects catalytic performance. In this project, monodisperse rhodium and platinum nanoparticles of controlled size and shape have been synthesized by solution phase polyol reduction, stabilized by polyvinylpyrrolidone (PVP). Model catalysts have been developed using these nanoparticles by two methods: synthesis of mesoporous silica (SBA-15) in the presence of nanoparticles (nanoparticle encapsulation, NE) to form a composite of metal nanoparticles supported on SBA-15 and by deposition of the particles onto a silicon wafer using Langmuir-Blodgett (LB) monolayer deposition. The particle shapes were analyzed by transmission electron microscopy (TEM) and high resolution TEM (HRTEM) and the sizes were determined by TEM, X-ray diffraction (XRD), and in the case of NE samples, room temperature H2 and CO adsorption isotherms. Catalytic studies were carried out in homebuilt gas-phase reactors. For the nanoparticles supported on SBA-15, the catalysts are in powder form and were studied using the homebuilt systems as plug-flow reactors. In the case of nanoparticles deposited on silicon wafers, the same systems were operated as batch reactors. This dissertation has focused on the synthesis, characterization, and reaction studies of model noble metal heterogeneous catalysts. Careful control of particle size and shape has been accomplished though solution phase synthesis of Pt and Rh nanoparticles in order to elucidate further structure-reactivity relationships in noble metal catalysis.

  9. Theoretical Heterogeneous Catalysis: Scaling Relationships and Computational Catalyst Design.

    Science.gov (United States)

    Greeley, Jeffrey

    2016-06-07

    Scaling relationships are theoretical constructs that relate the binding energies of a wide variety of catalytic intermediates across a range of catalyst surfaces. Such relationships are ultimately derived from bond order conservation principles that were first introduced several decades ago. Through the growing power of computational surface science and catalysis, these concepts and their applications have recently begun to have a major impact in studies of catalytic reactivity and heterogeneous catalyst design. In this review, the detailed theory behind scaling relationships is discussed, and the existence of these relationships for catalytic materials ranging from pure metal to oxide surfaces, for numerous classes of molecules, and for a variety of catalytic surface structures is described. The use of the relationships to understand and elucidate reactivity trends across wide classes of catalytic surfaces and, in some cases, to predict optimal catalysts for certain chemical reactions, is explored. Finally, the observation that, in spite of the tremendous power of scaling relationships, their very existence places limits on the maximum rates that may be obtained for the catalyst classes in question is discussed, and promising strategies are explored to overcome these limitations to usher in a new era of theory-driven catalyst design.

  10. Ascorbate-Promoted Surface Iron Cycle for Efficient Heterogeneous Fenton Alachlor Degradation with Hematite Nanocrystals.

    Science.gov (United States)

    Huang, Xiaopeng; Hou, Xiaojing; Jia, Falong; Song, Fahui; Zhao, Jincai; Zhang, Lizhi

    2017-03-15

    This study reports the H2O2 activation with different hematite nanocrystals and ascorbate ions for the herbicide alachlor degradation at pH 5. We found that hematite nanoplates (HNPs) exposed with {001} facets exhibited better catalytic performance than hematite nanocubes (HNCs) exposed with {012} facets, which was attributed to the formation of inner-sphere iron-ascorbate complexes on the hematite facets. The 3-fold undercoordination Fe cations of {001} facet favors the formation of inner-sphere iron-ascorbate complexes, while the 5-fold undercoordination Fe cations of {012} facet has stereo-hindrance effect, disfavoring the complex formation. The surface area normalized alachlor degradation rate constant (23.3 × 10-4 min-1 L m-2) of HNPs-ascorbate Fenton system was about 2.6 times that (9.1 × 10-4 min-1 L m-2) of HNCs-ascorbate counterpart. Meanwhile, the 89.0% of dechlorination and 30.0% of denitrification in the HNPs-ascorbate Fenton system were also significantly higher than those (60.9% and 13.1%) of the HNCs-ascorbate one. More importantly, the reductive dissolution of hematite by ascorbate was strongly coupled with the subsequent H2O2 decomposition by surface bound ferrous ions through surface iron cycle on the hematite facets in the hematite-ascorbate Fenton systems. This coupling could significantly inhibit the conversion of surface bound ferrous ions to dissolved ones, and thus account for the stability of hematite nanocrystals. This work sheds light on the internal relationship between iron geochemical cycling and contaminants degradation, and also inspires us to utilize surface iron cycle of widely existent hematite for environmental remediation.

  11. Treatment of Actual Chemical Wastewater by a Heterogeneous Fenton Process Using Natural Pyrite

    OpenAIRE

    Liang Sun; Yan Li; Aimin Li

    2015-01-01

    Wastewater from chemical plants has remarkable antibiotic effects on the microorganisms in traditional biological treatment processes. An enhanced Fenton system catalyzed by natural pyrite was developed to degrade this kind of wastewater. Approximately 30% chemical oxygen demand (COD) was removed within 120 min when 50 mmol/L H2O2 and 10 g/L natural pyrite were used at initial pH from 1.8 to 7. A BOD5/COD enhancement efficiency of 210% and an acute biotoxicity removal efficiency of 84% were a...

  12. Iron oxide-mediated semiconductor photocatalysis vs. heterogeneous photo-Fenton treatment of viruses in wastewater. Impact of the oxide particle size.

    Science.gov (United States)

    Giannakis, Stefanos; Liu, Siting; Carratalà, Anna; Rtimi, Sami; Talebi Amiri, Masoud; Bensimon, Michaël; Pulgarin, César

    2017-10-05

    The photo-Fenton process is recognized as a promising technique towards microorganism disinfection in wastewater, but its efficiency is hampered at near-neutral pH operating values. In this work, we overcome these obstacles by using the heterogeneous photo-Fenton process as the default disinfecting technique, targeting MS2 coliphage in wastewater. The use of low concentrations of iron oxides in wastewater without H2O2 (wüstite, maghemite, magnetite) has demonstrated limited semiconductor-mediated MS2 inactivation. Changing the operational pH and the size of the oxide particles indicated that the isoelectric point of the iron oxides and the active surface area are crucial in the success of the process, and the possible underlying mechanisms are investigated. Furthermore, the addition of low amounts of Fe-oxides (1mgL-1) and H2O2 in the system (1, 5 and 10mgL-1) greatly enhanced the inactivation process, leading to heterogeneous photo-Fenton processes on the surface of the magnetically separable oxides used. Additionally, photo-dissolution of iron in the bulk, lead to homogeneous photo-Fenton, further aided by the complexation by the dissolved organic matter in the solution. Finally, we assess the impact of the presence of the bacterial host and the difference caused by the different iron sources (salts, oxides) and the Fe-oxide size (normal, nano-sized). Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Iron modified bentonite: Enhanced adsorption performance for organic pollutant and its regeneration by heterogeneous visible light photo-Fenton process at circumneutral pH

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Yaowen; Guo, Yongzhao; Zhang, Hui, E-mail: eeng@whu.edu.cn

    2016-01-25

    Highlights: • The iron modification markedly improved the adsorption performance of FeMB for RhB. • LED lamps emitting white light were employed as visible light source. • FeMB can be regenerated by visible light photo-Fenton process at circumneutral pH. • FeMB can be reused repeatedly after the heterogeneous photo-Fenton regeneration. - Abstract: Iron modified bentonite (FeMB) was prepared and used as an inexpensive adsorbent to rapidly remove organic pollutant (Rhodamine B, RhB) from aqueous solution. The iron modification significantly improved the adsorption performance of FeMB for RhB and permitted an easy separation of FeMB from the treated effluent. The equilibrium adsorption studies indicated that the dye molecules obeyed Langmuir type of adsorption with the calculated maximum adsorption capacity of 168.13 mg g{sup −1} for FeMB. The heterogeneous photo-Fenton process operated at circumneutral pH in the presence of visible light irradiation was found to be effective for the regeneration of the spent FeMB. Furthermore, the regeneration efficiency of as high as 79% was still achieved after 5 consecutive adsorption-regeneration cycles. Considering that, the visible light photo-Fenton approach could be applied as an excellent alternative for regenerating clay-based adsorbents by avoiding the use of dissolved iron salts.

  14. Preparation of nickel ferrite/carbon nanotubes composite by microwave irradiation technique for use as catalyst in photo-fenton reaction

    Energy Technology Data Exchange (ETDEWEB)

    Foletto, E.L.; Rigo, C.; Severo, E.C.; Mazutti, M.A.; Dotto, G.L.; Jahn, S.L.; Sales, J.C. [Universidade Federal de Santa Maria (UFSM), RS (Brazil); Chiavone-Filho, O. [Universidade Federal do Rio Grande do Sul (UFRGS), RS (Brazil); Gundel, A.; Lucchese, M. [Universidade Federal do Pampa (UNIPAMPA), Bage, RS (Brazil)

    2016-07-01

    Full text: Nickel ferrite/multi-walled carbon nanotubes (NiFe2O4/MWCNTs) composite has been rapidly synthesized via microwave irradiation technique. The structural properties of the formed product was investigated by X-ray diffraction (XRD), N2 adsorption/desorption isotherms, thermogravimetric analysis (TGA), Raman spectroscopy and, scanning electron microscopy (SEM). The catalytic behavior of composite material was evaluated by the degradation of Amaranth dye in the photo-Fenton reaction under visible light irradiation. The overall results showed that the prepared composite was successfully synthesized, demonstrating good performance in the dye degradation, with higher degradation rate compared to the NiFe2O4. The high efficiency in dye degradation can be attributed to synergism between NiFe2O4 and MWCNTs. Therefore, NiFe2O4/MWCNTs composite can be used as promising photo-Fenton catalyst to degrade Amaranth dye from aqueous solutions. (author)

  15. Adsorption-regeneration by heterogeneous Fenton process using modified carbon and clay materials for removal of indigo blue.

    Science.gov (United States)

    Almazán-Sánchez, Perla Tatiana; Solache-Ríos, Marcos J; Linares-Hernández, Ivonne; Martínez-Miranda, Verónica

    2016-01-01

    Indigo blue dye is mainly used in dyeing of denim clothes and its presence in water bodies could have adverse effects on the aquatic system; for this reason, the objective of this study was to promote the removal of indigo blue dye from aqueous solutions by iron and copper electrochemically modified clay and activated carbon and the saturated materials were regenerated by a Fenton-like process. Montmorillonite clay was modified at pH 2 and 7; activated carbon at pH 2 and pH of the system. The elemental X-ray dispersive spectroscopy analysis showed that the optimum pH for modification of montmorillonite with iron and copper was 7 and for activated carbon was 2. The dye used in this work was characterized by infrared. Unmodified and modified clay samples showed the highest removal efficiencies of the dye (90-100%) in the pH interval from 2 to 10 whereas the removal efficiencies decrease as pH increases for samples modified at pH 2. Unmodified clay and copper-modified activated carbon at pH 2 were the most efficient activated materials for the removal of the dye. The adsorption kinetics data of all materials were best adjusted to the pseudo-second-order model, indicating a chemisorption mechanism and the adsorption isotherms data showed that the materials have a heterogeneous surface. The iron-modified clay could be regenerated by a photo-Fenton-like process through four adsorption-regeneration cycles, with 90% removal efficiency.

  16. Heterogeneous photo-Fenton degradation of acid red B over Fe{sub 2}O{sub 3} supported on activated carbon fiber

    Energy Technology Data Exchange (ETDEWEB)

    Lan, Huachun [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences,China (China); Wang, Aiming [Department of Municipal and Environmental Engineering, School of Civil Engineering, Beijing Jiaotong University,China (China); Liu, Ruiping, E-mail: liuruiping@rcees.ac.cn [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences,China (China); Liu, Huijuan; Qu, Jiuhui [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences,China (China)

    2015-03-21

    Highlights: • Fe{sub 2}O{sub 3} with small particle size was highly dispersed on activated carbon fiber. • Fe{sub 2}O{sub 3}/ACF exhibited higher photo-Fenton activity toward ARB degradation. • Fe{sub 2}O{sub 3}/ACF has an excellent long-term stability without obvious deactivation. - Abstract: Fe{sub 2}O{sub 3} supported on activated carbon fiber (Fe{sub 2}O{sub 3}/ACF) was prepared via an impregnation method and characterized by X-ray diffraction, scanning electron microscopy and BET analysis. The results indicated that Fe{sub 2}O{sub 3} with small particle size was highly dispersed on the surface of the ACF and the introduction of Fe{sub 2}O{sub 3} did not change the ACF pore structure. Fe{sub 2}O{sub 3}/ACF exhibited a higher Fenton efficiency for the degradation of acid red B (ARB), especially under simulated solar irradiation. Complete decoloration of the ARB solution and 43% removal of TOC could be achieved within 200 min under optimal conditions. It was verified that more ·OH radicals were generated in the photo-assisted Fenton process and involved as active species in ARB degradation. FTIR analysis indicated that the degradation of ARB was initiated through the cleavage of −N=N−, followed by hydroxylation and opening of phenyl rings to form aliphatic acids, and further oxidation of aliphatic acids would produce CO{sub 2} and H{sub 2}O. Moreover, Fe{sub 2}O{sub 3}/ACF maintained its activity after being reused 4 times and the release of iron from the catalyst was found to be insignificant during the Fenton and photo-Fenton processes, indicating that Fe{sub 2}O{sub 3}/ACF had good long-term stability.

  17. Ultrasound assisted synthesis of methyl butyrate using heterogeneous catalyst.

    Science.gov (United States)

    Dange, P N; Kulkarni, A V; Rathod, V K

    2015-09-01

    Ultrasound assisted esterification of butyric acid with methanol was investigated in an ultrasound irradiated isothermal batch reactor using acid ion-exchange resin (amberlyst-15) as a catalyst. Effect of parameters such as temperature (323-353 K), catalyst loading (0-8.5%w/w), alcohol to acid ratio, M (2-6), ultrasound power (0-145 W), duty cycle (0-85%) and amount of molecular sieves added (0-11%w/w) on the rate of reaction was studied. At optimized parameters, a maximum conversion of 91.64% was obtained in 120 min in presence of ultrasound. Experimental kinetic data were correlated by using Eley-Rideal (ER) and Langmuir-Hinshelwood-Hougen-Watson (LHH W) models taking into account reverse reaction. Studies showed that single site LHHW with reactants and products both adsorbing on catalyst surface was most suited for the obtained experimental data. Activation energy determined based on heterogeneous kinetics was in the range 49.31-57.54 kJ/mol while it was 18.29 kJ/mol using homogeneous model. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Production of Catalyst-Free Hyperpolarised Ethanol Aqueous Solution via Heterogeneous Hydrogenation with Parahydrogen

    National Research Council Canada - National Science Library

    Salnikov, Oleg G; Kovtunov, Kirill V; Koptyug, Igor V

    2015-01-01

    An experimental approach for the production of catalyst-free hyperpolarised ethanol solution in water via heterogeneous hydrogenation of vinyl acetate with parahydrogen and the subsequent hydrolysis...

  19. A ''well-known'' advanced oxidation reaction revisited. The photo-Fenton-oxidation of 4-chlorophenol and 2,4-dichloro-phenol in a homogeneous and a heterogeneous system

    Energy Technology Data Exchange (ETDEWEB)

    Rios-Enriquez, M.A.; Bossmann, S.H.; Oliveros, E.; Shahin, N.; Braun, A.M. [Lehrstuhl fuer Umweltmesstechnik, am Engler-Bunte Inst. der Univ. Karlsruhe (Germany); Duran-de-Bazua, C. [Facultad de Quimica, Univ. Nacional Autonoma de Mexico (Mexico)

    2003-07-01

    The oxidative degradation of 4-chlorophenol and 2,4-dichlorophenol by the thermal and photochemically enhanced Fenton reactions has served as a model reaction for the comparison of different reaction conditions. The process of dechlorination of the chlorinated phenols is generally monitored by the determination of the chloride anion by ion chromatography. Some authors even proposed the measurement of the released chloride as a convenient measure for the advancement of Fenton reactions of reaction mixtures occurring in the environment. Therefore, we revisited these ''well-known'' reactions and combined mechanistic investigations of the formed chemical intermediates by GC-mass spectroscopy with the determinations of thorough chloride balances. This mechanistic tool was further employed for the comparison of the homogeneous and the heterogeneous photochemically enhanced Fenton degradation of 4-chlorophenol and 2,4-dichlorophenol. A mixture of ferric sulphate and hydrogen peroxide was employed for the homogeneous Fenton reactions, whereas the heterogeneous Fenton experiments were performed using an iron(III)-exchanged zeolite Y photocatalyst. Different reaction pathways for the homogenous and heterogeneous (photo)Fenton reactions and especially for the oxidative degradation of 4-chlorophenol and 2,4-dichlorophenol were observed. Consequences for the comparison of different operating conditions of (photo)Fenton processes are discussed. (orig.)

  20. Effect of heterogeneous catalyst during combustion of diesel fuel

    Science.gov (United States)

    Arefeen, Quamrul

    1999-11-01

    With the increase in number of vehicles using diesel engines, the contributions to environmental pollution made by diesel engines is also on the rise. Carbon monoxide, oxides of nitrogen and sulfur, hydrocarbons, and particulates are currently regulated as harmful emissions from diesel engines. Recent technologies to control harmful engine emissions have been almost exclusively directed towards gasoline engines. It is generally held that fuel quality will have to play an important role with all IC engines to meet future stringent regulations. The objective of the present study was to determine the effects of heterogeneous catalyst on combustion. Micron sized solid catalyst, suspended in a specific organic peroxide, has been found to promote better combustion by modifying kinetics and changing the thermodynamics of the reactions. The catalyst reduces emissions without dramatically changing the properties of the fuel. The characteristic parameters of a baseline fuel, and the same fuel with the additive, were analyzed. The dosage of additive used was found to be compatible with commercial diesel. Diesel vehicles were driven unloaded at normal road conditions during the experiments. Exhaust emissions were measured when the trucks were at static conditions and the engine running on idle and at 2000 rpm. The gaseous components in the exhaust, O2, CO2, CO, NO, NO2, NOx, SO2, and CxH y were monitored. Particulates were trapped on a pre-weighed glass filter. Some of the filters were sent to an independent laboratory for microscopic and elemental analysis of the collected debris. Zinc oxide/peroxide suspended in tert-butyl hydro peroxide were used as the heterogeneous fuel catalyst. This combination increased the cetane rating of a commercial diesel fuel from 45 to a level of 70 depending on treatment ratio. A treatment ratio of one ounce additive per 5 gallons of diesel increased cetane number by an average of 5 points. Road mileage with the additive increased by an average

  1. Synergetic Effect of Ultrasound, the Heterogeneous Fenton Reaction and Photocatalysis by TiO2 Loaded on Nickel Foam on the Degradation of Pollutants

    Science.gov (United States)

    Qiu, Shan; Xu, Shanwen; Li, Guangming; Yang, Jixian

    2016-01-01

    The synergistic effect of ultrasound, the heterogeneous Fenton reaction and photocatalysis was studied using a nickel foam (NF)-supporting TiO2 system and rhodamine B (RhB) as a target. The NF-supporting TiO2 system was prepared by depositing TiO2 on the skeleton of NF repeatedly and then calcining it. To optimize the conditions and parameters, the catalytic activity was tested in four systems (ultrasound alone (US), nickel foam (NF), US/NF and NF/US/H2O2). The optimal conditions were fixed at 0.1 g/mL NF, initial 5.00 mg/L RhB, 300 W ultrasonic power, pH = 3 and 5.00 mg/L H2O2. The effects of the dissolution of nickel from NF and quenching of the Fenton reaction were studied on degradation efficiency. When the heterogeneous Fenton reaction is combined with TiO2-photocatalysis, the pollutant removal efficiency is enhanced significantly. Through this synergistic effect, 22% and 80% acetochlor was degraded within 10 min and 80 min, respectively. PMID:28773580

  2. Synergetic Effect of Ultrasound, the Heterogeneous Fenton Reaction and Photocatalysis by TiO₂ Loaded on Nickel Foam on the Degradation of Pollutants.

    Science.gov (United States)

    Qiu, Shan; Xu, Shanwen; Li, Guangming; Yang, Jixian

    2016-06-08

    The synergistic effect of ultrasound, the heterogeneous Fenton reaction and photocatalysis was studied using a nickel foam (NF)-supporting TiO₂ system and rhodamine B (RhB) as a target. The NF-supporting TiO₂ system was prepared by depositing TiO₂ on the skeleton of NF repeatedly and then calcining it. To optimize the conditions and parameters, the catalytic activity was tested in four systems (ultrasound alone (US), nickel foam (NF), US/NF and NF/US/H₂O₂). The optimal conditions were fixed at 0.1 g/mL NF, initial 5.00 mg/L RhB, 300 W ultrasonic power, pH = 3 and 5.00 mg/L H₂O₂. The effects of the dissolution of nickel from NF and quenching of the Fenton reaction were studied on degradation efficiency. When the heterogeneous Fenton reaction is combined with TiO₂-photocatalysis, the pollutant removal efficiency is enhanced significantly. Through this synergistic effect, 22% and 80% acetochlor was degraded within 10 min and 80 min, respectively.

  3. Heterogeneous Fenton-like degradation of methylene blue (MB) by magnetic nanoparticles Fe3O4@TiO2 in neutral condition

    Science.gov (United States)

    Hua, Junfeng; Huang, Mei

    2017-09-01

    The traditional Fenton system (Fe2+–H2O2) only works in an acidic environment and produces a large quantity of sludge. In this study, magnetic nanoparticles Fe3O4@TiO2 were used as a high-performance Fenton-like catalyst for the degradation of MB. The surface morphology was characterized by Transmission Electron Microscopy (TEM). And the Fenton-like catalytic activity of Fe3O4@TiO2 was evaluated under different pH condition and various H2O2 in feed concentration, respectively. The results indicated that nanoparticles Fe3O4@TiO2 show high efficiency for methylene blue (MB) degradation under the reaction condition of H2O2 40mM, Fe3O4@TiO2 20mM, MB 300mg/L, pH 7 and 30 °C, the mineralization of persistent MB can achieve 72% COD removal ratio.

  4. UV-VIS-NIR spectroscopy and microscopy of heterogeneous catalysts.

    Science.gov (United States)

    Schoonheydt, Robert A

    2010-12-01

    This critical review article discusses the characterization of heterogeneous catalysts by UV-VIS-NIR spectroscopy and microscopy with special emphasis on transition metal ion containing catalysts. A review is given of the transitions, that can be observed in the UV-VIS-NIR region and the peculiarities of catalytic solids that have to be taken into account. This is followed by a short discussion of the techniques that have been developed over the years: diffuse reflectance spectroscopy, UV-VIS microscopy, in situ or operando spectroscopy, the combination of UV-VIS spectroscopy with other spectroscopic techniques, with chemometrics and with quantum chemistry. In the third part of this paper four successes of UV-VIS-NIR spectroscopy and microscopy are discussed; (1) coordination of transition metal ions to surface oxygens; (2) quantitative determination of the oxidation states of transition metal ions; (3) characterization of active sites and (4) study of the distribution of transition metal ions and carbocations in catalytic bodies, particles and crystals (104 references).

  5. An Erbium-Based Bifuctional Heterogeneous Catalyst: A Cooperative Route Towards C-C Bond Formation

    Directory of Open Access Journals (Sweden)

    Manuela Oliverio

    2014-07-01

    Full Text Available Heterogeneous bifuctional catalysts are multifunctional synthetic catalysts enabling efficient organic transformations by exploiting two opposite functionalities without mutual destruction. In this paper we report the first Er(III-based metallorganic heterogeneous catalyst, synthesized by post-calcination MW-assisted grafting and modification of the natural aminoacid L-cysteine. The natural acid–base distance between sites was maintained to assure the cooperation. The applicability of this new bifunctional heterogeneous catalyst to C-C bond formation and the supposed mechanisms of action are discussed as well.

  6. Facile preparation of magnetic mesoporous Fe{sub 3}O{sub 4}/C/Cu composites as high performance Fenton-like catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Li, Keyan; Zhao, Yongqin [State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China); Janik, Michael J. [Department of Chemical Engineering, The Pennsylvania State University, University Park, PA 16802 (United States); Song, Chunshan [State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China); EMS Energy Institute, PSU-DUT Joint Center for Energy Research and Department of Energy & Mineral Engineering, The Pennsylvania State University, University Park, PA 16802 (United States); Guo, Xinwen, E-mail: guoxw@dlut.edu.cn [State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China)

    2017-02-28

    , cheap and green method for the synthesis of mesoporous composites as excellent Fenton-like catalysts, without any additional reductants or organic surfactants.

  7. EPR approaches to heterogeneous catalysis. The chemistry of titanium in heterogeneous catalysts and photocatalysts.

    Science.gov (United States)

    Morra, Elena; Giamello, Elio; Chiesa, Mario

    2017-07-01

    Paramagnetic species are often involved in catalytic or photocatalytic reactions occurring at the solid-gas interface of heterogeneous catalysts. In this contribution we will provide an overview of the wealth and breadth of information that can be obtained from EPR in the characterization of paramagnetic species in such systems, illustrating the advantages that modern pulsed EPR methodologies can offer in monitoring the elementary processes occurring within the coordination sphere of surface transition-metal ions. To do so we selected three representative systems, where titanium ions in low oxidation states act as active catalytic sites, trying to outline the methodological approaches which characterize the application of EPR techniques and the questions that can be answered and addressed relative to the characterization of heterogeneous catalytic materials. Copyright © 2017 Elsevier Inc. All rights reserved.

  8. EPR approaches to heterogeneous catalysis. The chemistry of titanium in heterogeneous catalysts and photocatalysts

    Science.gov (United States)

    Morra, Elena; Giamello, Elio; Chiesa, Mario

    2017-07-01

    Paramagnetic species are often involved in catalytic or photocatalytic reactions occurring at the solid-gas interface of heterogeneous catalysts. In this contribution we will provide an overview of the wealth and breadth of information that can be obtained from EPR in the characterization of paramagnetic species in such systems, illustrating the advantages that modern pulsed EPR methodologies can offer in monitoring the elementary processes occurring within the coordination sphere of surface transition-metal ions. To do so we selected three representative systems, where titanium ions in low oxidation states act as active catalytic sites, trying to outline the methodological approaches which characterize the application of EPR techniques and the questions that can be answered and addressed relative to the characterization of heterogeneous catalytic materials.

  9. Degradation of Anthraquinone Dye Reactive Blue 4 in Pyrite Ash Catalyzed Fenton Reaction

    Directory of Open Access Journals (Sweden)

    Milena Becelic-Tomin

    2014-01-01

    Full Text Available Pyrite ash (PA is created by burning pyrite in the chemical production of sulphuric acid. The high concentration of iron oxide, mostly hematite, present in pyrite ash, gives the basis for its application as a source of catalytic iron in a modified Fenton process for anthraquinone dye reactive blue 4 (RB4 degradation. The effect of various operating variables such as catalyst and oxidant concentration, initial pH and RB4 concentration on the abatement of total organic carbon, and dye has been assessed in this study. Here we show that degradation of RB4 in the modified Fenton reaction was efficient under the following conditions: pH=2.5; [PA]0=0.2 g L−1; [H2O2]0=5 mM and initial RB4 concentration up to 100 mg L−1. The pyrite ash Fenton reaction can overcome limitations observed from the classic Fenton reaction, such as the early termination of the Fenton reaction. Metal (Pb, Zn, and Cu content of the solution after the process suggests that an additional treatment step is necessary to remove the remaining metals from the water. These results provide basic knowledge to better understand the modified, heterogeneous Fenton process and apply the PA Fenton reaction for the treatment of wastewaters which contains anthraquinone dyes.

  10. Computationally Probing the Performance of Hybrid, Heterogeneous, and Homogeneous Iridium-Based Catalysts for Water Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    García-Melchor, Max [SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford CA (United States); Vilella, Laia [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST),Tarragona (Spain); Departament de Quimica, Universitat Autonoma de Barcelona, Barcelona (Spain); López, Núria [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Tarragona (Spain); Vojvodic, Aleksandra [SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park CA (United States)

    2016-04-29

    An attractive strategy to improve the performance of water oxidation catalysts would be to anchor a homogeneous molecular catalyst on a heterogeneous solid surface to create a hybrid catalyst. The idea of this combined system is to take advantage of the individual properties of each of the two catalyst components. We use Density Functional Theory to determine the stability and activity of a model hybrid water oxidation catalyst consisting of a dimeric Ir complex attached on the IrO2(110) surface through two oxygen atoms. We find that homogeneous catalysts can be bound to its matrix oxide without losing significant activity. Hence, designing hybrid systems that benefit from both the high tunability of activity of homogeneous catalysts and the stability of heterogeneous systems seems feasible.

  11. Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

    Directory of Open Access Journals (Sweden)

    Shouyun Cheng

    2016-12-01

    Full Text Available The massive consumption of fossil fuels and associated environmental issues are leading to an increased interest in alternative resources such as biofuels. The renewable biofuels can be upgraded from bio-oils that are derived from biomass pyrolysis. Catalytic cracking and hydrodeoxygenation (HDO are two of the most promising bio-oil upgrading processes for biofuel production. Heterogeneous catalysts are essential for upgrading bio-oil into hydrocarbon biofuel. Although advances have been achieved, the deactivation and regeneration of catalysts still remains a challenge. This review focuses on the current progress and challenges of heterogeneous catalyst application, deactivation, and regeneration. The technologies of catalysts deactivation, reduction, and regeneration for improving catalyst activity and stability are discussed. Some suggestions for future research including catalyst mechanism, catalyst development, process integration, and biomass modification for the production of hydrocarbon biofuels are provided.

  12. Comparison of Ethylene/1-Hexene Copolymers Microstructures Synthesized by Homogeneous and Heterogeneous Metallocene Catalysts

    Directory of Open Access Journals (Sweden)

    Saeid Ahmadjo

    2013-05-01

    Full Text Available The substituted (bis-2-PhIndZrCl2 and non-substituted (bis-IndZrCl2 indenylbased metallocene catalysts were synthesized and used in homogenous and heterogeneous forms for copolymerization of ethylene and 1-hexene. The MCM-41 nano silica was used as support in heterogenization of the catalysts. The substituted (bis-2-PhIndZrCl2 metallocene catalyst in homogenous and heterogeneous forms showed lower activities in comparison to non-substituted (bis-IndZrCl2 metallocene catalyst. The microstructures of the obtained copolymers were investigated by techniques such as DSC, CNMR and TRRF. The kinetic study showed that the decay index (DI was decreased for both homogeneous catalysts due to unstable kinetic behaviors. However, the decay index contents approached one, using heterogeneous forms of catalyst which was an indication of stable kinetic behaviors. The kinetic results also displayed negative effect on the catalysts activities both in the homogeneous and heterogeneous forms by addition of comonomer on the polymerization. The triad distributions of obtained polymer by NMR technique exhibited the higher ratio of EEH, EHE, EEE triads than the other triads. The comonomer incorporationacceptability of substituted metallocene catalyst (bis-2-PhIndZrCl2 was higher than non-substituted catalyst (bis-IndZrCl2 as its comonomer acceptability increased from 1.3% to 5.4% by substitution mechanism. Microstructures of copolymers obtained by supported metallocene catalyst showed more non-uniform comonomer distribution in comparison with unsupported catalyst. The lamella thickness distributions for polymer obtained by supported substituted metallocene catalyst (bis-2-PhIndZrCl2 were in the ranges (3-8 . However, for supported metallocene non-substituted catalysts (bis-IndZrCl2 the lamella thickness were in the ranges (3-16 .

  13. Synthesis of magnetic porous Fe3O4/C/Cu2O composite as an excellent photo-Fenton catalyst under neutral condition.

    Science.gov (United States)

    Chai, Fanfan; Li, Keyan; Song, Chunshan; Guo, Xinwen

    2016-08-01

    Magnetic porous Fe3O4/C/Cu2O composites were prepared by a simple two-step process. Porous Fe3O4/C was synthesized via calcining iron tartrate precursor and then Cu2O was composited with Fe3O4/C by a precipitation-reduction method. The as-prepared samples were characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) elemental mapping. Results show that Fe3O4/C has porous nanorod structure, which is composed of numerous small nanoparticles of about 50nm. Fe3O4 and carbon are uniformly distributed in the Fe3O4/C/Cu2O composite and Cu2O is dispersed on the surface of Fe3O4/C. Fe3O4/C/Cu2O composite exhibits excellent photo-Fenton catalytic performance for the degradation of methylene blue (MB) under visible light irradiation and neutral pH conditions, and MB (100mg/L) could be almost completely removed within 60min. The composite shows good recyclability and could be conveniently separated by an applied magnetic field. These results demonstrate that the Fe3O4/C/Cu2O composite is a powerful Fenton-like catalyst for degradation of organic pollutants from wastewater. Copyright © 2015 Elsevier Inc. All rights reserved.

  14. Biodiesel production from waste cooking oil using a heterogeneous catalyst from pyrolyzed rice husk.

    Science.gov (United States)

    Li, Ming; Zheng, Yan; Chen, Yixin; Zhu, Xifeng

    2014-02-01

    A solid acid catalyst was prepared by sulfonating pyrolyzed rice husk with concentrated sulfuric acid, and the physical and chemical properties of the catalyst were characterized in detail. The catalyst was then used to simultaneously catalyze esterification and transesterification to produce biodiesel from waste cooking oil (WCO). In the presence of the as-prepared catalyst, the free fatty acid (FFA) conversion reached 98.17% after 3h, and the fatty acid methyl ester (FAME) yield reached 87.57% after 15 h. By contrast, the typical solid acid catalyst Amberlyst-15 obtained only 95.25% and 45.17% FFA conversion and FAME yield, respectively. Thus, the prepared catalyst had a high catalytic activity for simultaneous esterification and transesterification. In addition, the catalyst had excellent stability, thereby having potential use as a heterogeneous catalyst for biodiesel production from WCO with a high FFA content. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Activities of Heterogeneous Acid-Base Catalysts for Fragrances Synthesis: A Review

    Directory of Open Access Journals (Sweden)

    Hartati Hartati

    2013-06-01

    Full Text Available This paper reviews various types of heterogeneous acid-base catalysts for fragrances preparation. Catalytic activities of various types of heterogeneous acid and base catalysts in fragrances preparation, i.e. non-zeolitic, zeolitic, and mesoporous molecular sieves have been reported. Generally, heterogeneous acid catalysts are commonly used in fragrance synthesis as compared to heterogeneous base catalysts. Heteropoly acids and hydrotalcites type catalysts are widely used as heterogeneous acid and base catalysts, respectively. © 2013 BCREC UNDIP. All rights reservedReceived: 20th January 2013; Revised: 31st March 2013; Accepted: 1st April 2013[How to Cite: Hartati, H., Santoso, M., Triwahyono, S., Prasetyoko, D. (2013. Activities of Heterogeneous Acid-Base Catalysts for Fragrances Synthesis: A Review. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (1: 14-33. (doi:10.9767/bcrec.8.1.4394.14-33][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.1.4394.14-33] | View in  |

  16. Molecular-level Design of Heterogeneous Chiral Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gellman, Andrew John [Carnegie Mellon University; Sholl, David S. [Georgia Institute of Technology; Tysoe, Wilfred T. [University of Wisconsin - Milwaukee; Zaera, Francisco [University of California at Riverside

    2013-04-28

    Understanding and controlling selectivity is one of the key challenges in heterogeneous catalysis. Among problems in catalytic selectivity enantioselectivity is perhaps the most the most challenging. The primary goal of the project on “Molecular-level Design of Heterogeneous Chiral Catalysts” is to understand the origins of enantioselectivity on chiral heterogeneous surfaces and catalysts. The efforts of the project team include preparation of chiral surfaces, characterization of chiral surfaces, experimental detection of enantioselectivity on such surfaces and computational modeling of the interactions of chiral probe molecules with chiral surfaces. Over the course of the project period the team of PI’s has made some of the most detailed and insightful studies of enantioselective chemistry on chiral surfaces. This includes the measurement of fundamental interactions and reaction mechanisms of chiral molecules on chiral surfaces and leads all the way to rationale design and synthesis of chiral surfaces and materials for enantioselective surface chemistry. The PI’s have designed and prepared new materials for enantioselective adsorption and catalysis. Naturally Chiral Surfaces • Completion of a systematic study of the enantiospecific desorption kinetics of R-3-methylcyclohexanone (R-3-MCHO) on 9 achiral and 7 enantiomeric pairs of chiral Cu surfaces with orientations that span the stereographic triangle. • Discovery of super-enantioselective tartaric acid (TA) and aspartic acid (Asp) decomposition as a result of a surface explosion mechanism on Cu(643)R&S. Systematic study of super-enantiospecific TA and Asp decomposition on five enantiomeric pairs of chiral Cu surfaces. • Initial observation of the enantiospecific desorption of R- and S-propylene oxide (PO) from Cu(100) imprinted with {3,1,17} facets by L-lysine adsorption. Templated Chiral Surfaces • Initial observation of the enantiospecific desorption of R- and S-PO from Pt(111) and Pd(111

  17. Intracluster atomic and electronic structural heterogeneities in supported nanoscale metal catalysts

    NARCIS (Netherlands)

    Elsen, A.; Jung, U.; Vila, F.; Li, Y.; Safonova, O.V.; Thomas, R.; Tromp, M.; Rehr, J.J.; Nuzzo, R.G.; Frenkel, A.I.

    2015-01-01

    This work reveals and quantifies the inherent intracluster heterogeneity in the atomic structure and charge distribution present in supported metal catalysts. The results demonstrate that these distributions are pronounced and strongly coupled to both structural and dynamic perturbations. They also

  18. Quantification of a Heterogeneous Ruthenium Catalyst on Carbon-black using ADF Imaging

    Science.gov (United States)

    Varambhia, A. M.; Jones, L.; Nellist, P. D.; Lozano-Perez, S.; Ozkaya, D.

    2015-10-01

    Using recent developments in ADF quantification techniques, we utilise a rapid atom counting procedure to document the evolution of a heterogeneous ruthenium catalyst on carbon black. Selected areas of the ruthenium catalyst were imaged for approximately 15 minutes. The imaged areas show that the Ru wets the support forming a thin amorphous layer that transforms to a crystalline layer under beam irradiation.

  19. A heterogeneous catalyst, SiO₂-ZnBr₂: An efficient neat access for ...

    Indian Academy of Sciences (India)

    ... Volume 128; Issue 8. A heterogeneous catalyst, SiO₂-ZnBr₂: An efficient neat access for α-aminophosphonates and antimicrobial activity evaluation ... The catalyst, SiO₂-ZnBr₂ afforded good yields of products in all the methods in the range of 85–97% but variation was observed in reaction time. Microwave irradiation ...

  20. Catalysts and conditions for the highly efficient, selective and stable heterogeneous oligomerisation of ethylene

    CSIR Research Space (South Africa)

    Heveling, J

    1998-10-11

    Full Text Available The oligomerisation of ethylene into products in the C-4-C-20 range over heterogeneous nickel catalysts in a fixed-bed reactor at low temperature and high pressure (LT-HP) is reported. The catalysts were obtained by Ni (II) exchange or impregnation...

  1. Controlled reduction of red mud waste to produce active systems for environmental applications: heterogeneous Fenton reaction and reduction of Cr(VI).

    Science.gov (United States)

    Costa, Regina C C; Moura, Flávia C C; Oliveira, Patrícia E F; Magalhães, Fabiano; Ardisson, José D; Lago, Rochel M

    2010-02-01

    In this work, controlled reduction of red mud with H(2) was used to produce active systems for two different environmental applications, i.e. the heterogeneous Fenton reaction and the reduction of Cr(VI). Mössbauer, powder X-ray diffraction, thermal analyses and scanning electron microscopy analyses showed that at different temperatures, i.e. 300, 400, 500 and 600 degrees C, H(2) reduces red mud to different phases, mainly Fe(3)O(4), Fe(0)/Fe(3)O(4) and Fe(0). These Fe phases are dispersed on Al, Si and Ti oxides present in the red mud and show high reactivity towards two environmental applications, i.e. the heterogeneous Fenton reaction and the reduction of Cr(VI). Reduction with H(2) at 400 degrees C showed the best results for the oxidation of the model dye methylene blue with H(2)O(2) at neutral pH due to the presence of the composite Fe(0)/Fe(3)O(4). The reduced red mud at 500-600 degrees C produced Fe(0) highly active for the reduction of Cr(VI) in aqueous medium. Another feature of these red mud based system is that after deactivation due to extensive use they can be completely regenerated by simple treatment with H(2). Copyright (c) 2009 Elsevier Ltd. All rights reserved.

  2. Solid acid catalysts in heterogeneous n-alkanes hydroisomerisation ...

    African Journals Online (AJOL)

    Both solid and gaseous acid modifiers could similarly modify their textural characteristics. The activities of all catalysts could under uncontrolled conditions lead to side reactions such as cracking, aromatisation and dehydrogenation. Keywords; Solid acids, n-alkanes, hydroisomerisation catalysts, gasoline, octane number.

  3. Productions of sunflower oil biodiesel and used cooking oil through heterogeneous catalysts compared to conventional homogeneous catalysts

    Science.gov (United States)

    Gutiérrez-Zapata, C. A.; Blanco Martínez, D.; Collazos, C. A.; Castellanos Acuña, H. E.; Cuervo, J. A.; Fernandez, C. P.

    2017-01-01

    This document compares homogeneous and heterogeneous catalysts used by production of biodiesel of sunflower oil and cooking oil used in frying. For this, NaOH was used as a catalyst homogeneous, and K2CO3 and Na2CO3 supported in gamma-alumina (K2CO3/γ Al2O3 y Na2CO3 /γ-Al2O3) were synthesized as heterogeneous catalysts, which were characterized by X-ray diffraction. The transesterification tests were carried out for the sunflower oil and used cooking oil, in a reflux system, to different molar relations methanol/oil, depending on the type of oil and characterization of the same. The reflux system is performed at a temperature of 55-60°C for one hour. Finally, biofuel was characterized and the yield of the reaction was calculated.

  4. Synergistic effect of UV pretreated Fe-ZSM-5 catalysts for heterogeneous catalytic complete oxidation of VOC: A technology development for sustainable use.

    Science.gov (United States)

    Aziz, Abdul; Kim, Kwang Soo

    2017-10-15

    In this work, the performance of benzene, toluene, ethylbenzene, and xylene (BTEX) removal and degradation from gas, air streams on UV pretreated Fe-ZSM-5 in a batch reactor at room temperature were studied. The Fe-ZSM-5 zeolite catalyst was prepared by hydrothermal reaction method. The influence of UV pre-irradiation time on the removal of BTEX were assessed by varying the time, ranging from 15min to 60smin. Then, sustainability of the activation of the catalyst resulted by UV pretreatment was studied by the four-cycle experiment with one time UV irradiation and after each cycle irradiation followed by BTEX removal after every cycle respectively. The results of BTEX removal depicted that 30min of UV pretreatment was sufficient for complete organics removal. The UV pretreatment effect on the catalytic oxidation and the stability of the catalyst were studied by modern instrumental techniques. The novelty of the process was the sustainable reuse of catalyst with persistent VOC removal, which works on the -adsorption-oxidation-regeneration-adsorption- cycle, which was confirmed by the characterization studies of the catalyst after four runs. The results revealed that the change in the structure, stability, morphology, and removal efficiency of the catalyst during the experiments was negligible. The VOC degradation mechanism studies showed that the oxidation occurs due to the formation of free radicals as well as hydroxyl ions, so named it heterogeneous photo-Fenton oxidation. The residual materials analysis showed the complete mineralization of VOC except small amount of acetone as oxidation product. Lastly, the kinetics of the VOC removal was studied. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. The generation of efficient supported (Heterogeneous) olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Grubbs, Robert H

    2013-04-05

    Over the past decade, a new family of homogeneous metathesis catalysts has been developed that will tolerate most organic functionalities as well as water and air. These homogeneous catalysts are finding numerous applications in the pharmaceutical industry as well as in the production of functional polymers. In addition the catalysts are being used to convert seed oils into products that can substitute for those that are now made from petroleum products. Seed oils are unsaturated, contain double bonds, and are a ready source of linear hydrocarbon fragments that are specifically functionalized. To increase the number of applications in the area of biomaterial conversion to petrol chemicals, the activity and efficiency of the catalysts need to be as high as possible. The higher the efficiency of the catalysts, the lower the cost of the conversion and a larger number of practical applications become available. Active supported catalysts were prepared and tested in the conversion of seed oils and other important starting materials. The outcome of the work was successful and the technology has been transferred to a commercial operation to develop viable applications of the discovered systems. A biorefinery that converts seed oils is under construction in Indonesia. The catalysts developed in this study will be considered for the next generation of operations.

  6. Nano copper and cobalt ferrites as heterogeneous catalysts for the ...

    Indian Academy of Sciences (India)

    trisubstituted imidazoles using magnetic recyclable spinel nano copper and cobalt ferrites by the condensation of benzil, aromatic aldehyde and ammonium acetate in ethanol as solvent. The reaction, with these catalysts was carried out under mild ...

  7. Tannic acid- and natural organic matter-coated magnetite as green Fenton-like catalysts for the removal of water pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Nadejde, C., E-mail: claudianadejde@gmail.com; Neamtu, M., E-mail: mariana.neamtu@uaic.ro [‘Alexandru Ioan Cuza’ University, Interdisciplinary Research Department – Field Science (Romania); Hodoroaba, V.-D.; Schneider, R. J.; Paul, A. [BAM Federal Institute for Materials Research and Testing (Germany); Ababei, G. [National Institute of Research and Development for Technical Physics (Romania); Panne, U. [BAM Federal Institute for Materials Research and Testing (Germany)

    2015-12-15

    The use of magnetic materials as heterogeneous catalysts has attracted increasing attention in the last years since they proved to be promising candidates for water treatment. In the present study, two types of surface-modified magnetite (Fe{sub 3}O{sub 4}) nanoparticles, coated with non-hazardous naturally occurring agents—either tannic acid (TA) or dissolved natural organic matter—were evaluated as magnetic heterogeneous catalysts. Chemical synthesis (co-precipitation) was chosen to yield the nanocatalysts due to its well-established simplicity and efficiency. Subsequently, the properties of the final products were fully assessed by various characterization techniques. The catalytic activity in heterogeneous oxidation of aqueous solutions containing a model pollutant, Bisphenol A (BPA), was comparatively studied. The effect of operational parameters (catalyst loading, H{sub 2}O{sub 2} dosage, and UV light irradiation) on the degradation performance of the oxidation process was investigated. The optimum experimental parameters were found to be 1.0 g/L of catalysts and 10 mM H{sub 2}O{sub 2}, under UV irradiation. The highest mineralization rates were observed for Fe{sub 3}O{sub 4}-TA catalyst. More than 80 % of BPA was removed after 30 min of reaction time under the specified experimental conditions. The obtained results showed that the two catalysts studied here are suitable candidates for the removal of pollutants in wastewaters by means of heterogeneous reaction using a green sustainable treatment method.

  8. Iron modified bentonite: Enhanced adsorption performance for organic pollutant and its regeneration by heterogeneous visible light photo-Fenton process at circumneutral pH.

    Science.gov (United States)

    Gao, Yaowen; Guo, Yongzhao; Zhang, Hui

    2016-01-25

    Iron modified bentonite (FeMB) was prepared and used as an inexpensive adsorbent to rapidly remove organic pollutant (Rhodamine B, RhB) from aqueous solution. The iron modification significantly improved the adsorption performance of FeMB for RhB and permitted an easy separation of FeMB from the treated effluent. The equilibrium adsorption studies indicated that the dye molecules obeyed Langmuir type of adsorption with the calculated maximum adsorption capacity of 168.13 mg g(-1) for FeMB. The heterogeneous photo-Fenton process operated at circumneutral pH in the presence of visible light irradiation was found to be effective for the regeneration of the spent FeMB. Furthermore, the regeneration efficiency of as high as 79% was still achieved after 5 consecutive adsorption-regeneration cycles. Considering that, the visible light photo-Fenton approach could be applied as an excellent alternative for regenerating clay-based adsorbents by avoiding the use of dissolved iron salts. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. A conceptual translation of homogeneous catalysis into heterogeneous catalysis: homogeneous-like heterogeneous gold nanoparticle catalyst induced by ceria supporter.

    Science.gov (United States)

    Li, Zhen-Xing; Xue, Wei; Guan, Bing-Tao; Shi, Fu-Bo; Shi, Zhang-Jie; Jiang, Hong; Yan, Chun-Hua

    2013-02-07

    Translation of homogeneous catalysis into heterogeneous catalysis is a promising solution to green and sustainable development in chemical industry. For this purpose, noble metal nanoparticles represent a new frontier in catalytic transformations. Many challenges remain for researchers to transform noble metal nanoparticles of heterogeneous catalytic active sites into ionic species of homogeneous catalytic active sites. We report here a successful design on translating homogeneous gold catalysis into a heterogeneous system with a clear understanding of the catalytic pathway. This study initiates a novel concept to immobilize a homogeneous catalyst based on electron transfer between supporting base and supported nanoparticles. Meanwhile, on the basis of theoretical calculation, it has deepened the understanding of the interactions between noble metal nanoparticles and the catalyst support.

  10. Synthesis of iron/GAC catalyst for wastewater treatment using ...

    Indian Academy of Sciences (India)

    38, No. 4, August 2015, pp. 1039–1042. c Indian Academy of Sciences. Synthesis of iron/GAC catalyst for wastewater treatment using heterogeneous Fenton reaction. STTLE1,2, T T NGO3, W KHANITCHAIDECHA1,2 and A NAKARUK4,5,∗. 1Department of Civil Engineering, Faculty of Engineering, Naresuan University, ...

  11. Dynamic Chemical and Structural Changes of Heterogeneous Catalysts Observed in Real Time: From Catalysis-Induced Fluxionality to Catalytic Cycles

    Science.gov (United States)

    2014-11-26

    Changes of Heterogeneous Catalysts Observed in Real Time: From Catalysis -Induced Fluxionality to Catalytic Cycles” (FA9550-12-1-0204) Robert M. Rioux...report The results from “Dynamic Chemical and Structural Changes of Heterogeneous Catalysts Observed in Real Time: From Catalysis -Induced...AFRL-OSR-VA-TR-2014-0321 Dynamic Chemical and Structural Changes of Heterogeneous Catalysts Robert Rioux PENNSYLVANIA STATE UNIVERSITY Final Report

  12. Removal of pharmaceuticals from water by homo/heterogonous Fenton-type processes - A review.

    Science.gov (United States)

    Mirzaei, Amir; Chen, Zhi; Haghighat, Fariborz; Yerushalmi, Laleh

    2017-05-01

    The presence of emerging contaminants such as pharmaceuticals in natural waters has raised increasing concern due to their frequent appearance and persistence in the aquatic ecosystem and the threat to health and safety of aquatic life, even at trace concentrations. Conventional water treatment processes are known to be generally inadequate for the elimination of these persistent contaminants. Therefore, the use of advanced oxidation processes (AOPs) which are able to efficiently oxidize organic pollutants has attracted a great amount of attention. The main limitation of AOPs lies in their high operating costs associated with the consumption of energy and chemicals. Fenton-based processes, which utilize nontoxic and common reagents and potentially can exploit solar energy, will considerably reduce the removal cost of recalcitrant contaminants. The disadvantages of homogeneous Fenton processes, such as the generation of high amounts of iron-containing sludge and limited operational range of pH, have prompted much attention to the use of heterogeneous Fenton processes. In this review, the impacts of some controlling parameters including the H2O2 and catalyst dosage, solution pH, initial contaminants concentrations, temperature, type of catalyst, intensity of irradiation, reaction time and feeding mode on the removal efficiencies of hetero/homogeneous Fenton processes are discussed. In addition, the combination of Fenton-type processes with biological systems as the pre/post treatment stages in pilot-scale operations is considered. The reported experimental results obtained by using Fenton and photo-Fenton processes for the elimination of pharmaceutical contaminants are also compiled and evaluated. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Tunable Heterogeneous Catalysis: N-Heterocyclic Carbenes as Ligands for Supported Heterogeneous Ru/K-Al2O3 Catalysts To Tune Reactivity and Selectivity.

    Science.gov (United States)

    Ernst, Johannes B; Muratsugu, Satoshi; Wang, Fei; Tada, Mizuki; Glorius, Frank

    2016-08-31

    Here we report, for the first time, an extensive characterization of an N-heterocyclic carbene (NHC)-modified supported heterogeneous catalyst. The existence of the metal-carbene bond could be proven by (13)C-SS-NMR experiments. Furthermore, it could be shown that the modification with NHCs does not structurally change the catalyst itself. The effect of the nature and the loading of the NHC on the activity and selectivity of the heterogeneous catalyst is presented by a hydrogenation study, finally leading to an NHC-enabled tunable heterogeneous catalyst for chemoselective hydrogenation.

  14. Review of Heterogeneous Catalysts for Catalytically Upgrading Vegetable Oils into Hydrocarbon Biofuels

    Directory of Open Access Journals (Sweden)

    Xianhui Zhao

    2017-03-01

    Full Text Available To address the issues of greenhouse gas emissions associated with fossil fuels, vegetable oilseeds, especially non-food oilseeds, are used as an alternative fuel resource. Vegetable oil derived from these oilseeds can be upgraded into hydrocarbon biofuel. Catalytic cracking and hydroprocessing are two of the most promising pathways for converting vegetable oil to hydrocarbon biofuel. Heterogeneous catalysts play a critical role in those processes. The present review summarizes current progresses and remaining challenges of vegetable oil upgrading to biofuel. The catalyst properties, applications, deactivation, and regeneration are reviewed. A comparison of catalysts used in vegetable oil and bio-oil upgrading is also carried out. Some suggestions for heterogeneous catalysts applied in vegetable oil upgrading to improve the yield and quality of hydrocarbon biofuel are provided for further research in the future.

  15. Effect of heterogeneous Fenton-like pre-treatment on anaerobic granular sludge performance and microbial community for the treatment of traditional Chinese medicine wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Su, Chengyuan, E-mail: suchengyuan2008@126.com [School of Environment and Resources, Guangxi Normal University, 15 Yucai Road, Guilin 541004 (China); School of Municipal and Environmental Engineering, Harbin Institute of Technology, 73 Huanghe Road, Harbin 150090 (China); Li, Weiguang [School of Municipal and Environmental Engineering, Harbin Institute of Technology, 73 Huanghe Road, Harbin 150090 (China); Lu, Yuxiang; Chen, Menglin; Huang, Zhi [School of Environment and Resources, Guangxi Normal University, 15 Yucai Road, Guilin 541004 (China)

    2016-08-15

    Highlights: • Rhein has metabolic or physiological toxicity on methanogens in anaerobic granular sludge. • TCM wastewater containing rhein can be successfully treated by the combined treatment. • The productions of the EPS of granular sludge increased after pre-treatment. • Methanoregula, Methanobacterium, Methanosphaerula were predominant in the DC reactor after pre-treatment. - Abstract: The effect of a heterogeneous Fenton-like pre-treatment on the anaerobic processes, characteristics and microbial community of sludge was investigated for traditional Chinese medicine (TCM) wastewater containing rhein. When the concentrations of rhein were 50 mg/L and 100 mg/L, the toxic effect was physiological toxicity for anaerobic granular sludge. Using a single double circle (DC) reactor for the treatment of TCM wastewater containing rhein at concentrations of 15–20 mg/L, the chemical oxygen demand (COD) removal rate was 69%, and coenzyme F{sub 420} was nearly undetectable in the 3D-excitation-emission matrix (EEM) spectra of soluble microbial products (SMP). The abundances of Methanoregula, Methanobacterium, Methanosphaerula were only 5.57%, 2.39% and 1.08% in the DC reactor, respectively. TCM wastewater containing rhein could be successfully treated by the combination of the heterogeneous Fenton-like pre-treatment and the DC reactor processes, and the COD removal rate reached 95%. Meanwhile, the abundances of Methanoregula, Methanobacterium, Methanosphaerula increased to 22.5%, 18.5%, and 13.87%, respectively. For the bacterial community, the abundance of Acidobacteria-Gp6 decreased from 6.99% to 1.07%, while the abundances of Acidobacteria-Gp1 and Acidobacteria-Gp2 increased from 1.61% to 6.55% and from 1.28% to 5.87%, respectively.

  16. Turning a Cr-based heterogeneous ethylene polymerisation catalyst into a selective ethylene trimerisation catalyst

    NARCIS (Netherlands)

    Nenu, N.C.; Bodart, P.; Weckhuysen, B.M.

    2007-01-01

    A Phillips Cr/SiO2 polymerisation catalyst was converted into an ethylene trimerisation catalyst after assembling new active sites on the silica surface in the presence of TAC (1,3,5-triphenylhexahydro 1,3,5-triazacyclohexane) as ligand and CH2Cl2 as solvent. The reaction conditions play a role in

  17. Application of Electro-Fenton Technology to Remediation of Polluted Effluents by Self-Sustaining Process

    Directory of Open Access Journals (Sweden)

    Maria Ángeles Fernández de Dios

    2014-01-01

    Full Text Available The applicability of electro-Fenton technology to remediation of wastewater contaminated by several organic pollutants such as dyes and polycyclic aromatic hydrocarbons has been evaluated using iron-enriched zeolite as heterogeneous catalyst. The electro-Fenton technology is an advanced oxidation process that is efficient for the degradation of organic pollutants, but it suffers from the high operating costs due to the need for power investment. For this reason, in this study microbial fuel cells (MFCs were designed in order to supply electricity to electro-Fenton processes and to achieve high treatment efficiency at low cost. Initially, the effect of key parameters on the MFC power generation was evaluated. Afterwards, the degradation of Reactive Black 5 dye and phenanthrene was evaluated in an electro-Fenton reactor, containing iron-enriched zeolite as catalyst, using the electricity supplied by the MFC. Near complete dye decolourization and 78% of phenanthrene degradation were reached after 90 min and 30 h, respectively. Furthermore, preliminary reusability tests of the developed catalyst showed high degradation levels for successive cycles. The results permit concluding that the integrated system is adequate to achieve high treatment efficiency with low electrical consumption.

  18. A multicomponent assembly approach for the design of deep desulfurization heterogeneous catalysts.

    Science.gov (United States)

    Xu, Yanqi; Xuan, Weimin; Zhang, Mengmeng; Miras, Haralampos N; Song, Yu-Fei

    2016-12-06

    Deep desulfurization is a challenging task and global efforts are focused on the development of new approaches for the reduction of sulfur-containing compounds in fuel oils. In this work, we have proposed a new design strategy for the development of deep desulfurization heterogeneous catalysts. Based on the adopted design strategy, a novel composite material of polyoxometalate (POM)-based ionic liquid-grafted layered double hydroxides (LDHs) was synthesized by an exfoliation/grafting/assembly process. The structural properties of the as-prepared catalyst were characterized using FT-IR, XRD, TG, NMR, XPS, BET, SEM and HRTEM. The heterogeneous catalyst exhibited high activity in deep desulfurization of DBT (dibenzothiophene), 4,6-DMDBT (4,6-dimethyldibenzothiophene) and BT (benzothiophene) at 70 °C in 25, 30 and 40 minutes, respectively. The catalyst can be easily recovered and reused at least ten times without obvious decrease of its catalytic activity. Such excellent sulfur removal ability as well as the cost efficiency of the novel heterogeneous catalyst can be attributed to the rational design, where the spatial proximity of the substrate and the active sites, the immobilization of ionic liquid onto the LDHs via covalent bonding and the recyclability of the catalyst are carefully considered.

  19. Acetic Acid Formation by Selective Aerobic Oxidation of Aqueous Ethanol over Heterogeneous Ruthenium Catalysts

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Hanning, Christopher William

    2012-01-01

    Heterogeneous catalyst systems comprising ruthenium hydroxide supported on different carrier materials, titania, alumina, ceria, and spinel (MgAl2O4), were applied in selective aerobic oxidation ethanol to form acetic acid, an important bulk chemical and food ingredient. The catalysts were...... of catalysts, oxidant pressure, reaction temperature, and substrate concentration were investigated. Quantitative yield of acetic acid was obtained with 1.2 wt % Ru(OH)x/CeO2 under optimized conditions (150 °C, 10 bar O2, 12 h of reaction time, 0.23 mol % Ru to substrate)....

  20. Competitive transesterification of soybean oil with mixed methanol/ethanol over heterogeneous catalysts.

    Science.gov (United States)

    Kim, M; Yan, S; Salley, S O; Ng, K Y S

    2010-06-01

    Methylesters and ethylesters of fatty acids were synthesized using homogeneous CH(3)ONa and CH(3)CH(2)ONa, anion exchanged resin, and CaO-La(2)O(3) catalysts. Methanol, ethanol, and methanol/ethanol mixtures were used as the alcohol feed for transesterification of soybean oil. With a homogeneous catalyst (CH(3)ONa) there was essentially no difference in conversion rates between methanolysis and ethanolysis in batch reactions. However, with a heterogeneous resin and CaO-La(2)O(3) catalysts, significant differences in the conversion rates between the methanolysis and ethanolysis were observed. The formation rate of methylesters over a CaO-La(2)O(3) catalyst was higher than that of ethylesters, which may be attributable to a steric hindrance effect. Conversely, with a heterogeneous resin catalyst, the conversion rate of ethylester was higher than that of methylesters which may be attributable to the surface hydrophobicity of the anion exchanged resin. When the transesterification of soybean oil was carried out with an equimolar methanol/ethanol mixture, the yield ratio of methylester to ethylester formed within the first 30 min was 2.6 for the homogeneous catalyst (0.3% CH(3)ONa), and 3.4 for the heterogeneous CaO-La(2)O(3)catalyst. These differences in selectivity are likely due to both the higher reactivity of methoxide and to a steric hindrance effect of ethoxide on the catalyst surface. In addition, the transformation of methylester to ethylester was observed when a methanol/ethanol mixture was used. (c) 2010. Published by Elsevier Ltd. All rights reserved.

  1. The catalytic activity of the iron-coated pumice particles used as heterogeneous catalysts in the oxidation of natural organic matter by H2O2.

    Science.gov (United States)

    Alver, Alper; Karaarslan, Mihrican; Kılıç, Ahmet

    2016-08-01

    The oxidative removal of natural organic matter (NOM) from waters was investigated by hydrogen peroxide (H2O2) and iron-coated pumice particles in heterogeneous catalytic oxidation process (HCOP). Removal of trihalomethane (THM) precursors, which is formed THM by the reacts with chloride, was performed with the hydroxyl radicals. Coating the original pumice particles with iron oxides significantly enhanced the removal of NOM with peroxide. The studies were carried out in two sections: (1) decomposition of hydrogen peroxide in pure water with iron-coated pumice and (2) oxidation of THM Precursor (NOM) by hydrogen peroxide with iron-coated pumice. The monitored parameters in this study include dissolved organic carbon and trihalomethanes formation potential. The results show that iron-coated pumice catalyst significantly increased the removal efficiency of NOM in the HCOP. The results show that iron-coated pumice catalyst significantly increased the removal efficiency of NOM in the HCOP. Results show that the oxidation of NOM and remaining NOM with H2O2 is improved by the addition of iron-coated pumice particles which activate the H2O2 molecule, leading to the formation of hydroxyl radicals in a Fenton-like process.

  2. Homogeneous and heterogeneous catalysts of Fe3+, Co2+ and Cu2+ for the degradation of methyl parathion in diluted aqueous medium

    Directory of Open Access Journals (Sweden)

    Cindy A. Vela-Monroy

    2016-07-01

    Full Text Available Degradation of pesticides (plaguicides, herbicides, fungicides, among others in aqueous media is a subject of great importance for ensuring the water quality into numerous hydric sources. This work reports the assessment of homogeneous (metal ion solutions and heterogeneous (oxides supported on alumina systems that are based on Fe3+, Co2+ y Cu2+, which were used as catalysts for oxidation (degradation of methyl parathion (a plaguicide in aqueous solution. Hydrogen peroxide was herein used as oxidizing molecule under mild condition of reaction (25 ºC and atmospheric pressure. The solids were characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM. Fe3+/H2O2 (Fenton system was the most active homogeneous catalyst compared to Co2+/H2O2 and Cu2+/H2O2 systems. Solids catalysts such as cobalt, copper or iron oxides as well as mixed oxides supported on alumina were active at pH close to neutrality. Fe-Co-Cu/Al2O3, Co-Cu/Al2O3 and FeCo/Al2O3 mixed systems were solids with the highest catalytic activity. In addition, an important effect of the support (-Al2O3 on the reaction pH was observed, allowing to reach values close to that of the neutrality, and thus increasing the catalytic activity of both cobalt oxide and copper oxide species. These results allow advancing on a new pathway for searching catalysts to remove organophosphorous pesticides from residual waters.

  3. Heterogeneous sono-Fenton-like process using martite nanocatalyst prepared by high energy planetary ball milling for treatment of a textile dye.

    Science.gov (United States)

    Dindarsafa, Mahsa; Khataee, Alireza; Kaymak, Baris; Vahid, Behrouz; Karimi, Atefeh; Rahmani, Amir

    2017-01-01

    High energy planetary ball milling was applied to prepare sono-Fenton nanocatalyst from natural martite (NM). The NM samples were milled for 2-6h at the speed of 320rpm for production of various ball milled martite (BMM) samples. The catalytic performance of the BMMs was greater than the NM for treatment of Acid Blue 92 (AB92) in heterogeneous sono-Fenton-like process. The NM and the BMM samples were characterized by XRD, FT-IR, SEM, EDX and BET analyses. The particle size distribution of the 6h-milled martite (BMM3) was in the range of 10-90nm, which had the highest surface area compared to the other samples. Then, the impact of main operational parameters was investigated on the process. Complete removal of the dye was obtained at the desired conditions including initial pH 7, 2.5g/L BMM3 dosage, 10mg/L AB92 concentration, and 150W ultrasonic power after 30min of treatment. The treatment process followed pseudo-first order kinetic. Environmentally-friendly modification of the NM, low leached iron amount and repeated application at milder pH were the significant benefits of the BMM3. The GC-MS was successfully used to identify the generated intermediates. Eventually, an artificial neural network (ANN) was applied to predict the AB92 removal efficiency based upon the experimental data with a proper correlation coefficient (R(2)=0.9836). Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Conversion of Sugars to Lactic Acid Derivatives Using Heterogeneous Zeotype Catalysts

    DEFF Research Database (Denmark)

    Holm, Martin Spangsberg; Shunmugavel, Saravanamurugan; Taarning, Esben

    2010-01-01

    of mono-and disaccharides that are dissolved in methanol to methyl lactate at 160 C. With sucrose as the substrate, methyl lactate yield reaches 68%, and the heterogeneous catalyst can be easily recovered by filtration and reused multiple times after calcination without any substantial change...

  5. PROCESS FOR HYDROGENOLYSIS OF ALPHA-HYDROXY ESTERS OR ACIDS USING A HETEROGENEOUS CATALYST

    DEFF Research Database (Denmark)

    2017-01-01

    The present invention relates to a method for hydrogenolysis of alpha-hydroxy esters or acids, comprising reacting the alpha-hydroxy ester or acid in the presence of a heterogeneous catalyst. The present invention also relates to a method for producing propionic acid ester, and the use of any...

  6. Nano-TiCl4/SiO2: an efficient heterogeneous solid acid catalyst for ...

    Indian Academy of Sciences (India)

    Mirjalili

    Nano-TiCl4/SiO2: an efficient heterogeneous solid acid catalyst for the one pot cascade five-component synthesis of densely functionalized tetrahydropyridines. ABDOLHAMID BAMONIRIa,*, BI BI FATEMEH MIRJALILIb and REZA TARAZIANa. aDepartment of Organic Chemistry, Faculty of Chemistry, University of Kashan, ...

  7. Nano-TiCl4/SiO2: An efficient heterogeneous solid acid catalyst for ...

    Indian Academy of Sciences (India)

    Abstract. Nano-TiCl4/SiO2 was found to be an inexpensive and efficient heterogeneous solid acid catalyst for the synthesis of one-pot cascade synthesis of highly functionalized asymmetric tetrahydropyridines from the five-component condensation reaction of the para-substituted anilines and aromatic aldehydes with ethyl.

  8. Direct aerobic oxidation of primary alcohols to methyl esters catalyzed by a heterogeneous gold catalyst

    DEFF Research Database (Denmark)

    Nielsen, Inger Staunstrup; Taarning, Esben; Egeblad, Kresten

    2007-01-01

    Methyl esters can be produced in high yield by oxidising methanolic solutions of primary alcohols with dioxygen over a heterogeneous gold catalyst. The versatility of this new methodology is demonstrated by the fact that alkylic, benzylic and allylic alcohols, as well as alcohols containing...... an amine functionality are oxidized in good to excellent yield....

  9. Application of Heterogeneous Catalysts in the First Steps of the Oseltamivir Synthesis

    Directory of Open Access Journals (Sweden)

    José M. Fraile

    2017-12-01

    Full Text Available The first steps of oseltamivir synthesis from quinic acid involve acetalization and ester formation. These reactions are catalyzed by either acids or bases, which may be accomplished by heterogeneous catalysts. Sulfonic solids are efficient acid catalysts for acetalization and esterification reactions. Supported tetraalkylammonium hydroxide or 1,5,7-triazabicyclo[4.4.0]dec-5-ene are also efficient base catalysts for lactone alcoholysis and in this work, these catalysts have been applied in two alternative synthetic routes that lead to oseltamivir. The classical route consists of an acetalization, followed by a lactonization, and then a lactone alcoholysis. This achieves a 66% isolated yield. The alternative route consists of esterification followed by acetalization and is only efficient when an acetone acetal is used.

  10. Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

    Science.gov (United States)

    Ramprasad, Dorai; Waller, Francis Joseph

    1999-01-01

    This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

  11. Chitosan as a Natural Polymer for Heterogeneous Catalysts Support: A Short Review on Its Applications

    Directory of Open Access Journals (Sweden)

    Mengshan Lee

    2015-11-01

    Full Text Available Chitosan, a bio-based polymer which has similar characteristics to those of cellulose, exhibits cationic behavior in acidic solutions and strong affinity for metals ions. Thus, it has received increased attention for the preparation of heterogeneous catalysts. Recent studies demonstrated that chitosan-based catalysts had high sorption capacities, chelating activities, stability and versatility, which could be potentially applied as green reactants in various scientific and engineering applications. This study intends to review the recent development of chitosan-based catalysts, particularly in the aspects of the main mechanisms for preparing the materials and their applications in environmental green chemistry. Studies on the preparation of catalyst nanoparticles/nanospheres supported on chitosan were also reviewed.

  12. Heterogeneous photo-Fenton processes using graphite carbon coating hollow CuFe2O4 spheres for the degradation of methylene blue

    Science.gov (United States)

    Guo, Xiaojun; Wang, Kebai; Li, Dai; Qin, Jiabin

    2017-10-01

    The novel graphite carbon coating hollow CuFe2O4 spheres were fabricated through solvothermal method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectra, etc. The catalytic performance of the graphite carbon coating hollow CuFe2O4 spheres was evaluated in photo-Fenton-like degradation of methylene blue (MB) using H2O2 as a green oxidant under light irradiation (λ > 400 nm). The results demonstrated that the hollow CuFe2O4 spheres with graphite carbon coating exhibited superior catalytic activity. In the preparation process of catalyst, the addition of glucose was very important to its catalytic performance. Photoresponse analysis of the typical samples proved that CuFe2O4@graphite carbon core-shell hollow spheres possessed excellent photocurrent response and lower electrochemical impedance. In addition, a possible mechanism for photocatalytic degradation of MB had been presumed. Moreover, after five regeneration cycles, the graphite carbon coating hollow CuFe2O4 spheres still exhibited better properties.

  13. Screening, optimization and kinetics of Jatropha curcas oil transesterification with heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zanette, Andreia F.; Barella, Rodrigo A.; Silva, Edson A. [Department of Chemical Engineering, Universidade Estadual do Oeste do Parana, Toledo (Brazil); Pergher, Sibele B.C.; Treichel, Helen; Oliveira, Debora; Mazutti, Marcio A.; Oliveira, J. Vladimir [Department of Food Engineering, URI, Campus de Erechim, CEP 99700-000, Erechim (Brazil)

    2011-02-15

    This work investigates the production of fatty acid methyl esters (FAME) from Jatropha curcas oil using a variety of heterogeneous catalysts: resins, zeolites, clays, hydrotalcites, aluminas and niobium oxide. For this purpose, a catalyst screening was first conducted in a batch reactor at the following operating conditions: oil to methanol molar ratio of 1:9, 6 h of reaction, 5 wt% catalyst, at 333 and 393 K. From the screening step, KSF clay and Amberlyst 15 catalysts were selected to carry out a 2{sup 3} full factorial central composite rotatable design so as to elucidate the effects of process variables on FAME yield. The optimum reaction conditions for both catalysts were found to be oil to methanol molar ratio of 1:12, 5 wt% of catalyst, 433 K and 6 h of reaction with a FAME yield of about 70 wt%. A kinetic study was then experimentally performed and a semi-empirical model was built to represent the experimental data. Finally, catalyst re-utilization in five successive batch experiments was evaluated at the optimized conditions. (author)

  14. Synthesis of ternary g-C3N4/Ag/γ-FeOOH photocatalyst: An integrated heterogeneous Fenton-like system for effectively degradation of azo dye methyl orange under visible light

    Science.gov (United States)

    He, Donglin; Chen, Yanfeng; Situ, Yue; Zhong, Li; Huang, Hong

    2017-12-01

    g-C3N4/Ag/γ-FeOOH photocatalyst was prepared and the synergy of photocatalysis with heterogeneous Fenton-like process was measured by degrading methyl Orange(MO). g-C3N4 can apply electron for γ-FeOOH to change Fe3+ to Fe2+, and γ-FeOOH can help g-C3N4 to enhance the absorption of visible light. The Ag nanoparticles were photo deposited on the layer of γ-FeOOH and g-C3N4 for the separation of electron-holes. g-C3N4(5%)/Ag/γ-FeOOH showed the great ability to degrade MO, and the optimal concentration of H2O2, the effect of pH and the stability of the photocatalyst and synergistic mechanism of photocatalysity with heterogeneous Fenton-like process were also discussed in this study.

  15. Synthesis of biodiesel from pongamia oil using heterogeneous ion-exchange resin catalyst.

    Science.gov (United States)

    Jaya, N; Selvan, B Karpanai; Vennison, S John

    2015-11-01

    Biodiesel is a clean-burning renewable substitute fuel for petroleum. Biodiesel could be effectively produced by transesterification reaction of triglycerides of vegetable oils with short-chain alcohols in the presence of homogeneous or heterogeneous catalysts. Conventionally, biodiesel manufacturing processes employ strong acids or bases as catalysts. But, separation of the catalyst and the by-product glycerol from the product ester is too expensive to justify the product use as an automobile fuel. Hence heterogeneous catalysts are preferred. In this study, transesterification of pongamia oil with ethanol was performed using a solid ion-exchange resin catalyst. It is a macro porous strongly basic anion exchange resin. The process parameters affecting the ethyl ester yield were investigated. The reaction conditions were optimized for the maximum yield of fatty acid ethyl ester (FAEE) of pongamia oil. The properties of FAEE were compared with accepted standards of biodiesel. Engine performance was also studied with pongamia oil diesel blend and engine emission characteristics were observed. Copyright © 2015 Elsevier Inc. All rights reserved.

  16. Coumarin Derivatives Solvent-Free Synthesis under Microwave Irradiation over Heterogeneous Solid Catalysts

    Directory of Open Access Journals (Sweden)

    Souad Bouasla

    2017-11-01

    Full Text Available A suitable methodology of synthesis of coumarin derivatives by Pechmann reaction over heterogeneous solid acid catalysts in a free solvent media under microwave irradiation is described. Resorcinol, phenol and ethyl acetoacetate were selected as model reactants in the Pechmann condensation. The catalytic activity of several materials—Amberlyst-15, zeolite β and sulfonic acid functionalized hybrid silica—in solvent-free microwave-assisted synthesis of the corresponding coumarin derivatives has been investigated in detail. 7-Hydroxy-4-methylcoumarin and 4-methylcoumarin were obtained in 97% and 43% yields, respectively, over Amberlyst-15. This was the most active catalyst in the Pechmann reaction under studied conditions.

  17. Optimization Study in Biodiesel Production via Response Surface Methodology Using Dolomite as a Heterogeneous Catalyst

    OpenAIRE

    Santos, Regina C. R.; Vieira, Rômulo B.; Valentini, Antoninho

    2014-01-01

    A carbonate mineral, dolomite, was used as a heterogeneous catalyst to produce methyl-esters from soybean oil. The samples were analyzed by XRF, TGA, XRD, TPD-CO2, and SEM. The calcination of dolomite at 800°C/1 h resulted in a highly active mixed metal oxides. In addition, the influence of the reaction variables such as the temperature, catalyst amount, and methanol/soybean oil molar ratio in methyl-ester production was optimized by the application of a central composite design in conjunctio...

  18. Environmentally benign heterogeneous nano-particle catalysts: synthesis, characterization and catalytic activity of 4-nitrophenol.

    Science.gov (United States)

    Murugan, Eagambaram; Jebaranjitham, J Nimita

    2011-02-01

    Pollution free catalyst is an attractive area of current interest. The p-Aminophenol is one of the most significant catalyst, because it involves the manufacture of various pharmaceuticals. Crosslinked poly(styrene)-co-poly(4-vinylimidazole) (PSPVIM) was prepared by varying the crosslinked monomer ratio as 2% and 10% respectively. The 2 (w%) of DVB, 25 (w%) of N-VIm as functional monomer and 73 (w%) of styrene as support monomer as organic phase and gelatin, boric acid and polyvinyl alcohol as aqueous phase was used to prepare cross-linked poly(styrene)-co-poly(N-vinyl imidazole) (PVIM) beads (Type-I). Similarly, Type II beads were also prepared by fixing the 10% as a cross linking ratio (DVB). The immobilization of Ag NPs onto the PS-VIm polymer matrix was performed using AgNO3 as a metal precursor solution. The k(obs) determined from UV-Vis results, reveals that the degree of reduction of 4-nitrophenol using Type-I catalysts is more effective than Type-II catalyst due to lower immobilization of AgNPs at higher cross-linked bead matrix. It was found that on increasing the amount of catalyst i.e., type-I PS-PVIm-AgNPs, the rate constant also increases. Therefore, PS-PVIm-AgNPs (Type-I) heterogeneous catalyst is superior for the reduction of 4-NP.

  19. C-C Coupling on Single-Atom-Based Heterogeneous Catalyst.

    Science.gov (United States)

    Zhang, Xiaoyan; Sun, Zaicheng; Wang, Bin; Tang, Yu; Nguyen, Luan; Li, Yuting; Tao, Franklin Feng

    2018-01-24

    Compared to homogeneous catalysis, heterogeneous catalysis allows for ready separation of products from the catalyst and thus reuse of the catalyst. C-C coupling is typically performed on a molecular catalyst which is mixed with reactants in liquid phase during catalysis. This homogeneous mixing at a molecular level in the same phase makes separation of the molecular catalyst extremely challenging and costly. Here we demonstrated that a TiO 2 -based nanoparticle catalyst anchoring singly dispersed Pd atoms (Pd 1 /TiO 2 ) is selective and highly active for more than 10 Sonogashira C-C coupling reactions (R≡CH + R'X → R≡R'; X = Br, I; R' = aryl or vinyl). The coupling between iodobenzene and phenylacetylene on Pd 1 /TiO 2 exhibits a turnover rate of 51.0 diphenylacetylene molecules per anchored Pd atom per minute at 60 °C, with a low apparent activation barrier of 28.9 kJ/mol and no cost of catalyst separation. DFT calculations suggest that the single Pd atom bonded to surface lattice oxygen atoms of TiO 2 acts as a site to dissociatively chemisorb iodobenzene to generate an intermediate phenyl, which then couples with phenylacetylenyl bound to a surface oxygen atom. This coupling of phenyl adsorbed on Pd 1 and phenylacetylenyl bound to O ad of TiO 2 forms the product molecule, diphenylacetylene.

  20. Efficient Absorption of Antibiotic from Aqueous Solutions over MnO2@SA/Mn Beads and Their In Situ Regeneration by Heterogeneous Fenton-Like Reaction

    Directory of Open Access Journals (Sweden)

    Yu Luo

    2017-01-01

    Full Text Available Alginate has been extensively used as absorbents due to its excellent properties. However, the practical application of pure alginate has been restricted since the saturated adsorbent has weak physical structure and could not be regenerated easily. In this study, a low-cost and renewable composite MnO2@alginate/Mn adsorbent has been prepared facilely for the absorptive removal of antibiotic wastewater. FE-SEM, FTIR, and XRD analyses were used to characterize the samples. The norfloxacin (NOR was used as an index of antibiotics. More specifically, the batch absorption efficiency of the adsorbents was evaluated by pH, contact time with different NOR concentration, and the temperature. Thus, the performance of absorption kinetic dynamics and isotherm equations were estimated for the adsorptive removal process. Parameters including ΔG0, ΔH0, and ΔS0 were utilized to describe the feasible adsorption process. To regenerate the saturated absorptive sites of the adsorbent, the heterogeneous Fenton-like reactions were trigged by introduction of H2O2. The results showed that the in situ regenerating has exhibited an excellent recycling stability. The high activity and the simple fabrication of the adsorbents make them attractive for the treatment of wastewater containing refractory organic compound and also provide fundamental basis and technology for further practical application.

  1. Biodiesel production from non-edible Silybum marianum oil using heterogeneous solid base catalyst under ultrasonication.

    Science.gov (United States)

    Takase, Mohammed; Chen, Yao; Liu, Hongyang; Zhao, Ting; Yang, Liuqing; Wu, Xiangyang

    2014-09-01

    The aim of this study is to investigate modified TiO2 doped with C4H4O6HK as heterogeneous solid base catalyst for transesterification of non-edible, Silybum marianum oil to biodiesel using methanol under ultrasonication. Upon screening the catalytic performance of modified TiO2 doped with different K-compounds, 0.7 C4H4O6HK doped on TiO2 was selected. The preparation of the catalyst was done using incipient wetness impregnation method. Having doped modified TiO2 with C4H4O6HK, followed by impregnation, drying and calcination at 600 °C for 6 h, the catalyst was characterized by XRD, FTIR, SEM, BET, TGA, UV and the Hammett indicators. The yield of the biodiesel was proportional to the catalyst basicity. The catalyst had granular and porous structures with high basicity and superior performance. Combined conditions of 16:1 molar ratio of methanol to oil, 5 wt.% catalyst amount, 60 °C reaction temperature and 30 min reaction time was enough for maximum yield of 90.1%. The catalyst maintained sustained activity after five cycles of use. The oxidative stability which was the main problem of the biodiesel was improved from 2.0 h to 3.2h after 30 days using ascorbic acid as antioxidant. The other properties including the flash point, cetane number and the cold flow ones were however, comparable to international standards. The study indicated that Ti-0.7-600-6 is an efficient, economical and environmentally, friendly catalyst under ultrasonication for producing biodiesel from S. marianum oil with a substantial yield. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Decolorization of ammonium lignosulfonate with H(2)O(2)/Cu(II) heterogeneous catalyst.

    Science.gov (United States)

    Dulman, Viorica; Ignat, Maurusa-Elena; Bunia, Ion

    2011-01-01

    The potential of ammonium lignosulfonate (ALS) decolorization and degradation in aqueous solution was studied in a heterogeneous system using hydrogen peroxide and a Cu (II)-chelating ion exchanger. This was based on acrylic copolymers functionalized with N,N dimethylamino propylamine (DMAPA) as a catalyst. In order to optimize the efficiency of the system, the influence of such process parameters like H(2)O(2) concentration, pH, contact time, temperature, ALS concentration and catalyst amount were evaluated. The apparent rate constant of decolorization calculated from the absorbance data indicates that the process profiles follow pseudo-first order kinetics. Lignosulfonate degradation was furthermore studied by FTIR spectroscopy, thermogravimetric analysis and determination in phenolic compounds. The catalyst stability and reusability have also been investigated. Our experimental results clearly indicate that, under optimum conditions, the ammonium lignosulfonate solutions exhibit a total bleaching associated with degradation and significant mineralization to CO(2).

  3. Solar-Driven Hydrogen Peroxide Production Using Polymer-Supported Carbon Dots as Heterogeneous Catalyst

    Science.gov (United States)

    Gogoi, Satyabrat; Karak, Niranjan

    2017-10-01

    Safe, sustainable, and green production of hydrogen peroxide is an exciting proposition due to the role of hydrogen peroxide as a green oxidant and energy carrier for fuel cells. The current work reports the development of carbon dot-impregnated waterborne hyperbranched polyurethane as a heterogeneous photo-catalyst for solar-driven production of hydrogen peroxide. The results reveal that the carbon dots possess a suitable band-gap of 2.98 eV, which facilitates effective splitting of both water and ethanol under solar irradiation. Inclusion of the carbon dots within the eco-friendly polymeric material ensures their catalytic activity and also provides a facile route for easy catalyst separation, especially from a solubilizing medium. The overall process was performed in accordance with the principles of green chemistry using bio-based precursors and aqueous medium. This work highlights the potential of carbon dots as an effective photo-catalyst.

  4. Highlights from Faraday Discussion: Designing New Heterogeneous Catalysts, London, UK, April 2016.

    Science.gov (United States)

    Fischer, Nico; Manyar, Haresh G; Roldan, Alberto

    2016-06-28

    The Faraday Discussion on the design of new heterogeneous catalysts took place from 4-6 April 2016 in London, United Kingdom. It brought together world leading scientists actively involved in the synthesis, characterisation, modelling and testing of solid catalysts, attracting more than one hundred delegates from a broad spectrum of backgrounds and experience levels - academic and industrial researchers, experimentalists and theoreticians, and students. The meeting was a reflection of how big of an impact the ability to control and design catalysts with specific properties for particular processes can potentially have on the chemical industry, environment, economy and society as a whole. In the following, we give an overview of the topics covered during this meeting and briefly highlight the content of each presentation.

  5. Biodiesel production from waste cooking oil using copper doped zinc oxide nanocomposite as heterogeneous catalyst.

    Science.gov (United States)

    Gurunathan, Baskar; Ravi, Aiswarya

    2015-01-01

    A novel CZO nanocomposite was synthesized and used as heterogeneous catalyst for transesterification of waste cooking oil into biodiesel using methanol as acyl acceptor. The synthesized CZO nanocomposite was characterized in FESEM with an average size of 80 nm as nanorods. The XRD patterns indicated the substitution of ZnO in the hexagonal lattice of Cu nanoparticles. The 12% (w/w) nanocatalyst concentration, 1:8 (v:v) O:M ratio, 55 °C temperature and 50 min of reaction time were found as optimum for maximum biodiesel yield of 97.71% (w/w). Hence, the use of CZO nanocomposite can be used as heterogeneous catalyst for biodiesel production from waste cooking oil. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Elimination of radiocontrast agent diatrizoic acid by photo-Fenton process and enhanced treatment by coupling with electro-Fenton process.

    Science.gov (United States)

    Bocos, Elvira; Oturan, Nihal; Pazos, Marta; Sanromán, M Ángeles; Oturan, Mehmet A

    2016-10-01

    The removal of radiocontrast agent diatrizoic acid (DIA) from water was performed using photo-Fenton (PF) process. First, the effect of H2O2 dosage on mineralization efficiency was determined using ultraviolet (UV) irradiation. The system reached a maximum mineralization degree of 60 % total organic carbon (TOC) removal at 4 h with 20 mM initial H2O2 concentration while further concentration values led to a decrease in TOC abatement efficiency. Then, the effect of different concentrations of Fenton's reagents was studied for homogeneous Fenton process. Obtained results revealed that 0.25 mM Fe(3+) and 20 mM H2O2 were the best conditions, achieving 80 % TOC removal efficiency at 4 h treatment. Furthermore, heterogeneous PF treatment was developed using iron-activated carbon as catalyst. It was demonstrated that this catalyst is a promising option, reaching 67 % of TOC removal within 4 h treatment without formation of iron leachate in the medium. In addition, two strategies of enhancement for process efficiency are proposed: coupling of PF with electro-Fenton (EF) process in two ways: photoelectro-Fenton (PEF) or PF followed by EF (PF-EF) treatments, achieving in both cases the complete mineralization of DIA solution within only 2 h. Finally, the Microtox tests revealed the formation of more toxic compounds than the initial DIA during PF process, while, it was possible to reach total mineralization by both proposed alternatives (PEF or PF-EF) and thus to remove the toxicity of DIA solution.

  7. Zirconium phenylphosphonate-anchored methyltrioxorhenium as novel heterogeneous catalyst for epoxidation of cyclohexene.

    Science.gov (United States)

    He, Sha; Liu, Xin; Zhao, Hongyue; Zhu, Yue; Zhang, Fazhi

    2015-01-01

    Epoxidation of olefins to epoxides is widely recognized as an important unit process in the manufacture of fine chemicals and intermediates. Developing an environmentally benign heterogeneous catalytic system for olefin epoxidation with high activity and selectivity is still a challenge in this research field. Herein, we report our attempts to synthesize novel zirconium phenylphosphonate-anchored methyltrioxorhenium (MTO/ZrPP) heterogeneous catalysts by a conventional impregnation method and evaluate their catalytic performance for epoxidation of cyclohexene using urea-hydrogen peroxide adduct (UHP) as oxidant without the addition of base ligands. The MTO/ZrPP catalyst samples are characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR), inductively coupled plasma emission spectrometry (ICP-ES), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and solid-state (1)H magic-angle spinning nuclear magnetic resonance ((1)H MAS NMR) techniques. Meanwhile, the density functional theory (DFT) calculation is carried out to further understand the structure feature and interactions of the MTO/ZrPP catalyst. It is revealed that MTO is anchored on support surface by the favored hydrogen-bonding interaction between two oxo ligands of MTO and two H atoms from the adjacent phenyls of ZrPP. MTO/ZrPP catalyst displays excellent catalytic activity for cyclohexene epoxidation. Moreover, only cyclohexene oxide production can be obtained under the employed reaction conditions. Copyright © 2014 Elsevier Inc. All rights reserved.

  8. Single-Site Heterogeneous Catalysts: Innovations, Advantages, and Future Potential in Green Chemistry and Sustainable Technology

    Science.gov (United States)

    Raja, Robert; Thomas, John Meurig

    The advantages that flow from the availability of single-site heterogeneous catalysts are many. They facilitate the determination of the kinetics and mechanism of catalytic turnover and render accessible the energetics of various intermediates. More importantly, it is possible to prepare soluble molecular fragments that circumscribe the single site, thus enabling a direct comparison to be made between the catalytic performance of the same active site when functioning as a heterogeneous or a homogeneous catalyst. Our approach adopts the principles and practices of solid-state chemistry, augmented by lessons derived from enzymology, as well as computational chemistry. We have succeeded in designing a range of new catalysts to effect, inter alia, shape-selective, regioselective, bifunctional, and enantioselective catalytic conversions. In particular, large fractions of these catalysts are ideally suited for the era of clean technology in which single-step and/or solvent-free processes abound, and in which benign oxidants such as air or oxygen and inexpensive nanoporous materials are employed.

  9. Practical synthesis of indoles and benzofurans in water using a heterogeneous bimetallic catalyst

    Directory of Open Access Journals (Sweden)

    Cybille Rossy

    2013-07-01

    Full Text Available This paper describes the preparation of indoles, azaindoles and benzofurans in pure water by using a new heterogeneous Pd–Cu/C catalyst through a cascade Sonogashira alkynylation–cyclization sequence. Details of the optimization studies and the substrate scope are discussed. This procedure allows the preparation of heterocycles with good yields and is tolerant to a wide variety of functional groups.

  10. New heterogeneous acid catalysts in the synthesis of biodiesel; Estudo de novos catalisadores heterogeneous acidos na sintese de biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Soldi, Rafael A.; Cesar-Oliveira, Maria Aparecida F. [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Quimica. Lab. de Polimeros Sinteticos], e-mail: mafco@quimica.ufpr.br; Oliveira, Angelo R.S.; Ramos, Luiz P. [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Quimica. Centro de Pesquisa em Quimica Aplicada (CEPESQ)

    2007-07-01

    In this work, sulfonated polystyrene compounds (PSS) were synthesized from linear polystyrene (PS). Several methods and experimental conditions were investigated for the sulfonation of PS, producing catalytically active polymeric materials with sulfonation degrees in the range of 5.0-6.2 mmol -SO{sub 3}H/g of dry polymer. The performance of these catalysts was evaluated in transesterification reactions of beef tallow and vegetable oils with ethanol and methanol. For the sake of comparison, the same reaction conditions employed for the PSS catalysts were also used for an Amberlyst 15 (3,7 mmol SO{sub 3}H/g - Aldrich). The PSS samples were shown to be insoluble in the reaction media, leading to conversion rates of 85%, 75% and 80% of the refined soybean oil, beef tallow and crude corn oil in to ethyl esters, respectively, and 94% of the refined soybean oil methyl esters. Amberlyst 15 was studied as an alternative to the process, but its conversion rate to alkyl esters was very low in the employed conditions. These results demonstrated that our synthetic PSS materials have a great potential to act as heterogeneous catalysts for transesterification. (author)

  11. Application of response surface methodology for optimization of azocarmine B removal by heterogeneous photo-Fenton process using hydroxy-iron-aluminum pillared bentonite

    Science.gov (United States)

    Xu, Tianyuan; Liu, Yun; Ge, Fei; Liu, Lin; Ouyang, Yuting

    2013-09-01

    Hydroxy-iron-aluminum pillared bentonite (H-Fe-Al-B) was synthesized with ion exchange method, and its catalyst characteristics were analyzed by using X-ray diffraction (XRD) and X-ray photoelectron spectrometry (XPS). The photo-Fenton catalytic activity of H-Fe-Al-B was tested under different reaction condition using azocarmine B (ACB) as model pollutant under ultraviolet light (UV) irradiation. The effects of three operating variables, initial dye concentration, initial pH value and H2O2 concentration on the decolorization efficiency of ACB were optimized by response surface methodology (RSM) based on Box-Behnken design. The results showed that hydroxy aluminum iron ions intercalated into the interlayer spaces of bentonite successfully and H-Fe-Al-B had high photocatalytic activity. Analysis of variance (ANOVA) indicated that the proposed quadratic model could be used to navigate the design space. The proposed model was approximately in accordance with the experimental case with correlation coefficients R2, Radj2 and Rpred2 correlation coefficients of 0.9996, 0.9991 and 0.9934, respectively. The optimum conditions for ACB decolorization were dye concentration of 143.7 mg/L, pH of 4.2 and H2O2 concentration of 17.7 mM, respectively. The predicted decolorization rate under the optimum conditions determined by the proposed model was 99.6%. Confirmatory tests were carried out under the optimum conditions and the decolorization rate of 99.5% was observed, which closely agreed with the predicted value.

  12. Application of response surface methodology for optimization of azocarmine B removal by heterogeneous photo-Fenton process using hydroxy-iron–aluminum pillared bentonite

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Tianyuan, E-mail: xutianyuan1988@126.com; Liu, Yun, E-mail: liuyunscut@163.com; Ge, Fei, E-mail: gefei@xtu.edu.cn; Liu, Lin, E-mail: liulin861@163.com; Ouyang, Yuting, E-mail: oyt0225@126.com

    2013-09-01

    Hydroxy-iron–aluminum pillared bentonite (H-Fe–Al-B) was synthesized with ion exchange method, and its catalyst characteristics were analyzed by using X-ray diffraction (XRD) and X-ray photoelectron spectrometry (XPS). The photo-Fenton catalytic activity of H-Fe–Al-B was tested under different reaction condition using azocarmine B (ACB) as model pollutant under ultraviolet light (UV) irradiation. The effects of three operating variables, initial dye concentration, initial pH value and H{sub 2}O{sub 2} concentration on the decolorization efficiency of ACB were optimized by response surface methodology (RSM) based on Box–Behnken design. The results showed that hydroxy aluminum iron ions intercalated into the interlayer spaces of bentonite successfully and H-Fe–Al-B had high photocatalytic activity. Analysis of variance (ANOVA) indicated that the proposed quadratic model could be used to navigate the design space. The proposed model was approximately in accordance with the experimental case with correlation coefficients R{sup 2}, R{sub adj}{sup 2} and R{sub pred}{sup 2} correlation coefficients of 0.9996, 0.9991 and 0.9934, respectively. The optimum conditions for ACB decolorization were dye concentration of 143.7 mg/L, pH of 4.2 and H{sub 2}O{sub 2} concentration of 17.7 mM, respectively. The predicted decolorization rate under the optimum conditions determined by the proposed model was 99.6%. Confirmatory tests were carried out under the optimum conditions and the decolorization rate of 99.5% was observed, which closely agreed with the predicted value.

  13. Enhanced furfural production from raw corn stover employing a novel heterogeneous acid catalyst.

    Science.gov (United States)

    Li, Wenzhi; Zhu, Yuanshuai; Lu, Yijuan; Liu, Qiyu; Guan, Shennan; Chang, Hou-Min; Jameel, Hasan; Ma, Longlong

    2017-12-01

    With the aim to enhance the direct conversion of raw corn stover into furfural, a promising approach was proposed employing a novel heterogeneous strong acid catalyst (SC-CaC t -700) in different solvents. The novel catalyst was characterized by elemental analysis, N 2 adsorption-desorption, FT-IR, XPS, TEM and SEM. The developed catalytic system demonstrated superior efficacy for furfural production from raw corn stover. The effects of reaction temperature, residence time, catalyst loading, substrate concentration and solvent were investigated and optimized. 93% furfural yield was obtained from 150mg corn stover at 200°C in 100min using 45mg catalyst in γ-valerolactone (GVL). In comparison, 51.5% furfural yield was achieved in aqueous media under the same conditions (200°C, 5h, and 45mg catalyst), which is of great industrial interest. Furfural was obtained from both hemicelluloses and cellulose in corn stover, which demonstrated a promising routine to make the full use of biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Model heterogeneous acid catalysts and metal-support interactions: A combined surface science and catalysis study

    Energy Technology Data Exchange (ETDEWEB)

    Boszormenyi, Istvan [Univ. of California, Berkeley, CA (United States)

    1991-05-01

    This (<100Å) silica-alumina layers were tested as potential model heterogeneous acid catalysts for combined surface science and catalysis studies. Three preparation methods were used: oxidation of r3 x r3 R30 Al/Si(111) structure in UHV; deposition on Si(lll) from aqueous solution; and argon ion beam sputter deposition in UHV. The homogeneous thin layers are amorphous, and the chemical environment of surface atoms is similar to that of Si, Al and oxygen atoms on high surface area acid catalysts. Since the ion beam-deposited thin layer of silica-alumina has the same composition as the target zeolite this deposition method is a promising tool to prepare model catalysts using practical catalyst targets. The silica-alumina layers are active in cumene cracking, a typical acid catalyzed reaction. In order to clearly distinguish background reactions and the acid catalyzed reaction at least 20 cm2 catalyst surface area is needed. Two series of model platinum-alumina catalysts were prepared in a combined UHV -- high pressure reactor cell apparatus by depositing alumina on polycrystalline Pt foil and by vapor depositing Pt on a thin alumina layer on Au. Both model surfaces have been prepared with and without chlorine. AES, CO desorption as well as methyl cyclopentane (MCP) hydrogenolysis studies indicate that the Pt surface area is always higher if a chlorination step is involved. Selectivity patterns in MCP ring opening on ``Pt-on-alumina`` and on ``alumina-on-Pt`` are different; only the former is a linear combination of selective and statistical ring opening. Product distribution, however, changes with coverage and reaction time. The properties of the two model catalyst systems and role of chlorine in MCP hydrogenolysis are also discussed.

  15. Model heterogeneous acid catalysts and metal-support interactions: A combined surface science and catalysis study

    Energy Technology Data Exchange (ETDEWEB)

    Boszormenyi, I.

    1991-05-01

    This (<100 [Angstrom]) silica-alumina layers were tested as potential model heterogeneous acid catalysts for combined surface science and catalysis studies. Three preparation methods were used: oxidation of r3 [times] r3 R30 Al/Si(111) structure in UHV; deposition on Si(lll) from aqueous solution; and argon ion beam sputter deposition in UHV. The homogeneous thin layers are amorphous, and the chemical environment of surface atoms is similar to that of Si, Al and oxygen atoms on high surface area acid catalysts. Since the ion beam-deposited thin layer of silica-alumina has the same composition as the target zeolite this deposition method is a promising tool to prepare model catalysts using practical catalyst targets. The silica-alumina layers are active in cumene cracking, a typical acid catalyzed reaction. In order to clearly distinguish background reactions and the acid catalyzed reaction at least 20 cm[sup 2] catalyst surface area is needed. Two series of model platinum-alumina catalysts were prepared in a combined UHV -- high pressure reactor cell apparatus by depositing alumina on polycrystalline Pt foil and by vapor depositing Pt on a thin alumina layer on Au. Both model surfaces have been prepared with and without chlorine. AES, CO desorption as well as methyl cyclopentane (MCP) hydrogenolysis studies indicate that the Pt surface area is always higher if a chlorination step is involved. Selectivity patterns in MCP ring opening on Pt-on-alumina'' and on alumina-on-Pt'' are different; only the former is a linear combination of selective and statistical ring opening. Product distribution, however, changes with coverage and reaction time. The properties of the two model catalyst systems and role of chlorine in MCP hydrogenolysis are also discussed.

  16. Design of Heterogeneous Hoveyda-Grubbs Second-Generation Catalyst-Lipase Conjugates.

    Science.gov (United States)

    Neville, Anthony; Iniesta, Javier; Palomo, Jose M

    2016-12-06

    Heterogeneous catalysts have been synthesi zed by the conjugation of Hoveyda-Grubbs second-generation catalyst with a lipase. The catalytic properties of the organometallic compound in solution were firstly optimized, evaluating the activity of Ru in the ring-closing metathesis of diethyldiallymalonate at 25 °C at different solvents and in the presence of different additives. The best result was found using tetrahydrofuran as a solvent. Some additives such as phenylboronic acid or polyetheneglycol slightly improved the activity of the Ru catalyst whereas others, such as pyridine or dipeptides affected it negatively. The organometallic compound immobilized on functionalized-surface materials activated with boronic acid or epoxy groups (around 50-60 µg per mg support) and showed 50% conversion at 24 h in the ring-closing metathesis. Cross-linked enzyme aggregates (CLEA's) of the Hoveyda-Grubbs second-generation catalyst with Candida antarctica lipase (CAL-B) were prepared, although low Ru catalyst was found to be translated in low conversion. Therefore, a sol-gel preparation of the Hoveyda-Grubbs second-generation and CAL-B was performed. This catalyst exhibited good activity in the metathesis of diethyldiallymalonate in toluene and in aqueous media. Finally, a new sustainable approach was used by the conjugation lipase-Grubbs in solid phase in aqueous media. Two strategies were used: one using lipase previously covalently immobilized on an epoxy-Sepharose support (hydrophilic matrix) and then conjugated with grubbs; and in the second, the free lipase was incubated with organometallic in aqueous solution and then immobilized on epoxy-Sepharose. The different catalysts showed excellent conversion values in the ring-closing metathesis of diethyldiallymalonate in aqueous media at 25 °C.

  17. Economic and ecological aspects of biodiesel production over homogeneous and heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kiss, Ferenc E.; Boskovic, Goran C. [University of Novi Sad, Faculty of Technology, Bulevar Cara Lazara 1, 21000 Novi Sad (RS); Jovanovic, Milenko [University of Novi Sad, Faculty of Agriculture, Dositeja Obradovica 8, 21000 Novi Sad (RS)

    2010-10-15

    The objective of this paper is to highlight the economic and ecological differences of biodiesel production over homogeneous and heterogeneous catalysts in large-scale industrial plants. Comparative economic assessment of the two processes revealed the advantage of the heterogeneous process in terms of higher yield of biodiesel and higher purity of glycerine, lower cost of catalyst and maintenance, with an estimated cumulative impact on the reduction of the operating cost of US$59 per tonne of biodiesel, relative to the homogeneous process. The biggest challenge for its economic competitiveness is its higher energy consumption. The analysis showed that if the energy costs are below US$85 per tonne of biodiesel, the heterogeneous process can be economically viable. The environmental benefits of the heterogeneous process include absence of strong acids and of energy intensive and waste generating glycerine purification step. However, its application would contribute to depletion of fossil energy resources and higher emission of greenhouse gases due to higher energy and methanol consumption. (author)

  18. Optimization of transesterification of rubber seed oil using heterogeneous catalyst calcium oxide

    Science.gov (United States)

    Inggrid, Maria; Kristanto, Aldi; Santoso, Herry

    2015-12-01

    Biodiesel is an alternative fuel manufactured with the help of alkali hydroxide catalyst through transesterification reaction of vegetable oil. This study aims to examine methods and the most suitable conditions for transesterification reaction producing biodiesel from crude rubber seed oil by varying process parameters such as the molar ratio of alcohol, CaO amount as the alkaline catalyst, and reaction time. The rubber seed oil has a high level of free fatty acid content, which means the use of homogenous alkaline catalyst gives some technological problems such as soap formation which leaded in difficulty in the separation and purification of the product. Calcium oxide (CaO) is one of the most favorable heterogeneous base catalysts because it's reusable, noncorrosive, and low cost. Pre-treatment was performed by acid esterification with H2SO4 as the catalyst to decrease the content of free fatty acid in the rubber seed oil, in this pretreatment process the 12% FFA of crude oil could be reduced to below 3% FFA. The product after esterification process was then transesterified by alkaline transesterification by varying process parameters to convert triglyceride into biodiesel. The study found that maximum curvature for biodiesel yield occurred at 9:1 molar ratio of alcohol, 5%w catalyst loading, and 3 hours reaction time. Design expert software is used to determine the optimum point from experimental data. The result showed that the optimum yield of methyl ester from transesterification was 73.5 % by mass with 0.69 degree of desirability. The yielded methyl ester was tested for its density, viscosity, acid number, and solubility to meet SNI requirement standards.

  19. Direct use of mineral fertilizers MAP, DAP, and TSP as heterogeneous catalysts in organic reactions

    Directory of Open Access Journals (Sweden)

    Imane Bahammou

    2016-07-01

    Full Text Available In this paper, we reported the first use of phosphate fertilizers (MAP, DAP, and TSP as heterogeneous catalysts for organic reactions.  Their catalytic activities were investigated in the first time in Knoevenagel condensation of various aromatic aldehydes with malononitrile at room temperature.  These minerals phosphate showed high catalytic activities and ability to be recovering and reusing without a significant loss in their catalytic activities.  In order to reach the optimal reaction conditions for Knoevenagel condensation, we carried out a kinetic study of the effect of reaction time, the effect of solvent, the amount of catalysts and the variation of the range of the particles size the more active.  The best conditions were obtained by the use of these fertilizers (MAP, DAP, and TSP in their commercial status, simply crashed in powder, without any purification, using ethanol as solvent.  These phosphate fertilizers prove to be very promising and effective heterogeneous catalysts for the condensation of Knoevenagel.

  20. Catalytic oxidation of pulping effluent by activated carbon-supported heterogeneous catalysts.

    Science.gov (United States)

    Yadav, Bholu Ram; Garg, Anurag

    2016-01-01

    The present study deals with the non-catalytic and catalytic wet oxidation (CWO) for the removal of persistent organic compounds from the pulping effluent. Two activated carbon-supported heterogeneous catalysts (Cu/Ce/AC and Cu/Mn/AC) were used for CWO after characterization by the following techniques: temperature-programmed reduction, Fourier transform infrared spectroscopy and thermo-gravimetric analysis. The oxidation reaction was performed in a batch high-pressure reactor (capacity = 0.7  L) at moderate oxidation conditions (temperature = 190°C and oxygen pressure = 0.9 MPa). With Cu/Ce/AC catalyst, the maximum chemical oxygen demand (COD), total organic carbon (TOC) and lignin removals of 79%, 77% and 88% were achieved compared to only 50% removal during the non-catalytic process. The 5-day biochemical oxygen demand (BOD5) to COD ratio (a measure for biodegradability) of the pulping effluent was improved to 0.52 from an initial value of 0.16. The mass balance calculations for solid recovered after CWO reaction showed 8% and 10% deduction in catalyst mass primarily attributed to the loss of carbon and metal leaching. After the CWO process, carbon deposition was also observed on the recovered catalyst which was responsible for around 3-4% TOC reduction.

  1. SELECTIVE SYNTHESIS OF PEG-MONOESTER USING CESIUM HETEROPOLY ACID AS HETEROGENEOUS CATALYST

    Directory of Open Access Journals (Sweden)

    Fatimah Zahara Abdullah

    Full Text Available Esterification of oleic acid with polyethylene glycol 600 (PEG-600 to produce polyethylene glycol monooleate (PEG-monooleate and polyethylene glycol dioleate (PEG-dioleate as by-product has been studied in the presence of heterogeneous acid catalysts, i.e. cesium heteropoly acid (Cs HPA. The results are compared with those obtained from a classical homogeneous acid catalyst; p-toluene sulphonic acid (p-TSA. The reaction was conducted under nitrogen flow with vigorous stirring at 130 ºC and 150 ºC. The catalyst loading kept at 4% and the reaction was monitored at 1, 3, 7 and 24 hours. Reaction samples were analyzed using high performance liquid chromatography (HPLC equipped with evaporative light scattering detector (ELSD. The results obtained showed that Cs HPAs exhibit 100% selectivity of PEG-monooleate from the first hour until 24 hours. However, this does not happen with homogeneous p-TSA, where formation of by-product; PEG-dioleate is observed in the initial stage. It is also showed that the mole ratio is the most important parameter not only to produce high yield of monoester but also to maintain it along the reaction. Chemical and physical properties of catalysts were characterized using Thermal Gravimetric Analysis (TGA, Differential Scanning Calorimetry (DSC, Fourier Tranmittance Infra-Red (FTIR, ammonia temperature programmed desorption (NH3-TPD and X-ray Diffraction (XRD.

  2. Uncovering structure-activity relationships in manganese-oxide-based heterogeneous catalysts for efficient water oxidation.

    Science.gov (United States)

    Indra, Arindam; Menezes, Prashanth W; Driess, Matthias

    2015-03-01

    Artificial photosynthesis by harvesting solar light into chemical energy could solve the problems of energy conversion and storage in a sustainable way. In nature, CO2 and H2 O are transformed into carbohydrates by photosynthesis to store the solar energy in chemical bonds and water is oxidized to O2 in the oxygen-evolving center (OEC) of photosystem II (PS II). The OEC contains CaMn4 O5 cluster in which the metals are interconnected through oxido bridges. Inspired by biological systems, manganese-oxide-based catalysts have been synthesized and explored for water oxidation. Structural, functional modeling, and design of the materials have prevailed over the years to achieve an effective and stable catalyst system for water oxidation. Structural flexibility with eg(1) configuration of Mn(III) , mixed valency in manganese, and higher surface area are the main requirements to attain higher efficiency. This Minireview discusses the most recent progress in heterogeneous manganese-oxide-based catalysts for efficient chemical, photochemical, and electrochemical water oxidation as well as the structural requirements for the catalyst to perform actively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Low cost heterogenous catalyst from (Achatina Fulica) snail shell and its application for biodiesel conversion via microwave irradiation

    Science.gov (United States)

    Fatimah, Is; Kurniastuti, E. A.; Basthiani, I. A.; Fakhri, A.

    2017-11-01

    Research on preparation of heterogenous catalyst from Achatina Fulica snail shell and its application biodiesel conversion has been investigation. Research aimed to obtain low cost and reusable catalyst for biodiesel production. The catalyst was prepared by grinding and calcining the snail shell at 900°C for 2 hours. The obtained solid was analysed by using XRD, SEM-EDX. FTIR, and also basicity measurement. Catalyst was used in the cenvertion of rice bran oil transesterification at varied volume of oil methanol ratio of 20-80 under microwave and reflux methode. The transesterification result were analyzed by using GCMS.

  4. Optimization Study in Biodiesel Production via Response Surface Methodology Using Dolomite as a Heterogeneous Catalyst

    Directory of Open Access Journals (Sweden)

    Regina C. R. Santos

    2014-01-01

    Full Text Available A carbonate mineral, dolomite, was used as a heterogeneous catalyst to produce methyl-esters from soybean oil. The samples were analyzed by XRF, TGA, XRD, TPD-CO2, and SEM. The calcination of dolomite at 800°C/1 h resulted in a highly active mixed metal oxides. In addition, the influence of the reaction variables such as the temperature, catalyst amount, and methanol/soybean oil molar ratio in methyl-ester production was optimized by the application of a central composite design in conjunction with the response surface methodology (RSM. The XRF analysis is carried out after the reuses procedure which shows that the deactivation process is mainly due to the selective calcium leaching. Overall, the calcined dolomite exhibited high catalytic activity at moderate operating conditions for biodiesel production.

  5. Biodiesel production from the lipid of wastewater sludge using an acidic heterogeneous catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Siddiquee, M.N.; Kazemian, H.; Rohani, S. [University of Western Ontario, Department of Chemical and Biochemical Engineering, London, ON (Canada)

    2011-12-15

    The production of biodiesel from the lipid of wastewater sludge was studied using SBA-15 impregnated with the heteropolyacid H{sub 3}PO{sub 4}.12WO{sub 3}.xH{sub 2}O (PW{sub 12}) as a mesoporous heterogeneous catalyst. X-ray diffraction, Brunauer-Emmett-Teller surface area, thermalgravimetric analysis, and scanning electron microscopy were applied to characterize the prepared catalysts. Catalytic performances were evaluated in a microreactor setup under different experimental conditions. The biodiesel yield for a sample impregnated with 15 % PW{sub 12} was 30.14 wt-% at a temperature of 135 C and a pressure of 135 psi for 3 h reaction time. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Process Parameters Optimization of Potential SO42-/ZnO Acid Catalyst for Heterogeneous Transesterification of Vegetable Oil to Biodiesel

    Directory of Open Access Journals (Sweden)

    Istadi Istadi

    2012-12-01

    Full Text Available Among the possible renewable energy resources, diesel fuels derived from triglycerides of vegetable oils and animal fats have shown potential as substitutes for petroleum-based diesel fuels. The biodiesel could be produced from vegetable oils over homogeneous catalyst, heterogeneous catalyst, or enzymatic catalyst. In this study, the synthesized SO42-/ZnO catalyst was explored to be used in the heterogeneous biodiesel production by using the vegetable oils and methanol. The study began with the preparation of SO42-/ZnO catalyst followed by the transesterification reaction between vegetable oil with methanol. The independent variables (reaction time and the weight ratio of catalyst/oil were optimized to obtain the optimum biodiesel (fatty acid methyl ester yield. The results of this study showed that the acid catalyst SO42-/ZnO was potential to be used as catalyst for biodiesel production through heterogeneous transesterification of vegetable oils. Optimum operating condition for this catalytic reaction was the weight ratio of catalyst/oil of 8:1 and reaction time of 2.6 h with respect to 75.5% yield of methyl ester products. The biodiesel product was also characterized to identify the respected fatty acid methyl ester components. Copyright © 2012 by BCREC UNDIP. All rights reserved. (Selected Paper from International Conference on Chemical and Material Engineering (ICCME 2012Received: 23rd October 2012, Revised: 25th November 2012, Accepted: 25th November 2012[How to Cite: I. Istadi, Didi D. Anggoro, Luqman Buchori, Inshani Utami, Roikhatus Solikhah, (2012. Process Parameters Optimization of Potential SO42-/ZnO Acid Catalyst for Heterogeneous Transesterification of Vegetable Oil to Biodiesel. Bulletin of Chemical Reaction Engineering & Catalysis, 7(2: 150-157. (doi:10.9767/bcrec.7.2.4064.150-157][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.2.4064.150-157 ] | View in 

  7. Calcium oxide derived from waste shells of mussel, cockle, and scallop as the heterogeneous catalyst for biodiesel production.

    Science.gov (United States)

    Buasri, Achanai; Chaiyut, Nattawut; Loryuenyong, Vorrada; Worawanitchaphong, Phatsakon; Trongyong, Sarinthip

    2013-01-01

    The waste shell was utilized as a bioresource of calcium oxide (CaO) in catalyzing a transesterification to produce biodiesel (methyl ester). The economic and environmen-friendly catalysts were prepared by a calcination method at 700-1,000°C for 4 h. The heterogeneous catalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), and the Brunauer-Emmett-Teller (BET) method. The effects of reaction variables such as reaction time, reaction temperature, methanol/oil molar ratio, and catalyst loading on the yield of biodiesel were investigated. Reusability of waste shell catalyst was also examined. The results indicated that the CaO catalysts derived from waste shell showed good reusability and had high potential to be used as biodiesel production catalysts in transesterification of palm oil with methanol.

  8. Calcium Oxide Derived from Waste Shells of Mussel, Cockle, and Scallop as the Heterogeneous Catalyst for Biodiesel Production

    Directory of Open Access Journals (Sweden)

    Achanai Buasri

    2013-01-01

    Full Text Available The waste shell was utilized as a bioresource of calcium oxide (CaO in catalyzing a transesterification to produce biodiesel (methyl ester. The economic and environmen-friendly catalysts were prepared by a calcination method at 700–1,000°C for 4 h. The heterogeneous catalysts were characterized by X-ray diffraction (XRD, X-ray fluorescence (XRF, scanning electron microscopy (SEM, and the Brunauer-Emmett-Teller (BET method. The effects of reaction variables such as reaction time, reaction temperature, methanol/oil molar ratio, and catalyst loading on the yield of biodiesel were investigated. Reusability of waste shell catalyst was also examined. The results indicated that the CaO catalysts derived from waste shell showed good reusability and had high potential to be used as biodiesel production catalysts in transesterification of palm oil with methanol.

  9. Nanolithographic Fabrication and Heterogeneous Reaction Studies ofTwo-Dimensional Platinum Model Catalyst Systems

    Energy Technology Data Exchange (ETDEWEB)

    Contreras, Anthony Marshall [Univ. of California, Berkeley, CA (United States)

    2006-05-20

    In order to better understand the fundamental components that govern catalytic activity, two-dimensional model platinum nanocatalyst arrays have been designed and fabricated. These catalysts arrays are meant to model the interplay of the metal and support important to industrial heterogeneous catalytic reactions. Photolithography and sub-lithographic techniques such as electron beam lithography, size reduction lithography and nanoimprint lithography have been employed to create these platinum nanoarrays. Both in-situ and ex-situ surface science techniques and catalytic reaction measurements were used to correlate the structural parameters of the system to catalytic activity.

  10. Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts.

    Science.gov (United States)

    Pelletier, Jérémie D A; Basset, Jean-Marie

    2016-04-19

    Heterogeneous catalysis, a field important industrially and scientifically, is increasingly seeking and refining strategies to render itself more predictable. The main issue is due to the nature and the population of catalytically active sites. Their number is generally low to very low, their "acid strengths" or " redox properties" are not homogeneous, and the material may display related yet inactive sites on the same material. In many heterogeneous catalysts, the discovery of a structure-activity reationship is at best challenging. One possible solution is to generate single-site catalysts in which most, if not all, of the sites are structurally identical. Within this context and using the right tools, the catalyst structure can be designed and well-defined, to reach a molecular understanding. It is then feasible to understand the structure-activity relationship and to develop predictable heterogeneous catalysis. Single-site well-defined heterogeneous catalysts can be prepared using concepts and tools of surface organometallic chemistry (SOMC). This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metal nanoparticles). This strategy has a solid track record to reveal structure-activity relationship to the extent that it is becoming now quite predictable. Almost all elements of the periodical table have been grafted on surfaces of oxides (from simple oxides such as silica or alumina to more sophisticated materials regarding composition or porosity). Considering catalytic hydrocarbon transformations, heterogeneous catalysis outcome may now be predicted based on existing mechanistic proposals and the rules of molecular chemistry (organometallic, organic) associated with some concepts of surface sciences. A thorough characterization of the grafted metal centers must be carried out using tools spanning from molecular organometallic or surface chemistry. By selection of the metal, its ligand set, and the support taken

  11. Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts

    KAUST Repository

    Pelletier, Jeremie

    2016-03-09

    ConspectusHeterogeneous catalysis, a field important industrially and scientifically, is increasingly seeking and refining strategies to render itself more predictable. The main issue is due to the nature and the population of catalytically active sites. Their number is generally low to very low, their "acid strengths" or " redox properties" are not homogeneous, and the material may display related yet inactive sites on the same material. In many heterogeneous catalysts, the discovery of a structure-activity reationship is at best challenging. One possible solution is to generate single-site catalysts in which most, if not all, of the sites are structurally identical. Within this context and using the right tools, the catalyst structure can be designed and well-defined, to reach a molecular understanding. It is then feasible to understand the structure-activity relationship and to develop predictable heterogeneous catalysis. Single-site well-defined heterogeneous catalysts can be prepared using concepts and tools of surface organometallic chemistry (SOMC). This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metal nanoparticles). This strategy has a solid track record to reveal structure-activity relationship to the extent that it is becoming now quite predictable. Almost all elements of the periodical table have been grafted on surfaces of oxides (from simple oxides such as silica or alumina to more sophisticated materials regarding composition or porosity).Considering catalytic hydrocarbon transformations, heterogeneous catalysis outcome may now be predicted based on existing mechanistic proposals and the rules of molecular chemistry (organometallic, organic) associated with some concepts of surface sciences. A thorough characterization of the grafted metal centers must be carried out using tools spanning from molecular organometallic or surface chemistry. By selection of the metal, its ligand set, and the

  12. Upgrading Lignocellulosic Biomasses: Hydrogenolysis of Platform Derived Molecules Promoted by Heterogeneous Pd-Fe Catalysts

    Directory of Open Access Journals (Sweden)

    Claudia Espro

    2017-03-01

    Full Text Available This review provides an overview of heterogeneous bimetallic Pd-Fe catalysts in the C–C and C–O cleavage of platform molecules such as C2–C6 polyols, furfural, phenol derivatives and aromatic ethers that are all easily obtainable from renewable cellulose, hemicellulose and lignin (the major components of lignocellulosic biomasses. The interaction between palladium and iron affords bimetallic Pd-Fe sites (ensemble or alloy that were found to be very active in several sustainable reactions including hydrogenolysis, catalytic transfer hydrogenolysis (CTH and aqueous phase reforming (APR that will be highlighted. This contribution concentrates also on the different synthetic strategies (incipient wetness impregnation, deposition-precipitaion, co-precipitaion adopted for the preparation of heterogeneous Pd-Fe systems as well as on the main characterization techniques used (XRD, TEM, H2-TPR, XPS and EXAFS in order to elucidate the key factors that influence the unique catalytic performances observed.

  13. Heterogenization of Ketone Catalyst for Epoxidation by Low Pressure Plasma Fluorination of Silica Gel Supports.

    Science.gov (United States)

    D'Accolti, Lucia; De Vietro, Nicoletta; Fanelli, Fiorenza; Fusco, Caterina; Nacci, Angelo; Fracassi, Francesco

    2017-11-30

    Low pressure plasma was used for preparing heterogeneous organocatalysts 2 -( A )-( C ) suitable for dioxirane-mediated epoxidations. Heterogenization was accomplished by adsorption of the methyl perfluoroheptyl ketone ( 2 ) on fluorinated supports ( A )-( C ) deriving from the treatment of commercial C₈-silica gel in low pressure plasma fed with fluorocarbons. Catalyst 2 -( C ) proved to be the most efficient one, promoting epoxidation of an array of alkenes, including unsaturated fatty esters like methyl oleate ( 10 ) and the triglyceride soybean oil ( 11 ), with the cheap potassium peroxymonosulfate KHSO₅ (caroate) as a green oxidant. Notably, the perfluorinated matrix gives rise to the activation of caroate, generating singlet oxygen. Materials were characterized by infrared Attenuated Total Reflectance spectroscopy (ATR-FTIR), X-ray Photoelectron Spectroscopy (XPS ) and Emission Scanning Electron Microscope (FESEM).

  14. Heterogenization of Ketone Catalyst for Epoxidation by Low Pressure Plasma Fluorination of Silica Gel Supports

    Directory of Open Access Journals (Sweden)

    Lucia D’Accolti

    2017-11-01

    Full Text Available Low pressure plasma was used for preparing heterogeneous organocatalysts 2-(A-(C suitable for dioxirane-mediated epoxidations. Heterogenization was accomplished by adsorption of the methyl perfluoroheptyl ketone (2 on fluorinated supports (A-(C deriving from the treatment of commercial C8-silica gel in low pressure plasma fed with fluorocarbons. Catalyst 2-(C proved to be the most efficient one, promoting epoxidation of an array of alkenes, including unsaturated fatty esters like methyl oleate (10 and the triglyceride soybean oil (11, with the cheap potassium peroxymonosulfate KHSO5 (caroate as a green oxidant. Notably, the perfluorinated matrix gives rise to the activation of caroate, generating singlet oxygen. Materials were characterized by infrared Attenuated Total Reflectance spectroscopy (ATR-FTIR, X-ray Photoelectron Spectroscopy (XPS and Emission Scanning Electron Microscope (FESEM.

  15. Genetic Manipulation of Outer Membrane Permeability: Generating Porous Heterogeneous Catalyst Analogs in Escherichia coli

    Energy Technology Data Exchange (ETDEWEB)

    Patel, TN; Park, AHA; Bantat, S

    2014-12-01

    The limited permeability of the E. coli outer membrane can significantly hinder whole-cell biocatalyst performance. In this study, the SARS coronavirus small envelope protein (SCVE) was expressed in E. coli cells previously engineered for periplasmic expression of carbonic anhydrase (CA) activity. This maneuver increased small molecule uptake by the cells, resulting in increased apparent CA activity of the biocatalysts. The enhancements in activity were quantified using methods developed for traditional heterogeneous catalysis. The expression of the SCVE protein was found to significantly reduce the Thiele moduli (phi), as well as increase the effectiveness factors (eta), effective diffusivities (D-e), and permeabilities (P) of the biocatalysts. These catalytic improvements translated into superior performance of the biocatalysts for the precipitation of calcium carbonate from solution which is an attractive strategy for long-term sequestration of captured carbon dioxide. Overall, these results demonstrate that synthetic biology approaches can be used to enhance heterogeneous catalysts incorporated into microbial whole-cell scaffolds.

  16. Highly Dispersed Pseudo-Homogeneous and Heterogeneous Catalysts Synthesized via Inverse Micelle Solutions for the Liquefaction of Coal

    Energy Technology Data Exchange (ETDEWEB)

    Hampden-Smith, M.; Kawola, J.S.; Martino, A.; Sault, A.G.; Yamanaka, S.A.

    1999-01-05

    The mission of this project was to use inverse micelle solutions to synthesize nanometer sized metal particles and test the particles as catalysts in the liquefaction of coal and other related reactions. The initial focus of the project was the synthesis of iron based materials in pseudo-homogeneous form. The frost three chapters discuss the synthesis, characterization, and catalyst testing in coal liquefaction and model coal liquefaction reactions of iron based pseudo-homogeneous materials. Later, we became interested in highly dispersed catalysts for coprocessing of coal and plastic waste. Bifunctional catalysts . to hydrogenate the coal and depolymerize the plastic waste are ideal. We began studying, based on our previously devised synthesis strategies, the synthesis of heterogeneous catalysts with a bifunctional nature. In chapter 4, we discuss the fundamental principles in heterogeneous catalysis synthesis with inverse micelle solutions. In chapter 5, we extend the synthesis of chapter 4 to practical systems and use the materials in catalyst testing. Finally in chapter 6, we return to iron and coal liquefaction now studied with the heterogeneous catalysts.

  17. Laser-Induced Fluorescence Detection in High-Throughput Screening of Heterogeneous Catalysts and Single Cells Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Su, Hui [Iowa State Univ., Ames, IA (United States)

    2001-01-01

    Laser-induced fluorescence detection is one of the most sensitive detection techniques and it has found enormous applications in various areas. The purpose of this research was to develop detection approaches based on laser-induced fluorescence detection in two different areas, heterogeneous catalysts screening and single cell study. First, we introduced laser-induced imaging (LIFI) as a high-throughput screening technique for heterogeneous catalysts to explore the use of this high-throughput screening technique in discovery and study of various heterogeneous catalyst systems. This scheme is based on the fact that the creation or the destruction of chemical bonds alters the fluorescence properties of suitably designed molecules. By irradiating the region immediately above the catalytic surface with a laser, the fluorescence intensity of a selected product or reactant can be imaged by a charge-coupled device (CCD) camera to follow the catalytic activity as a function of time and space. By screening the catalytic activity of vanadium pentoxide catalysts in oxidation of naphthalene, we demonstrated LIFI has good detection performance and the spatial and temporal resolution needed for high-throughput screening of heterogeneous catalysts. The sample packing density can reach up to 250 x 250 subunits/cm2 for 40-μm wells. This experimental set-up also can screen solid catalysts via near infrared thermography detection.

  18. Lanthanum cobaltite perovskite supported on zirconia as an efficient heterogeneous catalyst for activating Oxone in water.

    Science.gov (United States)

    Lin, Kun-Yi Andrew; Chen, Yu-Chien; Lin, Tien-Yu; Yang, Hongta

    2017-07-01

    Zirconia-supported LaCoO3 perovskite (LaCoO3/ZrO2 (LCZ)) is prepared and adopted for the first time as a heterogeneous catalyst for activating Oxone to degrade organic pollutants. The resulting LCZ exhibits a significantly higher surface area (i.e., 10 times) than bulk LaCoO3 powder as nanoscale LaCoO3 particles were easily afforded on the surface of ZrO2 support. As Rhodamine B (RB) decolorization is selected as a model test to evaluate catalytic activity for activating Oxone, LCZ showed a much higher catalytic activity to activate Oxone than LaCoO3 even though LCZ contained only 12.5wt% of LaCoO3. LCZ-activated Oxone also remained effective for RB decolorization even in the presence of salts and other organic contaminant. The mechanism of RB decolorization by LCZ-activated Oxone was revealed and involved sulfate radical and other reactive oxygen species. The mechanism of Oxone activation by LCZ could be owing to both La3+ and Co3+ of LCZ. LCZ was recycled to activate Oxone for RB decolorization over multiple times without loss of catalytic activity. These results demonstrate that LCZ is a promising LaCoO3-based nanocomposite as a heterogeneous catalyst for activating Oxone to degrade organic pollutants. Copyright © 2017 Elsevier Inc. All rights reserved.

  19. Superstructure-based Design and Optimization of Batch Biodiesel Production Using Heterogeneous Catalysts

    Science.gov (United States)

    Nuh, M. Z.; Nasir, N. F.

    2017-08-01

    Biodiesel as a fuel comprised of mono alkyl esters of long chain fatty acids derived from renewable lipid feedstock, such as vegetable oil and animal fat. Biodiesel production is complex process which need systematic design and optimization. However, no case study using the process system engineering (PSE) elements which are superstructure optimization of batch process, it involves complex problems and uses mixed-integer nonlinear programming (MINLP). The PSE offers a solution to complex engineering system by enabling the use of viable tools and techniques to better manage and comprehend the complexity of the system. This study is aimed to apply the PSE tools for the simulation of biodiesel process and optimization and to develop mathematical models for component of the plant for case A, B, C by using published kinetic data. Secondly, to determine economic analysis for biodiesel production, focusing on heterogeneous catalyst. Finally, the objective of this study is to develop the superstructure for biodiesel production by using heterogeneous catalyst. The mathematical models are developed by the superstructure and solving the resulting mixed integer non-linear model and estimation economic analysis by using MATLAB software. The results of the optimization process with the objective function of minimizing the annual production cost by batch process from case C is 23.2587 million USD. Overall, the implementation a study of process system engineering (PSE) has optimized the process of modelling, design and cost estimation. By optimizing the process, it results in solving the complex production and processing of biodiesel by batch.

  20. Development of a Photo-Fenton Catalyst Supported on Modified Polymer Films: Preparation, Characterization and Implication for Water Decontamination by Solar Photocatalysis

    OpenAIRE

    Mazille, Félicien

    2010-01-01

    The work presented in this thesis is a part of the European project INNOWATECH. The global objective of this project was to provide effective technological solutions for the treatment of industrial wastewater, to propose new concepts in wastewater treatment with potential benefits for the protection of the environment. In particular photo-assisted Fenton oxidation was investigated. It is a promising technology to decontaminate industrial wastewater ...

  1. Amberlyst-15: An Efficient and reusable heterogeneous catalyst for the synthesis of β-amino carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Pathakota Venkata Ramana

    2015-12-01

    Full Text Available A simple and efficient method has been developed for the synthesis of β-amino carbonyl compounds from aromatic ketones, aldehydes and amines by Mannich reaction in the presence of amberlyst-15 as a reusable heterogeneous catalyst at room temperature under solvent-free conditions. The noteworthy advantages of the present method are short reaction times, good product yields, simple procedures and use of non-toxic catalyst.

  2. Preparation and Characterization of Anadara Granosa Shells and CaCO3 as Heterogeneous Catalyst for Biodiesel Production

    Directory of Open Access Journals (Sweden)

    Hadiyanto Hadiyanto

    2016-03-01

    Full Text Available Nowadays, the use of homogenous catalyst has been gradually reduced for its operational reason. The homogenous catalyst leads in difficulty of separation after the process completed and the life cycle is shorter. Therefore, most of researches are introducing heterogenous catalyst for its substitution. This research was aimed to evaluate the use of shell of Anadara granosa and CaCO3 as source of CaO based catalyst through impregnation method. The preparation of the catalyst was started by decomposition of shells and CaCO3 at temperature of 800 oC for 3 hours, followed by impregnation at 70 oC for 4 hours and then calcined at 800 oC for 2 hours. The CaCO3 based catalyst gained high yield of biodiesel (94% as compared to Anadara granoasa based catalyst (92%. The reusability study showed that these catalysts could be used until three times recycle with 40-60% yield of biodiesel. The CaO contents of catalyst decreased up to 90% after three times recycles. Copyright © 2016 BCREC GROUP. All rights reserved Received: 10th November 2015; Revised: 6th January 2016; Accepted: 6th January 2016 How to Cite: Hadiyanto, H., Lestari, S.P., Widayat, W. (2016. Preparation and Characterization of Anadara Granosa Shells and CaCO3 as Heterogeneous Catalyst for Biodiesel Production. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 21-26. (doi:10.9767/bcrec.11.1.402.21-26 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.402.21-26

  3. Recent Advances in the Synthesis, Characterization and Application of Zn+-containing Heterogeneous Catalysts.

    Science.gov (United States)

    Chen, Guangbo; Zhao, Yufei; Shang, Lu; Waterhouse, Geoffrey I N; Kang, Xiaofeng; Wu, Li-Zhu; Tung, Chen-Ho; Zhang, Tierui

    2016-07-01

    Monovalent Zn+ (3d104s1) systems possess a special electronic structure that can be exploited in heterogeneous catalysis and photocatalysis, though it remains challenge to synthesize Zn+-containing materials. By careful design, Zn+-related species can be synthesized in zeolite and layered double hydroxide systems, which in turn exhibit excellent catalytic potential in methane, CO and CO2 activation. Furthermore, by utilizing advanced characterization tools, including electron spin resonance, X-ray absorption fine structure and density functional theory calculations, the formation mechanism of the Zn+ species and their structure-performance relationships can be understood. Such advanced characterization tools guide the rational design of high-performance Zn+-containing catalysts for efficient energy conversion.

  4. Recent Advances in the Synthesis, Characterization and Application of Zn+‐containing Heterogeneous Catalysts

    Science.gov (United States)

    Chen, Guangbo; Zhao, Yufei; Shang, Lu; Waterhouse, Geoffrey I. N.; Kang, Xiaofeng; Wu, Li‐Zhu; Tung, Chen‐Ho

    2016-01-01

    Monovalent Zn+ (3d104s1) systems possess a special electronic structure that can be exploited in heterogeneous catalysis and photocatalysis, though it remains challenge to synthesize Zn+‐containing materials. By careful design, Zn+‐related species can be synthesized in zeolite and layered double hydroxide systems, which in turn exhibit excellent catalytic potential in methane, CO and CO2 activation. Furthermore, by utilizing advanced characterization tools, including electron spin resonance, X‐ray absorption fine structure and density functional theory calculations, the formation mechanism of the Zn+ species and their structure‐performance relationships can be understood. Such advanced characterization tools guide the rational design of high‐performance Zn+‐containing catalysts for efficient energy conversion. PMID:27818902

  5. Enhanced esterification of oleic acid and methanol by deep eutectic solvent assisted Amberlyst heterogeneous catalyst.

    Science.gov (United States)

    Pan, Ying; Alam, Md Asraful; Wang, Zhongming; Wu, Jingcheng; Zhang, Yi; Yuan, Zhenhong

    2016-11-01

    In present study, esterification of oleic acid with methanol using deep eutectic solvent (DES) assisted Amberlyst heterogeneous catalyst was investigated to produce biodiesel. Results showed that esterification efficiency was enhanced by the DES. The combined effect of DES on Amberlyst BD20 (BD20) is better than Amberlyst 15 (A-15) due to different structure. The optimal reaction conditions were 12:1M ratio of methanol to oleic acid, 20%(wt/wt) catalyst (BD20-DES (2:8) and A-15-DES (8:2)) at 85°C for 100min with agitating at 200rpm. The mechanism involved in catalysis and their capacity to reuse were studied. We proposed, Choline chloride-glycerol (Chcl-gly) DES could enhance the Amberlyst function due to the hydrogen bond effect on both DES and water. BD20 has fewer pores than A-15, have desirable performance in decreasing the inhibition the water during esterification of high FFA content and provide better performance in reuse. Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin.

    Science.gov (United States)

    Yépez, Rebeca; Illescas, Juan F; Gijón, Paulina; Sánchez-Sánchez, Manuel; González-Zamora, Eduardo; Santillan, Rosa; Álvarez, J Raziel; Ibarra, Ilich A; Aguilar-Pliego, Julia

    2016-07-23

    Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately 200 different odorant compounds in addition to vanillin. The natural extraction of vanillin (from the orchid Vanilla planifolia, Vanilla tahitiensis and Vanilla pompon) represents only 1% of the worldwide production and since this process is expensive and very long, the rest of the production of vanillin is synthesized. Many biotechnological approaches can be used for the synthesis of vanillin from lignin, phenolic stilbenes, isoeugenol, eugenol, guaicol, etc., with the disadvantage of harming the environment since these processes use strong oxidizing agents and toxic solvents. Thus, eco-friendly alternatives on the production of vanillin are very desirable and thus, under current investigation. Porous coordination polymers (PCPs) are a new class of highly crystalline materials that recently have been used for catalysis. HKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzene-tricarboxylate) is a very well known PCP which has been extensively studied as a heterogeneous catalyst. Here, we report a synthetic strategy for the production of vanillin by the oxidation of trans-ferulic acid using HKUST-1 as a catalyst.

  7. Amino-functionalized metal-organic frameworks as tunable heterogeneous basic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, M.; Hartmann, M. [Erlangen-Nuernberg Univ., Erlangen (Germany). Erlangen Catalysis Resource Center

    2011-07-01

    Metal-organic framework (MOF) materials have been explored for applications in heterogeneous catalysis in recent years. In addition to the use of MOFs as supports for the deposition of highly dispersed metal particles, the incorporation of active centers such as coordinatively unsaturated metal sites and the functionalization of the organic linkers with acidic or basic groups seems to be most promising. In our contribution, three different MOFs carrying amino groups at their organic linkers, namely Fe-MIL-101-NH{sub 2} (S{sub BET} = 3438 m{sup 2}g{sup -1}), Al-MIL-101-NH{sub 2} (S{sub BET} = 3099 m{sup 2}g{sup -1}) and CAU-1 (S{sub BET} = 1492 m{sup 2}g{sup -1}), were synthesized and tested in the Knoevenagel condensation of benzaldehyde with malononitrile and with ethyl cyanoacetate, respectively. It is shown that the expected products benzylidenemalononitrile (BzMN) and ethyl a-cyanocinnamate (EtCC) are formed with selectivities of more than 99 % and yields of 90 to 95 % after 3 h (for BzMN). Due to the very small pore windows of CAU-1 (0.3 to 0.4 nm) the reaction proceeds much slower over this catalyst in comparison to the amino-MIL-101 derivatives, which possess open pore windows of up to 1.6 nm. Finally, leaching tests confirm that the reaction is heterogeneously catalyzed. Moreover, the catalysts are recyclable without significant loss of activity. (orig.)

  8. The enhanced catalytic degradation of SiO2/Fe3O4/C@TiO2 photo-Fenton system on p-nitrophenol

    Science.gov (United States)

    Hou, Yanhui; Wang, Yechen; Yuan, Huili; Chen, Hang; Chen, Guowei; Shen, Junhai; Li, Liangchao

    2016-11-01

    Heterogeneous photo-Fenton SiO2/Fe3O4/C@TiO2 (SFCT) catalyst with a core-multishell structure and a diameter of about 550 nm was successfully prepared and was characterized by scanning electron microscopy (SEM), TEM, XRD, Raman, and Fourier transform infrared (FT-IR). The results illustrated that anatase TiO2 coexisted with rutile TiO2, in which the anatase phase was the main crystal phase. In addition, the catalytic activity of SFCT catalyst had been evaluated in the catalytic degradation on p-nitrophenol (PNP). The influence factors on the PNP degradation, including SFCT component ratio ( m SFC/ m TiO2), H2O2 dosage, solution pH, and PNP concentration, had been investigated. And the contrast experiments about the photo-Fenton catalytic mechanism revealed that the SFCT-2 catalyst possessed a superior activity in the neutral environment due to the optimal activity matching between Fe3O4 and TiO2, and it exhibited the stable catalytic performance after five successive recycles. Therefore, the SFCT-2 catalyst had a promising application for the photo-Fenton degradation of organic contaminant.

  9. Natural soil mediated photo Fenton-like processes in treatment of pharmaceuticals: Batch and continuous approach.

    Science.gov (United States)

    Changotra, Rahil; Rajput, Himadri; Dhir, Amit

    2017-12-01

    This paper manifests the potential viability of soil as a cost-free catalyst in photo-Fenton-like processes for treating pharmaceuticals at large scale. Naturally available soil without any cost intensive modification was utilized as a catalyst to degrade pharmaceuticals, specifically ornidazole (ORZ) and ofloxacin (OFX). Soil was characterized and found enriched with various iron oxides like hematite, magnetite, goethite, pyrite and wustite, which contributes toward enhanced dissolution of Fe3+ than Fe2+ in the aqueous solution resulting in augmented rate of photo-Fenton reaction. The leached iron concentration in solution was detected during the course of experiments. The degradation of ORZ and OFX was assessed in solar induced batch experiments using H2O2 as oxidant and 95% ORZ and 92% OFX removal was achieved. Elevated efficiencies were achieved due to Fe2+/Fe3+ cycling, producing more hydroxyl radical leading to the existence of homogeneous and heterogeneous reactions simultaneously. The removal efficiency of solar photo-Fenton like process was also compared to photo-Fenton process with different irradiation sources (UV-A and UV-B) and were statistically analysed. Continuous-scale studies were conducted employing soil either in the form of soil beads or as a thin layer spread on the surface of baffled reactor. Soil beads were found to have satisfactory reusability and stability. 84 and 79% degradation of ORZ and OFX was achieved using soil as thin layer while with soil beads 71 and 68% degradation, respectively. HPLC and TOC study confirmed the efficient removal of both the compounds. Toxicity assessment demonstrates the inexistence of toxic intermediates during the reaction. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Effect of Support in Heterogeneous Ruthenium Catalysts Used for the Selective Aerobic Oxidation of HMF in Water

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Riisager, Anders

    2011-01-01

    Heterogeneous ruthenium-based catalysts were applied in the selective, aerobic oxidation of 5-hydroxymethylfurfural, a versatile biomass-derived chemical, to form 2,5-furandicarboxylic acid. The oxidation reactions were performed in water with dioxygen as the oxidant at different pressures without...

  11. Kinetics studies of synthesis of biodiesel from waste frying oil using a heterogeneous catalyst derived from snail shell.

    Science.gov (United States)

    Birla, Ashish; Singh, Bhaskar; Upadhyay, S N; Sharma, Y C

    2012-02-01

    Waste frying oil was used to produce biodiesel using calcined snail shell as a heterogeneous base catalyst. Trans esterification reactions were carried out and the yield and conversion of the product were optimized by varying the methanol to oil molar ratio, catalyst amount, reaction temperature, and time. A biodiesel conversion of 99.58% was obtained with a yield of 87.28%. The reaction followed first order kinetics. The activation energy (E(A)) was 79kJ/mol and the frequency factor (A) was 2.98×10(10)min(-1). The fuel properties of the biodiesel were measured according to ASTM D 6751 and found to be within the specifications. Snail shell is a novel source for the production of heterogeneous base catalyst that can be successfully utilized for synthesis of biodiesel of high purity. Copyright © 2011 Elsevier Ltd. All rights reserved.

  12. Effect of Reaction Temperature on Biodiesel Production from Chlorella vulgaris using CuO/Zeolite as Heterogeneous Catalyst

    Science.gov (United States)

    Dianursanti; Delaamira, M.; Bismo, S.; Muharam, Y.

    2017-02-01

    Human needs for fossil energy increase every year. Biodiesel is the main way to resolve this world problem. Biodiesel produces from vegetable oil. But then, the alternative way came from the uses of microalgae in Chlorella vulgaris type causes by its simplicity of growing. In the other hand, this microalgae known for its high lipid content by considering several parameter such as light intensity, medium nutrition, pH and also salinity. Lipid content will be extracted by using Bligh-Dryer method which will be reacted with methanol along transesterification. Beside, there come another matter which is the utilization of homogeny catalyst. The difficulty of separation is the main matter so then biodiesel need to be washed in case normalizing the pH and this process will decrease the quality of biodiesel. To resolve this problem, we’ll be using a heterogeneous catalyst, zeolite, with ability to catalyst the process. Zeolite is easier to separate from the biodiesel so there will not be needed washing process. Heterogeneous catalyst work as well as homogeneous. Variation implemented on transesterification included reaction temperature of 40°C, 60°C, and 80°C. Reaction time, catalyst percentage and the solvent amount remain steady on 4 hours, 3% and 1:400. Complete best result obtained at 60°C with the yield of 36,78%. Through this, heterogeneous catalyst CuO/Zeolite proved to have a capability for replacing homogeneous catalyst and simplify the production of biodiesel particularly in separation step.

  13. Laser-Induced Fluorescence Detection in High-Throughput Screening of Heterogeneous Catalysts and Single Cells Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Su, Hui [Iowa State Univ., Ames, IA (United States)

    2001-01-01

    Laser-induced fluorescence detection is one of the most sensitive detection techniques and it has found enormous applications in various areas. The purpose of this research was to develop detection approaches based on laser-induced fluorescence detection in two different areas, heterogeneous catalysts screening and single cell study. First, the author introduced laser-induced imaging (LIFI) as a high-throughput screening technique for heterogeneous catalysts to explore the use of this high-throughput screening technique in discovery and study of various heterogeneous catalyst systems. This scheme is based on the fact that the creation or the destruction of chemical bonds alters the fluorescence properties of suitably designed molecules. By irradiating the region immediately above the catalytic surface with a laser, the fluorescence intensity of a selected product or reactant can be imaged by a charge-coupled device (CCD) camera to follow the catalytic activity as a function of time and space. By screening the catalytic activity of vanadium pentoxide catalysts in oxidation of naphthalene, they demonstrated LIFI has good detection performance and the spatial and temporal resolution needed for high-throughput screening of heterogeneous catalysts. The sample packing density can reach up to 250 x 250 subunits/cm2 for 40-μm wells. This experimental set-up also can screen solid catalysts via near infrared thermography detection. In the second part of this dissertation, the author used laser-induced native fluorescence coupled with capillary electrophoresis (LINF-CE) and microscope imaging to study the single cell degranulation. On the basis of good temporal correlation with events observed through an optical microscope, they have identified individual peaks in the fluorescence electropherograms as serotonin released from the granular core on contact with the surrounding fluid.

  14. Kinetic comparison of two basic heterogenous catalysts obtained from sustainable resources for transesterification of waste cooking oil

    Directory of Open Access Journals (Sweden)

    G.R. Moradi

    2015-06-01

    Full Text Available Alkaline earth metal oxides are appropriate catalysts for biodiesel production and among them, CaO and MgO are known for possessing the best efficiency. In this study, catalysts synthesized from economical and sustainable resources were used for biodiesel production. More specifically, waste mussel shells and demineralized (DM water treatment precipitates as calcium and magnesium carbonate sources, were converted into calcium and magnesium oxides at temperatures above 900 oC. Methanol and waste cooking oil were reacted in a 250 mL two-necked flask at 24:1 and 22.5:1 ratios in presence of 12 and 9.08 wt% of mussel shell-based and DM water treatment precipitates-based catalysts, respectively. The effects of temperature (328, 333, 338, 343 and 348 K and time (1, 3, 5, 7 and 8 h at a stirrer speed of 350 rpm on the conversion of the oil into biodiesel were investigated. The results obtained indicated a pseudo-first order kinetics for the transesterification reaction using both catalysts. The activation energies in the presence of the DM water treatment precipitates and mussel shell catalysts were measured at 77.09 and 79.83 kJ.mol-1, respectively. Accordingly, the DM water treatment precipitates catalyst resulted in a faster reaction due to its lower activation energy value. Moreover, the catalysts were reused five times and the results obtained showed that the methanol-driven extraction of CaO contained in the DM water treatment precipitates catalyst was lower than the waste mussel shell catalyst proving the higher stability of the new heterogeneous catalyst i.e. the calcinated DM water treatment precipitates.

  15. Biodiesel Production using Heterogeneous Catalyst in CSTR: Sensitivity Analysis and Optimization

    Science.gov (United States)

    Keong, L. S.; Patle, D. S.; Shukor, S. R.; Ahmad, Z.

    2016-03-01

    Biodiesel as a renewable fuel has emerged as a potential replacement for petroleum-based diesels. Heterogeneous catalyst has become the focus of researches in biodiesel production with the intention to overcome problems associated with homogeneous catalyzed processes. The simulation of heterogeneous catalyzed biodiesel production has not been thoroughly studied. Hence, a simulation of carbon-based solid acid catalyzed biodiesel production from waste oil with high FFA content (50 weight%) was developed in the present work to study the feasibility and potential of the simulated process. The simulated process produces biodiesel through simultaneous transesterification and esterification with the consideration of reaction kinetics. The developed simulation is feasible and capable to produce 2.81kmol/hr of FAME meeting the international standard (EN 14214). Yields of 68.61% and 97.19% are achieved for transesterification and esterification respectively. Sensitivity analyses of FFA composition in waste oil, methanol to oil ratio, reactor pressure and temperature towards FAME yield from both reactions were carried out. Optimization of reactor temperature was done to maximize FAME products.

  16. UV-Raman spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption studies of model and bulk heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Tewell, Craig Richmond [Univ. of California, Berkeley, CA (United States)

    2002-01-01

    X-ray photoelectron spectroscopy (XPS) and Temperature Programmed Desorption (TPD) have been used to investigate the surface structure of model heterogeneous catalysts in ultra-high vacuum (UHV). UV-Raman spectroscopy has been used to probe the structure of bulk model catalysts in ambient and reaction conditions. The structural information obtained through UV-Raman spectroscopy has been correlated with both the UHV surface analysis and reaction results. The present day propylene and ethylene polymerization catalysts (Ziegler-Natta catalysts) are prepared by deposition of TiCl4 and a Al(Et)3 co-catalyst on a microporous Mg-ethoxide support that is prepared from MgCl2 and ethanol. A model thin film catalyst is prepared by depositing metallic Mg on a Au foil in a UHV chamber in a background of TiCl4 in the gas phase. XPS results indicate that the Mg is completely oxidized to MgCl2 by TiCl4 resulting in a thin film of MgCl2/TiClx, where x = 2, 3, and 4. To prepare an active catalyst, the thin film of MgCl2/TiClx on Au foil is enclosed in a high pressure cell contained within the UHV chamber and exposed to ~1 Torr of Al(Et)3.

  17. Synthesis of biodiesel from sunflower oil over potassium loaded alumina as heterogeneous catalyst: The effect of process parameters

    Directory of Open Access Journals (Sweden)

    Marinkovic Milos M.

    2016-01-01

    Full Text Available Heterogeneous catalysis is in recent focus of research for biodiesel production from vegetable oils because of advantages such as easy separation and reuse of catalysts, although homogeneous catalysis is most commonly used method. The aim of this study was preparation of γ-Al2O3 support by modified sol-gel procedure, synthesis of the KI/Al2O3 catalyst and testing its activity in the transesterification of sunflower oil with methanol. Influences of different process parameters on conversion of sunflower oil to methyl esters were examined. The gained results implicate that the potassium iodide incorporation into/onto the structure of γ-Al2O3 significantly influences textural and structural properties of the catalyst. Additionally, the catalyst basic strength is increased and all together those properties are positively affecting the activity of the catalyst in the reaction of transesterification of sunflower oil with methanol. The impregnation of alumina with potassium iodide resulted in the additional formation of basic catalytically active sites. The surface properties of the catalyst have an essential impact on its catalytic performance. Under relatively mild process conditions and relatively short reaction time, the usage of the KI/Al2O3 catalyst resulted in very high conversion to fatty acids methyl esters (i.e. 99.99 %. [Projekat Ministarstva nauke Republike Srbije, br. 172061 i br. TR 34008

  18. Molecular Mixed-Metal Manganese Oxido Cubanes as Precursors to Heterogeneous Oxygen Evolution Catalysts.

    Science.gov (United States)

    Suseno, Sandy; McCrory, Charles C L; Tran, Rosalie; Gul, Sheraz; Yano, Junko; Agapie, Theodor

    2015-09-14

    Well-defined mixed-metal [CoMn3 O4 ] and [NiMn3 O4 ] cubane complexes were synthesized and used as precursors for heterogeneous oxygen evolution reaction (OER) electrocatalysts. The discrete clusters were dropcasted onto glassy carbon (GC) and indium tin oxide (ITO) electrodes, and the OER activities of the resulting films were evaluated. The catalytic surfaces were analyzed by various techniques to gain insight into the structure-function relationships of the electrocatalysts' heterometallic composition. Depending on preparation conditions, the Co-Mn oxide was found to change metal composition during catalysis, while the Ni-Mn oxides maintained the NiMn3 ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn3 O4 cubane-like geometry was maintained in the absence of thermal treatment (2-Ni). In contrast, the thermally generated 3-Ni develops an oxide-like extended structure. Both 2-Ni and 3-Ni undergo structural changes upon electrolysis, but they do not convert into the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological oxygen-evolving complex in Photosystem II, including the MMn3 O4 cubane moiety. The reported studies demonstrate the use of discrete heterometallic oxide clusters as precursors for heterogeneous water oxidation catalysts of novel composition and the distinct behavior of two sets of mixed metal oxides. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. SIMULTANEOUS DEGRADATION OF SOME PHTHALATE ESTERS UNDER FENTON AND PHOTO-FENTON OXIDATION PROCESSES

    Directory of Open Access Journals (Sweden)

    BELDEAN-GALEA M.S.

    2015-03-01

    Full Text Available In this study the assessment of the degradation efficiency of five phthalates, DEP, BBP, DEHP, DINP and DIDP, found in a mixture in a liquid phase, using the Fenton and Photo Fenton oxidation processes, was conducted. It was observed that the main parameters that influence the Fenton oxidative processes of phthalates were the concentration of the oxidizing agent, H2O2, the concentration of the catalyst used, Fe2+, the pH value, UV irradiation and the reaction time. For the Fenton oxidative process, the highest degradation efficiencies were 19% for DEP, 50% for BBP, 84% for DEHP, 90% for DINP and 48% for DIDP, when the experiments were carried out using concentrations of 20 mg L-1 phthalate mixture, 100 mg L-1 H2O2, 10 mg L-1 Fe2+ at a pH value of 3, with a total reaction time of 30 minutes. For the Photo-Fenton oxidative process carried out in the same conditions as Fenton oxidative process, it was observed that after an irradiation time of 90 minutes under UV radiation the degradation efficiencies of phthalates were improved, being 22% for DEP, 71% for BBP, 97% for DEHP, 97% for DINP and 81% for DIDP.

  20. Heterogeneous photodegradation of methylene blue with iron and tea or coffee polyphenols in aqueous solutions.

    Science.gov (United States)

    Morikawa, Claudio Kendi; Shinohara, Makoto

    2016-01-01

    Recently, we developed two new Fenton catalysts using iron (Fe) and spent tea leaves or coffee grounds as raw material. In this study, Fe-to-tea or Fe-to-coffee polyphenol complexes were successfully tested as heterogeneous photo-Fenton catalysts. The photodegradation efficiency of methylene blue solutions with Fe-to-polyphenol complexes was higher than that of homogeneous iron salts in the photo-Fenton process. Furthermore, the tested Fe-to-polyphenol complexes could be reused by simply adding H2O2 to the solutions. After three sequential additions of H2O2, the conventional catalysts FeCl2·4H2O and FeCl3 removed only 16.6% and 53.6% of the dye, while the catalysts made using spent coffee grounds and tea leaves removed 94.4% and 96.0% of the dye, respectively. These results showed that the complexes formed between Fe and chlorogenic acid, caffeic acid, gallic acid and catechin, which are the main polyphenols in tea and coffee, can be used to improve the photo-Fenton process.

  1. Production of a Biofuel that Keeps the Glycerol as a Monoglyceride by Using Supported KF as Heterogeneous Catalyst

    Directory of Open Access Journals (Sweden)

    Juan Calero

    2014-06-01

    Full Text Available This study describes the results obtained in the synthesis of a biofuel that avoids the production of glycerol by applying supported KF as alkaline heterogeneous catalyst, to generate two moles of fatty acid methyl esters and one mole of monoglyceride from one mol of triglyceride. In this respect, the selective transesterification process of sunflower oil with methanol was carried out with KF (10 wt% supported on three different solids, Al2O3, ZnO and MgO. The standard experimental conditions employed in the heterogeneous selective methanolysis reaction were: 12 mL of sunflower oil, 2.7 mL of methanol, 0.8 g of catalyst, at 65 °C temperature and one hour of reaction time. In all cases 100% conversion was obtained, with high selectivity values, greater than 90%, and quite suitable viscosity values, 4.5–8.5 cSt. In this way, the best catalytic behavior in the first use was obtained by using Al2O3 as support. However, although in the five consecutive reuses all catalysts exhibited a continuous decrease in their catalytic activities; the lower one was for KF catalyst using MgO as support. In summary, these three KF supported catalysts are very suitable to obtain a new biofuel, similar to conventional biodiesel, applicable to diesel engines.

  2. Asymmetric catalysis at the mesoscale: gold nanoclusters embedded in chiral self-assembled monolayer as heterogeneous catalyst for asymmetric reactions.

    Science.gov (United States)

    Gross, Elad; Liu, Jack H; Alayoglu, Selim; Marcus, Matthew A; Fakra, Sirine C; Toste, F Dean; Somorjai, Gabor A

    2013-03-13

    Research to develop highly versatile, chiral, heterogeneous catalysts for asymmetric organic transformations, without quenching the catalytic reactivity, has met with limited success. While chiral supramolecular structures, connected by weak bonds, are highly active for homogeneous asymmetric catalysis, their application in heterogeneous catalysis is rare. In this work, asymmetric catalyst was prepared by encapsulating metallic nanoclusters in chiral self-assembled monolayer (SAM), immobilized on mesoporous SiO2 support. Using olefin cyclopropanation as an example, it was demonstrated that by controlling the SAM properties, asymmetric reactions can be catalyzed by Au clusters embedded in chiral SAM. Up to 50% enantioselectivity with high diastereoselectivity were obtained while employing Au nanoclusters coated with SAM peptides as heterogeneous catalyst for the formation of cyclopropane-containing products. Spectroscopic measurements correlated the improved enantioselectivity with the formation of a hydrogen-bonding network in the chiral SAM. These results demonstrate the synergetic effect of the catalytically active metallic sites and the surrounding chiral SAM for the formation of a mesoscale enantioselective catalyst.

  3. Potential of LiNO3/Al2O3 Catalyst for Heterogeneous Transesterification of Palm Oil to Biodiesel

    Directory of Open Access Journals (Sweden)

    Istadi Istadi

    2010-10-01

    Full Text Available Production of biodiesel through transesterification process using heterogenous catalysts in order to avoid the saponification problem was studied. In this process, palm oil reacted with methanol to form a mixture of glycerol and biodiese over a solid basic catalyst. One type of the catalysts used in this research is basic catalyst of LiNO3/Al2O3. The parameters studied in this research are concentration of LiNO3 loading on Al2O3 and effect of different reaction time. The products was analyzed using Gas Chromatography to determine composition and yield of resulted methyl esters as well as conversion of palm oil to biodiesel. The major products in this transesterification reaction were biodiesel and glycerol. It can be concluded that the 20 wt% LiNO3/Al2O3 catalyst is potential for producing biodiesel from palm oil over transesterification reaction. Advantages of the usage of this catalyst is that the soap formation was not observed in this research. ©2010 BCREC UNDIP. All rights reserved(Received: 24th April 2010, Revised: 20th May 2010; Accepted: 21st May 2010[How to Cite: I. Istadi, B. Pramudono, S. Suherman, and S. Priyanto. (2010. Potential of LiNO3/Al2O3 Catalyst for Heterogeneous Transesterification of Palm Oil to Biodiesel. Bulletin of Chemical Reaction Engineering and Catalysis, 5(1: 51-56. doi:10.9767/bcrec.5.1.7128.51-56][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.5.1.7128.51-56

  4. Potential of LiNO3/Al2O3 Catalyst for Heterogeneous Transesterification of Palm Oil to Biodiesel

    Directory of Open Access Journals (Sweden)

    Bambang Pramudono

    2010-10-01

    Full Text Available Production of biodiesel through transesterification process using heterogenous catalysts in order to avoid the saponification problem was studied. In this process, palm oil reacted with methanol to form a mixture of glycerol and biodiese over a solid basic catalyst. One type of the catalysts used in this research is basic catalyst of LiNO3/Al2O3. The parameters studied in this research are concentration of LiNO3 loading on Al2O3 and effect of different reaction time. The products was analyzed using Gas Chromatography to determine composition and yield of resulted methyl esters as well as conversion of palm oil to biodiesel. The major products in this transesterification reaction were biodiesel and glycerol. It can be concluded that the 20 wt% LiNO3/Al2O3 catalyst is potential for producing biodiesel from palm oil over transesterification reaction. Advantages of the usage of this catalyst is that the soap formation was not observed in this research. ©2010 BCREC UNDIP. All rights reserved(Received: 24th April 2010, Revised: 20th May 2010; Accepted: 21st May 2010[How to Cite: I. Istadi, B. Pramudono, S. Suherman, and S. Priyanto. (2010. Potential of LiNO3/Al2O3 Catalyst for Heterogeneous Transesterification of Palm Oil to Biodiesel. Bulletin of Chemical Reaction Engineering and Catalysis, 5(1: 51-56. doi:10.9767/bcrec.5.1.777.51-56][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.5.1.777.51-56

  5. Mesocrystalline Zn-Doped Fe3O4 Hollow Submicrospheres: Formation Mechanism and Enhanced Photo-Fenton Catalytic Performance.

    Science.gov (United States)

    Nguyen, Xuan Sang; Zhang, Gaoke; Yang, Xianfeng

    2017-03-15

    Uniform and magnetic recyclable mesocrystalline Zn-doped Fe3O4 hollow submicrospheres (HSMSs) were successfully synthesized via a simple one-pot solvothermal route and were used for efficient heterogeneous photo-Fenton catalyst. XRD, XPS, Raman spectroscopy, Mössbauer spectroscopy, SEM, HRTEM, and EDX analyses revealed that the shell of HSMSs is highly porous and assembled by oriented attachment of magnetite nanocrystal building blocks with Zn-rich surfaces. Furthermore, a possible formation mechanism of mesocrystalline hollow materials was proposed. First, Fe3O4 mesocrystals were assembled by oriented nanocrystals, and a Zn-rich amorphous shell grew on the surfaces. Then, Zn gradually diffused into Fe3O4 crystals to form Zn-doped Fe3O4 due to the Kirkendall effect with increasing the reaction time. Meanwhile, the inner nanocrystals would be dissolved, and outer particles would grow larger owing to the Ostwald ripening process, leading to the formation of a hollow structure with porous shell. The Zn-doped Fe3O4 HSMSs exhibited high and stable photo-Fenton activity for degradation of rhodamine B (RhB) and cephalexin under visible-light irradiation in the presence of H2O2, which results from their hollow mesocrystal structure and Zn doping. It could be easily separated and reused by an external magnetic field. The results suggested that the as-obtained magnetite hollow mesocrystals could be a promising catalyst in the photo-Fenton process.

  6. Heterogeneities of the Nanostructure of Platinum/Zeolite Y Catalysts Revealed by Electron Tomography

    NARCIS (Netherlands)

    Zecevic, J.|info:eu-repo/dai/nl/341386715; van der Eerden, A.M.J.|info:eu-repo/dai/nl/304840483; Friedrich, H.|info:eu-repo/dai/nl/304837350; de Jongh, P.E.|info:eu-repo/dai/nl/186125372; de Jong, K.P.|info:eu-repo/dai/nl/06885580X

    2013-01-01

    To develop structure–performance relationships for important catalysts, a detailed characterization of their morphology is essential. Using electron tomography, we determined in three dimensions the structure of Pt/zeolite Y bifunctional catalysts. Optimum experimental conditions enabled for the

  7. Magnetically Separable Fe3O4@DOPA-Pd: A Heterogeneous Catalyst for Aqueous Heck Reaction

    Science.gov (United States)

    Magnetically separable Fe3O4@DOPA-Pd catalyst has been synthesized via anchoring of palladium over dopamine-coated magnetite via non-covalent interaction and the catalyst is utilized for expeditious Heck coupling in aqueous media.

  8. Fenton-like degradation of Bisphenol A catalyzed by mesoporous Cu/TUD-1

    Science.gov (United States)

    Pachamuthu, Muthusamy P.; Karthikeyan, Sekar; Maheswari, Rajamanickam; Lee, Adam F.; Ramanathan, Anand

    2017-01-01

    A family of copper oxide catalysts with loadings spanning 1-5 wt% were dispersed on a three dimensional, mesoporous TUD-1 silica through a hydrothermal, surfactant-free route employing tetraethylene glycol as a structure-directing agent. Their bulk and surface properties were characterized by N2 physisorption, XRD, DRUVS, EPR, TEM and Raman spectroscopy, confirming the expected mesoporous wormhole/foam support morphology and presence of well-dispersed CuO nanoparticles (∼5-20 nm). The catalytic performance of Cu/TUD-1 was evaluated as heterogeneous Fenton-like catalysts for Bisphenol A (BPA) oxidative degradation in the presence of H2O2 as a function of [H2O2], and CuO loading. Up to 90.4% of 100 ppm BPA removal was achieved over 2.5 wt% Cu/TUD-1 within 180 min, with negligible Cu leaching into the treated water.

  9. A polyoxometalate-encapsulating cationic metal-organic framework as a heterogeneous catalyst for desulfurization.

    Science.gov (United States)

    Hao, Xiu-Li; Ma, Yuan-Yuan; Zang, Hong-Ying; Wang, Yong-Hui; Li, Yang-Guang; Wang, En-Bo

    2015-02-23

    A new cationic triazole-based metal-organic framework encapsulating Keggin-type polyoxometalates, with the molecular formula [Co(BBPTZ)3][HPMo12O40]⋅24 H2O [compound 1; BBPTZ = 4,4'-bis(1,2,4-triazol-1-ylmethyl)biphenyl] is hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The structure of compound 1 contains a non-interpenetrated 3D CdSO4 (cds)-type framework with two types of channels that are interconnected with each other; straight channels that are occupied by the Keggin-type POM anions, and wavelike channels that contain lattice water molecules. The catalytic activity of compound 1 in the oxidative desulfurization reaction indicates that it is not only an effective and size-selective heterogeneous catalyst, but it also exhibits distinct structural stability in the catalytic reaction system. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Evaluation of PVP/Au Nanocomposite Fibers as Heterogeneous Catalysts in Indole Synthesis

    Directory of Open Access Journals (Sweden)

    Ioanna Savva

    2016-09-01

    Full Text Available Electrospun nanocomposite fibers consisting of crosslinked polyvinylpyrrolidone (PVP chains and gold nanoparticles (Au NPs were fabricated, starting from highly stable PVP/Au NP colloidal solutions with different NP loadings, followed by thermal treatment. Information on the morphological characteristics of the fibers and of the embedded Au NPs was obtained by electron microscopy. Cylindrical, bead-free fibers were visualized by Scanning Electron Microscopy (SEM while Transmission Electron Microscopy (TEM and Energy Diffraction X-ray (EDX analysis supported the presence of Au NPs within the fibers and gave information on their morphologies and average diameters. These materials were briefly evaluated as heterogeneous catalytic supports for the gold-catalyzed intramolecular cyclisation of 2‑(phenylethynylaniline to form 2-phenyl-1H-indole. The performance of the gold catalyst was strongly dependent on the Au NP size, with the system containing the smallest Au NPs being the more effective. Moreover, a slight drop of their catalytic efficiency was observed after three consecutive reaction runs, which was attributed to morphological changes as a consequence of fiber merging.

  11. Study of KOH/Al2O3 as heterogeneous catalyst for biodiesel production via in situ transesterification from microalgae.

    Science.gov (United States)

    Ma, Guixia; Hu, Wenrong; Pei, Haiyan; Jiang, Liqun; Ji, Yan; Mu, Ruimin

    2015-01-01

    Heterogeneous KOH/Al2O3 catalysts, synthesized by the wet impregnation method with different KOH loadings (20-40 wt%) and calcination temperatures from 400°C to 800°C, were used to produce biodiesel from Chlorella vulgaris biomass by in situ transesterification. The highest yield of biodiesel of 89.53±1.58% was achieved at calcination temperature of 700°C for 2 h and 35 wt% loading of KOH, and at the optimal reaction condition of 10 wt% of catalyst content, 8 mL/g of methanol to biomass ratio and at 60°C for 5 h. The characteristics of the catalysts were analysed by X-ray diffraction, scanning electron microscopy and Brunauer-Emmett-Teller.

  12. Magnetic diatomite(Kieselguhr)/Fe2O3/TiO2 composite as an efficient photo-Fenton system for dye degradation

    Science.gov (United States)

    Barbosa, Isaltino A.; Zanatta, Lucas D.; Espimpolo, Daniela M.; da Silva, Douglas L.; Nascimento, Leandro F.; Zanardi, Fabrício B.; de Sousa Filho, Paulo C.; Serra, Osvaldo A.; Iamamoto, Yassuko

    2017-10-01

    We explored the potential use of diatomite/Fe2O3/TiO2 composites as catalysts for heterogeneous photo-Fenton degradation of methylene blue under neutral pH. Such system consists in magnetic solids synthesized by co-precipitation with Fe2+/Fe3+ in the presence of diatomite, followed by impregnation of TiO2. The results showed that the optimal amount of the catalyst was 2.0 g L-1, since aggregation phenomena become significant above this concentration, which decreases the photodegradation activity. The catalyst is highly efficient in the degradation of methylene blue and shows an easy recovery by an external magnetic field. This allows for an effective catalyst reuse without significant loss of activity in catalytic cycles, which is a highly interesting prospect for recyclable dye degradation systems.

  13. High Efficient Photo-Fenton Catalyst of α-Fe2O3/MoS2 Hierarchical Nanoheterostructures: Reutilization for Supercapacitors

    Science.gov (United States)

    Yang, Xijia; Sun, Haiming; Zhang, Lishu; Zhao, Lijun; Lian, Jianshe; Jiang, Qing

    2016-08-01

    A novel three-dimensional (3D) α-Fe2O3/MoS2 hierarchical nanoheterostructure is effectively synthesized via a facile hydrothermal method. The zero-dimensional (0D) Fe2O3 nanoparticles guide the growth of two-dimensional (2D) MoS2 nanosheets and formed 3D flower-like structures, while MoS2 facilitates the good dispersion of porous Fe2O3 with abundant oxygen vacancies. This charming 3D-structure with perfect match of non-equal dimension exhibits high recyclable photo-Fenton catalytic activity for Methyl orange pollutant and nice specific capacity in reusing as supercapacitor after catalysis. The synergistic effect between Fe2O3 and MoS2, the intermediate nanointerfaces, the 3D porous structures, and the abundant oxygen vacancies both contribute to highly active catalysis, nice electrochemical performance and stable cycling. This strategy is simple, cheap, and feasible for maximizing the value of the materials, as well as eliminating the secondary pollution.

  14. Production of biodiesel from mixed waste vegetable oil using an aluminium hydrogen sulphate as a heterogeneous acid catalyst.

    Science.gov (United States)

    Ramachandran, Kasirajan; Sivakumar, Pandian; Suganya, Tamilarasan; Renganathan, Sahadevan

    2011-08-01

    Al(HSO(4))(3) heterogeneous acid catalyst was prepared by the sulfonation of anhydrous AlCl(3). This catalyst was employed to catalyze transesterification reaction to synthesis methyl ester when a mixed waste vegetable oil was used as feedstock. The physical and chemical properties of aluminum hydrogen sulphate catalyst were characterized by scanning electron microscopy (SEM) measurements, energy dispersive X-ray (EDAX) analysis and titration method. The maximum conversion of triglyceride was achieved as 81 wt.% with 50 min reaction time at 220°C, 16:1 molar ratio of methanol to oil and 0.5 wt.% of catalyst. The high catalytic activity and stability of this catalyst was related to its high acid site density (-OH, Brönsted acid sites), hydrophobicity that prevented the hydration of -OH group, hydrophilic functional groups (-SO(3)H) that gave improved accessibility of methanol to the triglyceride. The fuel properties of methyl ester were analyzed. The fuel properties were found to be observed within the limits of ASTM D6751. Copyright © 2011 Elsevier Ltd. All rights reserved.

  15. Assessment of research needs for advanced heterogeneous catalysts for energy applications. Final report: Volume 2, Topic reports

    Energy Technology Data Exchange (ETDEWEB)

    Mills, G.A.

    1994-04-01

    This report assesses the direction, technical content, and priority of research needs judged to provide the best chance of yielding new and improved heterogeneous catalysts for energy-related applications over the period of 5-20 years. It addresses issues of energy conservation, alternate fuels and feedstocks, and the economics and applications that could alleviate pollution from energy processes. Recommended goals are defined in 3 research thrusts: catalytic science, environmental protection by catalysis, and industrial catalytic applications. This study was conducted by an 11-member panel of experts from industry and academia, including one each from Japan and Europe. This volume first presents an in-depth overview of the role of catalysis in future energy technology in chapter 1; then current catalytic research is critically reviewed and research recommended in 8 topic chapters: catalyst preparation (design and synthesis), catalyst characterization (structure/function), catalyst performance testing, reaction kinetics/reactor design, catalysis for industrial chemicals, catalysis for electrical applications (clean fuels, pollution remediation), catalysis for control of exhaust emissions, and catalysts for liquid transportation fuels from petroleum, coal, residual oil, and biomass.

  16. Graphene Oxide Foam Supported Titanium(IV): Recoverable Heterogeneous Catalyst for Efficient, Selective Oxidation of Arylalkyl Sulfides to Sulfoxides Under Mild Conditions

    National Research Council Canada - National Science Library

    Qinghe Wang; Wenxi Ma; Qiaolin Tong; Guijie Du; Jian Wang; Meng Zhang; Hailun Jiang; Huali Yang; Yongxiang Liu; Maosheng Cheng

    2017-01-01

    An efficient and environmentally friendly method was designed for the oxidation of sulfides to sulfoxides with a recyclable, carbon-skeleton-based heterogeneous catalyst developed by titanium sulfate [Ti(SO4)2...

  17. Synthesis of long alkyl chain ethers through direct etherification of biomass-based alcohols with 1-octene over heterogeneous acid catalysts

    NARCIS (Netherlands)

    Ruppert, A.M.; Parvulescu, A.N.; Arias, M.J.; Bruijnincx, P.C.A.; Klein Gebbink, R.J.M.; Weckhuysen, B.M.

    2009-01-01

    Heterogeneous etherification of various biomass-based alcohols with 1-octene was investigated as a direct route for the synthesis of long alkyl chain ethers. Several acid catalyst materials including Amberlyst resins and various zeolites were screened as etherification catalysts in a solventless

  18. The Simple, Effective Synthesis of Highly Dispersed Pd/C and CoPd/C Heterogeneous Catalysts via Charge-Enhanced Dry Impregnation

    Directory of Open Access Journals (Sweden)

    Lawrence D’Souza

    2016-05-01

    Full Text Available Pd/C and CoPd/C heterogeneous catalysts have been synthesized by adopting Charge Enhanced Dry Impregnation (CEDI. The particles size distribution, their high metal surface-to-bulk ratios, and synthesis feasibility are unmatchable to any known noble metal bimetallic heterogeneous catalyst preparation techniques. Next generation Fuel Cells and Fischer-Tropsch catalytic processes economy will be benefited from the proposed methodology.

  19. The enhanced catalytic degradation of SiO{sub 2}/Fe{sub 3}O{sub 4}/C@TiO{sub 2} photo-Fenton system on p-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Yanhui; Wang, Yechen; Yuan, Huili; Chen, Hang; Chen, Guowei; Shen, Junhai; Li, Liangchao, E-mail: sky52@zjnu.cn [Zhejiang Normal University, Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry (China)

    2016-11-15

    Heterogeneous photo-Fenton SiO{sub 2}/Fe{sub 3}O{sub 4}/C@TiO{sub 2} (SFCT) catalyst with a core-multishell structure and a diameter of about 550 nm was successfully prepared and was characterized by scanning electron microscopy (SEM), TEM, XRD, Raman, and Fourier transform infrared (FT-IR). The results illustrated that anatase TiO{sub 2} coexisted with rutile TiO{sub 2}, in which the anatase phase was the main crystal phase. In addition, the catalytic activity of SFCT catalyst had been evaluated in the catalytic degradation on p-nitrophenol (PNP). The influence factors on the PNP degradation, including SFCT component ratio (m{sub SFC}/ m{sub TiO2}), H{sub 2}O{sub 2} dosage, solution pH, and PNP concentration, had been investigated. And the contrast experiments about the photo-Fenton catalytic mechanism revealed that the SFCT-2 catalyst possessed a superior activity in the neutral environment due to the optimal activity matching between Fe{sub 3}O{sub 4} and TiO{sub 2}, and it exhibited the stable catalytic performance after five successive recycles. Therefore, the SFCT-2 catalyst had a promising application for the photo-Fenton degradation of organic contaminant.

  20. Rapid decolorization of dye Orange G by microwave enhanced Fenton-like reaction with delafossite-type CuFeO2.

    Science.gov (United States)

    Cai, Mei-Qiang; Zhu, Yi-Zu; Wei, Zong-Su; Hu, Jian-Qiang; Pan, Sheng-Dong; Xiao, Rui-Yang; Dong, Chun-Ying; Jin, Mi-Cong

    2017-02-15

    Bimetallic oxide CuFeO2 as a new heterogeneous catalyst has shown much higher catalytic ability for activating peroxide than single-metal oxides. The present work demonstrated a synergistic microwave (MW) enhanced Fenton-like process with CuFeO2 for rapid decolorization of azo dye Orange G (OG). The MW irradiation dramatically enhanced the OG degradation efficiency, achieving 99.9% decolorization within 15min at pH5. The XRD analysis of reused CuFeO2, together with metal leaching tests, indicated merits of recycling for CuFeO2. The subsequent surface element analysis by XPS for fresh and used CuFeO2 showed a complex network for reactions between copper-iron redox pairs and surface hydroxyl groups, leading to a synergistic Fenton-like system accelerated by MW irradiation. In the CuFeO2 initiated Fenton-like reactions, several oxidant species (i.e., OH, O2-, electron hole, and FeIVO) responsible to the OG oxidation were identified by quenching experiments, showing the MW generated high temperature and "hot spots" enhanced the yield of OH by generation of electron-hole pairs. Further, the 26 detected degradation products confirmed the OH dominant oxidation of OG. This study shows that the MW-enhanced Fenton-like reaction using CuFeO2 has potential applications for rapid decolorization of dye effluent. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Ba/ZrO2 nanoparticles as efficient heterogeneous base catalyst for ...

    Indian Academy of Sciences (India)

    activity of the Ba/ZrO2 catalyst was evaluated for synthesis of β-nitro alcohols and 2-amino 2-chromenes. .... synthesized using malonic acid dihydrazide as fuel at ... from the ethanolic solution. The crude product was recrystallized using acetonitrile to afford the β-nitro alcohol in 89% yield. The used catalyst particles were.

  2. Ba/ZrO₂ nanoparticles as efficient heterogeneous base catalyst for ...

    Indian Academy of Sciences (India)

    The surface area, basicity and barium content of the material depend strongly on the method of synthesis. The Ba/ZrO₂ catalyst prepared by urea hydrolysis method exhibited higher surface area and barium content compared to other samples. The catalytic activity of the Ba/ZrO₂ catalyst was evaluated for synthesis of ...

  3. Application of Heterogeneous Copper Catalyst in a Continuous Flow Process: Dehydrogenation of Cyclohexanol

    Science.gov (United States)

    Glin´ski, Marek; Ulkowska, Urszula; Iwanek, Ewa

    2016-01-01

    In this laboratory experiment, the synthesis of a supported solid catalyst (Cu/SiO2) and its application in the dehydrogenation of cyclohexanol performed under flow conditions was studied. The experiment was planned for a group of two or three students for two 6 h long sessions. The copper catalyst was synthesized using incipient wetness…

  4. PMO-immobilized Au(I)-NHC complexes: Heterogeneous catalysts for sustainable processes

    KAUST Repository

    van der Voort, Pascal

    2017-11-08

    A stable Periodic Mesoporous Organosilica (PMO) with accessible sulfonic acid functionalities is prepared via a one-pot-synthesis and is used as solid support for highly active catalysts, consisting of gold(I)-N-heterocyclic carbene (NHC) complexes. The gold complexes are successfully immobilized on the nanoporous hybrid material via a straightforward acid-base reaction with the corresponding [Au(OH)(NHC)] synthon. This catalyst design strategy results in a boomerang-type catalyst, allowing the active species to detach from the surface to perform the catalysis and then to recombine with the solid after all the starting material is consumed. This boomerang behavior is assessed in the hydration of alkynes. The tested catalysts were found to be active in the latter reaction, and after an acidic work-up, the IPr*-based gold catalyst can be recovered and then reused several times without any loss in efficiency

  5. Development and characterisation of novel heterogeneous palm oil mill boiler ash-based catalysts for biodiesel production.

    Science.gov (United States)

    Ho, Wilson Wei Sheng; Ng, Hoon Kiat; Gan, Suyin

    2012-12-01

    Novel heterogeneous catalysts from calcium oxide (CaO)/calcined calcium carbonate (CaCO(3)) loaded onto different palm oil mill boiler ashes were synthesised and used in the transesterification of crude palm oil (CPO) with methanol to yield biodiesel. Catalyst preparation parameters including the type of ash support, the weight percentage of CaO and calcined CaCO(3) loadings, as well as the calcination temperature of CaCO(3) were optimised. The catalyst prepared by loading of 15 wt% calcined CaCO(3) at a fixed temperature of 800°C on fly ash exhibited a maximum oil conversion of 94.48%. Thermogravimetric analysis (TGA) revealed that the CaCO(3) was transformed into CaO at 770°C and interacted well with the ash support, whereas rich CaO, Al(2)O(3) and SiO(2) were identified in the composition using X-ray diffraction (XRD). The fine morphology size (<5 μm) and high surface area (1.719 m(2)/g) of the fly ash-based catalyst rendered it the highest catalytic activity. Copyright © 2012 Elsevier Ltd. All rights reserved.

  6. Economical and green biodiesel production process using river snail shells-derived heterogeneous catalyst and co-solvent method.

    Science.gov (United States)

    Roschat, Wuttichai; Siritanon, Theeranun; Kaewpuang, Teadkait; Yoosuk, Boonyawan; Promarak, Vinich

    2016-06-01

    River snail shells-derived CaO was used as a heterogeneous catalyst to synthesize biodiesel via transesterification of palm oil with methanol. The shell materials were calcined in air at 600-1000°C for 3h. Physicochemical properties of the resulting catalysts were characterized by TGA-DTG, XRD, SEM, BET, XRF, FT-IR and TPD. CaO catalyzed transesterification mechanism of palm oil into biodiesel was verified. The effects of adding a co-solvent on kinetic of the reaction and %FAME yield were investigated. %FAME yield of 98.5%±1.5 was achieved under the optimal conditions of catalyst/oil ratio of 5wt.%; methanol/oil molar ratio of 12:1; reaction temperature of 65°C; 10%v/v of THF in methanol and reaction time of 90min. The results ascertained that river snail shells is a novel raw material for preparation of CaO catalyst and the co-solvent method successfully decreases the reaction time and biodiesel production cost. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Biodiesel production from yellow horn (Xanthoceras sorbifolia Bunge.) seed oil using ion exchange resin as heterogeneous catalyst.

    Science.gov (United States)

    Li, Ji; Fu, Yu-Jie; Qu, Xue-Jin; Wang, Wei; Luo, Meng; Zhao, Chun-Jian; Zu, Yuan-Gang

    2012-03-01

    In this study, biodiesel production from yellow horn (Xanthoceras sorbifolia Bunge.) seed oil using ion exchange resin as heterogeneous catalyst was investigated. After illustration of the mechanisms of transesterification reactions catalyzed by typical ion exchange resins, the factors affecting microwave-assisted transesterification process were studied. A high conversion yield of about 96% was achieved under optimal conditions using high alkaline anion exchange resins as catalyst. Analyzing the FAMEs composition by GC-MS and main physical-chemical properties demonstrated that the biodiesel product prepared from yellow horn seed oil was of high quality. Compared with conventional alkali catalyst, the outstanding characteristics of reusability and operational stability made the resin catalyst more predominant for biodiesel production. In addition, a comprehensive kinetic model was established for analyzing the reaction. The results of present research showed that microwave-assisted transesterification process catalyzed by high alkaline anion exchange resin was a green, effective and economic technology for biodiesel industry. Copyright © 2012 Elsevier Ltd. All rights reserved.

  8. Certain aspects of the formation and identification of nanosized oxide components in heterogeneous catalysts prepared by different methods

    Science.gov (United States)

    Ellert, Ol'ga G.; Tsodikov, Mark V.; Novotortsev, Vladimir M.

    2010-10-01

    The results of studies into the relationship 'methods and synthesis conditions of a catalyst→catalyst structure→catalytic properties' in highly efficient crystallo-graphically amorphous copper- and iron-containing heterogeneous systems obtained by different chemical methods are generalized. Polymorphism of active phases and catalytic properties of nanostructured copper-containing zinc, zirconium, manganese and cerium oxides are discussed. Unusual transformations of nanosized Pt- and Pd-containing components on the γ-Al2O3 surface in nanostructured catalysts of ethanol steam reforming into synthesis gas and reductive dehydration of ethanol to alkanes are considered. The results of comparative studies on the crystallographically amorphous mixed iron oxide catalysts synthesized by either the alkoxy method or the deposition on various supports obtained by the Mössbauer and XAFS spectroscopy and magnetic susceptibility measurements are presented. These materials are shown to be efficient catalysts of important processes such as liquid-phase oxidation of hydrocarbons, synthesis of alkenes and alkylaromatic hydrocarbons from CO and H2, hydrogenative transformation of brown coal organic mass to hydrocarbons.

  9. The Use of Heterogeneous Catalysts of Chitosan Sulfonate Bead on the Esterification Reaction of Oleic Acid and Methanol

    Science.gov (United States)

    Chamidy, H. N.; Riniati

    2017-05-01

    Biodiesel is one of the ester compounds with physical properties closer to a biodiesel which can be produced by the esterification reaction between methanol and oleic acid (one of major components present in Palm Fatty Acid Distillate, PFAD). The purpose of this study was to obtain an optimum condition of esterification reaction by using chitosan sulfonate bead as heterogeneous catalysts. Chitosan sulfonate bead was made from chitosan undergo sulfonation process using acidic reagents cross-linked with sulfosalicylic and glutaraldehyde with a high enough value of ion exchange capacity. The stage of esterification reactions was carried by varying the amount of catalyst being added (4, 6, 8, 10, 12% by oleic acid), the operating temperature was varied of 40, 50 and 60 °C, and the reaction time of 1, 2, 3, 4 and 5 hours. Conversion determination of the products was done by analysing the free fatty acids content in each sample. Having obtained from the optimum amount of catalyst being added, temperature, and time, it was found that the catalyst was at 8%, 50 °C, during 5 hours in operation. The maximum conversion of oleic acid into biodiesel was 73.12%.

  10. Chitosan supported bimetallic Pd/Co nanoparticles as a heterogeneous catalyst for the reduction of nitroaromatics to amines

    Directory of Open Access Journals (Sweden)

    Sajjad Keshipour

    2017-01-01

    Full Text Available A new bimetallic nanocomposite of chitosan was prepared. Pd and Co nanoparticles were deposited on chitosan to produce a new heterogeneous recyclable catalyst for use in the bimetallic catalytic reduction reaction. The catalyst was characterized with common analysis methods for nanocomposites including Energy Dispersive X-Ray Spectroscopy, X-Ray Diffraction pattern, Thermal Gravimetric Analysis, Flame Atomic Absorption Spectroscopy and Scanning Electron Microscopy, and applied in the reduction reaction of nitroaromatics using NaBH4 at room temperature. The bimetallic system gave good results compared to each of the applied metals. Various aromatic amines and diamines were used in the reduction reaction. The aromatic amines were obtained as the sole product of the reduction reaction with 15 mol% Pd and 12 mol% Co during 2h. This reaction had some advantages such as mild reaction conditions, high yield, green solvent, and a recyclable catalyst. Also, the recovered catalyst was applicable in the reduction reaction without a significant decrease in the activity for up to six times.

  11. Aerobic oxidation of aqueous ethanol using heterogeneous gold catalysts: Efficient routes to acetic acid and ethyl acetate

    DEFF Research Database (Denmark)

    Jørgensen, Betina; Christiansen, Sofie Egholm; Thomsen, M.L.D.

    2007-01-01

    conditions, yields of 90-95% of acetic acid could be achieved at moderate temperatures and pressures. Based on our findings, a reaction pathway for the catalytic oxidation of ethanol via acetaldehyde to acetic acid is proposed, and the rate-determining step (RDS) in the mechanism is found to be the (possibly......The aerobic oxidation of aqueous ethanol to produce acetic acid and ethyl acetate was studied using heterogeneous gold catalysts. Comparing the performance of Au/MgAl2O4 and Au/TiO2 showed that these two catalysts exhibited similar performance in the reaction. By proper selection of the reaction...... oxygen-assisted) dehydrogenation of ethanol to produce acetaldehyde. It also is concluded that most of the CO2 formed as a byproduct in the reaction results from the absorbed intermediate in the dehydrogenation of ethanol to produce acetaldehyde. By varying the amount of water in the reaction mixture...

  12. [Decolorization of reactive blue P-3R with microsphere-supported binuclear Manganese complex as a novel heterogeneous CWPO catalyst].

    Science.gov (United States)

    Song, Min; Zhang, Lin-Ping; Zhong, Yi; Xu, Hong; Mao, Zhi-Ping

    2015-03-01

    Binuclear manganese complex (MnL), with high catalytic activity, was encapsulated into ethyl cellulose microspheres via a microencapsulation technique. The characterization of the catalyst through ICP, UV-VIS, SEM and TEM revealed that MnL was well distributed within the ethyl cellulose matrix. The results of UV-VIS confirmed the structural integrity of MnL after the encapsulation process. The MnL loaded microspheres exhibited an excellent catalytic property in the oxidative decolorization of Reactive Blue P-3R, which was used to simulate the dyestuff wastewater. The dye solution was completely decolorized under the catalyzing action of these microspheres. What's more, these MnL loaded microspheres could be reused for at least 4 times and the decolorization degree of Reactive Blue P-3R was maintained above 70%. The results demonstrated the potential application of the microsphere-supported MnL as a novel heterogeneous CWPO catalyst for the decolorization of wastewater containing dyestuff.

  13. THE WILKINSON COMPLEX AS A HETEROGENEOUS CATALYST IN THE PARTIAL HYDROGENATION OF 1-HEPTYNE. REGENERATION OF THE COMPLEX

    Directory of Open Access Journals (Sweden)

    Edgardo Cagnola

    2016-06-01

    Full Text Available The Wilkinson complex was tested as a catalyst in the partial hydrogenation of 1-heptyne, a medium chain alkyne, at a temperature of T = 303 K and hydrogen pressure PH2 = 150 kPa. The tests were performed in homogeneous system as well as heterogeneous system, supporting the complex on i γ-Al2O3 and ii a commercial carbonaceous material, RX3. Characterization by means of XPS and FTIR revealed that the anchored complex did not lose its chemical identity, being the catalytically active species. The Wilkinson complex on RX3 showed better conversions and selectivities, higher than the Lindlar catalyst, used as a reference. Additionally, it was proposed a method to recover Rh as a metal from the remaining solutions, and from it regenerate the complex to be reused from it.

  14. Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides.

    Science.gov (United States)

    Lennon, David; Winfield, John M

    2017-01-28

    Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials.

  15. Potent Heterogeneous Catalyst for Low Temperature Selective Oxidation of Cyclohexanol by Molecular Oxygen

    Directory of Open Access Journals (Sweden)

    Haroon ur Rashid

    2016-01-01

    Full Text Available Platinum supported on zirconium dioxide catalyst was prepared by standard method and characterized by SEM, EDX, XRD, BET surface area and pore size analyzer, and FT-IR. The catalyst was screened for its catalytic activity in a model reaction, selective oxidation of cyclohexanol. The only one major product, cyclohexanone 31%, with 99.8% selectivity was obtained. Experimental data was analyzed through different kinetic models and we deduced that the reaction follows Langmuir-Hinshelwood mechanism. The apparent activation energy for the model reaction was calculated as 45 kJ/mole. The catalyst was regenerated several times with same efficiency.

  16. Alkaline earth layered benzoates as reusable heterogeneous catalysts for the methyl esterification of benzoic acid

    Directory of Open Access Journals (Sweden)

    Swamy Arêa Maruyama

    2012-01-01

    Full Text Available This paper describes the synthesis and characterization of layered barium, calcium and strontium benzoates and evaluates the potential of these materials as catalysts in the synthesis of methyl benzoate. The methyl esterification of benzoic acid was investigated, where the effects of temperature, alcohol:acid molar ratio and amount of catalyst were evaluated. Ester conversions of 65 to 70% were achieved for all the catalysts under the best reaction conditions. The possibility of recycling these metallic benzoates was also demonstrated, evidenced by unaltered catalytic activity for three consecutive reaction cycles.

  17. Zero-valent iron supported on nitrogen-doped carbon xerogel as catalysts for the oxidation of phenol by fenton-like system.

    Science.gov (United States)

    Messele, S A; Soares, O S G P; Órfão, J J M; Bengoa, C; Font, J

    2017-09-03

    Nitrogen-free and nitrogen-doped carbon xerogel materials, from urea and melamine precursors, were prepared at different pH and evaluated as adsorbents/catalysts in the removal of phenol. Then, zero-valent iron (ZVI) was supported on these carbon xerogel materials and its activity was again evaluated for phenol removal by adsorption and catalytic wet peroxide oxidation (CWPO). The prepared samples were characterized by N2 adsorption at -196°C, pH at the point of zero charge (pHPZC) and elemental analysis. The textural properties of the N-free and N-doped carbon xerogels are strongly influenced by pH of the preparation solution and precursor used. The presence of ZVI on all carbon xerogel supports improved the phenol removal efficiency. ZVI supported on urea- and melamine-doped carbon xerogels show a good performance, reaching above 87% phenol conversion after 60 min of CWPO. On the contrary, pure adsorption and CWPO using the same materials without the presence of ZVI gives low phenol removal efficiency. A correlation was found between the activity of ZVI catalysts in CWPO and the N-content of the supports.

  18. Ultrasonic biodiesel synthesis from crude Jatropha curcas oil with heterogeneous base catalyst: mechanistic insight and statistical optimization.

    Science.gov (United States)

    Choudhury, Hanif A; Goswami, Partha Pratim; Malani, Ritesh S; Moholkar, Vijayanand S

    2014-05-01

    This paper reports studies in ultrasound-assisted heterogeneous solid catalyzed (CaO) synthesis of biodiesel from crude Jatropha curcas oil. The synthesis has been carried out in two stages, viz. esterification and trans-esterification. The esterification process is not influenced by ultrasound. The transesterification process, however, shows marked enhancement with ultrasound. A statistical experimental design has been used to optimize the process conditions for the synthesis. XRD analysis confirms formation of Ca(OMe)2, which is the active catalyst for transesterification reaction. The optimum values of parameters for the highest yield of transesterification have been determined as follows: alcohol to oil molar ratio ≈ 11, catalyst concentration ≈ 5.5 wt.%, and temperature ≈ 64°C. The activation energy of the reaction is calculated as 133.5 kJ/mol. The heterogeneity of the system increases mass transfer constraints resulting in approx. 4 × increase in activation energy as compared to homogeneous alkali catalyzed system. It is also revealed that intense micro-convection induced by ultrasound enhances the mass transfer characteristics of the system with ∼ 20% reduction in activation energy, as compared to mechanically agitated systems. Influence of catalyst concentration and alcohol to oil molar ratio on the transesterification yield is inter-linked through formation of methoxy ions and their diffusion to the oil-alcohol interface, which in turn is determined by the volume fractions of the two phases in the reaction mixture. As a result, the highest transesterification yield is obtained at the moderate values of catalyst concentration and alcohol to oil molar ratio. Copyright © 2013. Published by Elsevier B.V.

  19. Spatially and temporally resolved gas distributions around heterogeneous catalysts using infrared planar laser-induced fluorescence

    Science.gov (United States)

    Zetterberg, Johan; Blomberg, Sara; Gustafson, Johan; Evertsson, Jonas; Zhou, Jianfeng; Adams, Emma C.; Carlsson, Per-Anders; Aldén, Marcus; Lundgren, Edvin

    2015-01-01

    Visualizing and measuring the gas distribution in close proximity to a working catalyst is crucial for understanding how the catalytic activity depends on the structure of the catalyst. However, existing methods are not able to fully determine the gas distribution during a catalytic process. Here we report on how the distribution of a gas during a catalytic reaction can be imaged in situ with high spatial (400 μm) and temporal (15 μs) resolution using infrared planar laser-induced fluorescence. The technique is demonstrated by monitoring, in real-time, the distribution of carbon dioxide during catalytic oxidation of carbon monoxide above powder catalysts. Furthermore, we demonstrate the versatility and potential of the technique in catalysis research by providing a proof-of-principle demonstration of how the activity of several catalysts can be measured simultaneously, either in the same reactor chamber, or in parallel, in different reactor tubes. PMID:25953006

  20. Magnetically separable Fe3O4@DOPA–Pd: a heterogeneous catalyst for aqueous Heck reaction

    Data.gov (United States)

    U.S. Environmental Protection Agency — Magnetically separable Fe3O4@DOPA–Pd catalyst has been synthesized via anchoring of palladium over dopamine-coated magnetite via co-ordinate interaction and the...

  1. Supramolecular organization in organic-inorganic heterogeneous hybrid catalysts formed from polyoxometalate and poly(ampholyte) polymer.

    Science.gov (United States)

    Raj, Gijo; Swalus, Colas; Guillet, Alain; Devillers, Michel; Nysten, Bernard; Gaigneaux, Eric M

    2013-04-02

    Hybridization of polyoxometalates (POMs) via the formation of an organic-inorganic association constitutes a new route to develop a heterogeneous POM catalyst with tunable functionality imparted through supramolecular assembly. Herein, we report on strategies to obtain tunable well-defined supramolecular architectures of an organic-inorganic heterogeneous hybrid catalyst formed by the association of a hydrophobically substituted polyampholyte copolymer (poly N, N-diallyl-N-hexylamine-alt-maleic acid) and phosphotungstic acid (H3PW12O40) POMs. The self-assembling property of the initial polyampholyte copolymer matrix is modulated by controlling the pH of the hybridization solution. When deposited on a mica surface, isolated, long and extended polymer chains are formed under basic conditions (pH 7.9), while globular or coiled structures are formed under acidic conditions (pH 2). The supramolecular assembly of the POM-polymer hybrid is found to be directed by the type and quantities of charges present on the polyampholyte copolymer, which themselves depend on the pH conditions. The hypothesis is that the Keggin type [PW12O40](3-) anions, which have a size of ~1 nm, electrostatically bind to the positive charge sites of the polymer backbone. The hybrid material stabilized at pH 5.3 consists of POM-decorated polymer chains. Statistical analysis of distances between pairs of POM entities show narrow density distributions, suggesting that POM entities are attached to the polymer chains with a high level of order. Conversely, under acidic conditions (pH 2), the hybrid shows the formation of a core-shell type of structure. The strategies reported here, to tune the supramolecular assembly of organic-inorganic hybrid materials, are highly valuable for the design and a more rational utilization of POM heterogeneous catalysts in several chemical transformations.

  2. Bifunctional heterogeneous catalysts from oil palm empty fruit bunches ash and alum for biodiesel synthesis simultaneously

    Science.gov (United States)

    Astar, Ismail; Usman, Thamrin; Wahyuni, Nelly; Rudiyansyah, Alimuddin, Andi Hairil

    2017-03-01

    Free fatty acids (FFA) contained in crude palm oil (CPO) and sludge oil has been used as the base material of biodiesel with the aid of a catalyst in the transesterification and esterification reactions. This study aims to synthesize and characterize bifunctional catalysts were synthesized from the ashes of palm empty fruit bunches (EFB) and alum based on the analysis of XRD, XRF and acidity test. Bifunctional catalyst obtained was used as a catalyst to production of biodiesel with different levels of FFA. The optimum ratio alum added was 0.2 mol at 3 hours of reaction time and 3% of catalyst by the FFA samples were used 67,40%. The catalyst with optimum alum mole variations subsequently used on samples with varying levels of FFA, namely 1.29%, 4.98%, 29.21%, 67.40% and 74.47%. Optimum conversion of methyl ester in the esterification reaction occurs in the sample with 67.40% FFA content, which reached 86.17%, while the conversion of methyl ester transesterification process optimum amounted to 45.70% in the samples with 4.98% FFA content. Methyl ester produced has a refractive index of 1.448 (29.8 ° C), density of 0.883 g / mL (25 °C) and a viscosity of 8.933 cSt (25 ° C). The results of GC-MS analysis showed that the main composition of methyl ester result of esterification of sludge oil methyl palmitate (36.84%), while the CPO transesterification shows the main composition of methyl ester is methyl oleic (38.87%). Based on the research results, the catalyst synthesized from alum and EFB ash can be used as a Bifunctional catalysts for biodiesel synthesis.

  3. Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions.

    Science.gov (United States)

    Kalz, Kai F; Kraehnert, Ralph; Dvoyashkin, Muslim; Dittmeyer, Roland; Gläser, Roger; Krewer, Ulrike; Reuter, Karsten; Grunwaldt, Jan-Dierk

    2017-01-09

    In the future, (electro-)chemical catalysts will have to be more tolerant towards a varying supply of energy and raw materials. This is mainly due to the fluctuating nature of renewable energies. For example, power-to-chemical processes require a shift from steady-state operation towards operation under dynamic reaction conditions. This brings along a number of demands for the design of both catalysts and reactors, because it is well-known that the structure of catalysts is very dynamic. However, in-depth studies of catalysts and catalytic reactors under such transient conditions have only started recently. This requires studies and advances in the fields of 1) operando spectroscopy including time-resolved methods, 2) theory with predictive quality, 3) kinetic modelling, 4) design of catalysts by appropriate preparation concepts, and 5) novel/modular reactor designs. An intensive exchange between these scientific disciplines will enable a substantial gain of fundamental knowledge which is urgently required. This concept article highlights recent developments, challenges, and future directions for understanding catalysts under dynamic reaction conditions.

  4. Production of a Biofuel that Keeps the Glycerol as a Monoglyceride by Using Supported KF as Heterogeneous Catalyst

    OpenAIRE

    Calero, Juan; Cumplido, Gema; Luna, Diego; Sancho, Enrique D.; Luna, Carlos; Posadillo, Alejandro; Bautista, F.M.; Romero, Antonio A.; Verdugo-Escamilla, Cristóbal

    2014-01-01

    This study describes the results obtained in the synthesis of a biofuel that avoids the production of glycerol by applying supported KF as alkaline heterogeneous catalyst, to generate two moles of fatty acid methyl esters and one mole of monoglyceride from one mol of triglyceride. In this respect, the selective transesterification process of sunflower oil with methanol was carried out with KF (10 wt%) supported on three different solids, Al2O3, ZnO and MgO. The standard experimental condition...

  5. Preservation of glutamic acid-iron chelate into montmorillonite to efficiently degrade Reactive Blue 19 in a Fenton system under sunlight irradiation at neutral pH

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zhujian [College of Natural Resources and Environment, South China Agricultural University, Guangzhou 510642 (China); Wu, Pingxiao, E-mail: pppxwu@scut.edu.cn [School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, Guangzhou 510006 (China); Gong, Beini; Yang, Shanshan; Li, Hailing [School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); Zhu, Ziao; Cui, Lihua [College of Natural Resources and Environment, South China Agricultural University, Guangzhou 510642 (China)

    2016-05-01

    Graphical abstract: - Highlights: • G–Fe chelate molecules were well preserved into montmorillonite. • The product shows an excellent catalytic activity under sunlight at neutral pH value. • G–Fe–Mt is a promising catalyst for advanced oxidation processes. - Abstract: To further enhance the visible light responsive property and the chemical stability of Fe/clay mineral catalysts, glutamic acid-iron chelate intercalated montmorillonite (G–Fe–Mt) was developed. The physiochemical properties of G–Fe–Mt were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy (DRS), etc. The results showed that glutamic acid-iron chelates were successfully intercalated into the gallery of montmorillonite and the intercalated glutamic acid-iron chelate molecules were well preserved. The product G–Fe–Mt displayed excellent catalytic performance in heterogeneous photo-Fenton reaction under sunlight irradiation at acidic and neutral pH values. The chelation and the visible light responsiveness of glutamic acid produce a synergistic effect leading to greatly enhanced sunlight-Fenton reaction catalyzed by the heterogeneous G–Fe–Mt under neutral pH. G–Fe–Mt is a promising catalyst for advanced oxidation processes.

  6. Continuous Bulk FeCuC Aerogel with Ultradispersed Metal Nanoparticles: An Efficient 3D Heterogeneous Electro-Fenton Cathode over a Wide Range of pH 3-9.

    Science.gov (United States)

    Zhao, Hongying; Qian, Lin; Guan, Xiaohong; Wu, Deli; Zhao, Guohua

    2016-05-17

    Novel iron-copper-carbon (FeCuC) aerogel was fabricated through a one-step process from metal-resin precursors and then activated with CO2 and N2 in environmentally friendly way. The activated FeCuC aerogel was applied in a heterogeneous electro-Fenton (EF) process and exhibited higher mineralization efficiency than homogeneous EF technology. High total organic carbon (TOC) removal of organic pollutants with activated FeCuC aerogel was achieved at a wide range of pH values (3-9). The chemical oxygen demand (COD) of real dyeing wastewater was below China's discharge standard after 30 min of treatment, and the specific energy consumption was low (9.2 kW·h·kg(-1)COD(-1)), corresponding to a power consumption of only ∼0.34 kW·h per ton of wastewater. The enhanced mineralization efficiency of FeCuC aerogel was mostly attributable to ultradispersed metallic Fe-Cu nanoparticles embedded in 3D carbon matrix and the CO2-N2 treatment. The CO2 activation enhanced the accessibility of the aerogel's pores, and the secondary N2 activation enlarged the porosity and regenerated the ultradispersed zerovalent iron (Fe(0)) with reductive carbon. Cu(0) acted as a reduction promoter for interfacial electron transfer. Moreover, activated FeCuC aerogel presented low iron leaching (<0.1 ppm) in acidic solution and can be molded into different sizes with high flexibility. Thus, this material could be used as a low-cost cathode and efficient heterogeneous EF technology for actual wastewater treatment.

  7. Improving Heterogeneous Catalyst Stability for Liquid-phase Biomass Conversion and Reforming.

    Science.gov (United States)

    Héroguel, Florent; Rozmysłowicz, Bartosz; Luterbacher, Jeremy S

    2015-01-01

    Biomass is a possible renewable alternative to fossil carbon sources. Today, many bio-resources can be converted to direct substitutes or suitable alternatives to fossil-based fuels and chemicals. However, catalyst deactivation under the harsh, often liquid-phase reaction conditions required for biomass treatment is a major obstacle to developing processes that can compete with the petrochemical industry. This review presents recently developed strategies to limit reversible and irreversible catalyst deactivation such as metal sintering and leaching, metal poisoning and support collapse. Methods aiming to increase catalyst lifetime include passivation of low-stability atoms by overcoating, creation of microenvironments hostile to poisons, improvement of metal stability, or reduction of deactivation by process engineering.

  8. Production of biodiesel from palm oil (Elaeis guineensis) using heterogeneous catalyst: An optimized process

    Energy Technology Data Exchange (ETDEWEB)

    Hameed, B.H.; Lai, L.F.; Chin, L.H. [School of Chemical Engineering, Engineering Campus, University of Science Malaysia, 14300 Nibong Tebal, Penang (Malaysia)

    2009-04-15

    Response surface methodology (RSM) based on central composite design (CCD) was used to optimize the three important reaction variables - methanol/oil molar ratio (x{sub 1}), reaction time (x{sub 2}) and amount of catalyst (x{sub 3}) for production of biodiesel from palm oil using KF/ZnO catalyst. Based on the CCD, a quadratic model was developed to correlate the reaction variables to the biodiesel yield. From the analysis of variance (ANOVA), the most influential factor on the experimental design response was identified. The predicted yield after process optimization was found to agree satisfactory with the experimental value. The optimum conditions for biodiesel production were found as follows: methanol/oil ratio of 11.43, reaction time of 9.72 h and catalyst amount of 5.52 wt%. The optimum biodiesel yield was 89.23%. (author)

  9. Fe-based heterogeneous catalysts for the Fischer-Tropsch reaction: Sonochemical synthesis and bench-scale experimental tests.

    Science.gov (United States)

    Comazzi, Alberto; Pirola, Carlo; Longhi, Mariangela; Bianchi, Claudia L M; Suslick, Kenneth S

    2017-01-01

    The sonochemical synthesis of nanostructured materials owes its origins to the extreme conditions created during acoustic cavitation, i.e., the formation of localized hot spots in the core of collapsing bubbles in a liquid irradiated with high intensity ultrasound (US). In particular, in the present work a sonochemical synthesis has been investigated for the production of three different iron-based samples supported on SiO2 and loaded with different metals and promoters (10 %wt of Fe; 30 %wt of Fe; 30 %wt of Fe, 2 %wt of K and 3.75 %wt of Cu) active in the Fischer-Tropsch (FT) process. Sonochemically synthesized heterogeneous catalysts were characterized by BET, XRPD, TPR, ICP, CHN, TEM, SEM and then tested in a fixed bed FT-bench-scale rig fed with a mixture of H2 and CO at a H2/CO molar ratio equal to 2, at activation temperatures of 350-400°C and reaction temperatures of 250-260°C. The experimental results showed that the ultrasonic samples are effective catalysts for the FT process. Notably, increasing the activation temperature increased CO conversion, while product selectivity did not diminish. All the sonochemically prepared samples presented in this work provided better catalytic results compared to the corresponding traditional FT impregnated catalysts. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Biodiesel synthesis from cottonseed oil using homogeneous alkali catalyst and using heterogeneous multi walled carbon nanotubes: Characterization and blending studies

    Directory of Open Access Journals (Sweden)

    A. Arun Shankar

    2017-03-01

    Full Text Available The trans-esterification of cottonseed oil using strong alkali catalyst and using multi walled carbon nano tubes as catalyst to produce biodiesel was studied. The interaction effects of various factors such as temperature, amount of alkali used, alcohol to oil ratio and reaction time on yield of biodiesel were studied. The maximum yield of 95% biodiesel was obtained. The biodiesel produced was characterized using FT-IR spectral analysis and GC–MS analysis to ascertain the various functional groups and compounds available in it. The properties of biodiesel using homogeneous alkali catalyst and heterogeneous multi walled carbon nanotubes such as calorific value (36.18 MJ/kg, 33.78 MJ/kg, flash point (160 °C, 156 °C and other properties such as viscosity, cloud point, pour point and density were found to determine the quality of biodiesel produced. The studies were done by blending the biodiesel produced with diesel and properties of blended samples were estimated to ascertain the use of blended samples in internal combustion engines.

  11. Application of calcined waste fish (Labeo rohita) scale as low-cost heterogeneous catalyst for biodiesel synthesis.

    Science.gov (United States)

    Chakraborty, R; Bepari, S; Banerjee, A

    2011-02-01

    This paper explores the feasibility of converting waste Rohu fish (Labeo rohita) scale into a high-performance, reusable, low-cost heterogeneous catalyst for synthesis of biodiesel from soybean oil. The thermo-gravimetric analysis (TGA) and X-ray diffraction (XRD) analysis revealed that a significant portion of the main component of fish scale i.e. HAP (hydroxyapatite) could be transformed into β-tri-calcium phosphate when calcined above 900°C for 2 h. Scanning Electron Microscopy (SEM) morphology studies of the calcined scale depicted a fibrous layer of porous structure; while a BET surface area of 39 m(2)/g was measured. Response surface methodology (RSM) was employed to determine the optimal parametric conditions viz. methanol/oil molar ratio, 6.27:1, calcination temperature, 997.42°C and catalyst concentration, 1.01 wt.% of oil corresponding to a maximum FAME yield of 97.73%. Reusability results confirmed that the prepared catalyst could be reemployed up to six times, procreating a potentially applicable avenue in biodiesel synthesis. Copyright © 2010 Elsevier Ltd. All rights reserved.

  12. Esterification of camphene over heterogeneous heteropoly acid catalysts: synthesis of isobornyl carboxylates.

    OpenAIRE

    Meireles, Augusto Luís Pereira de; Rocha, Kelly Alessandra da Silva; Kozhevnikov, Ivan V.; Goussevskaia, Elena Vitalievna

    2011-01-01

    Silica supported H3PW12O40 (PW), the strongest heteropoly acid in the Keggin series, is an active and environmentally friendly solid acid catalyst for liquid-phase esterification of camphene, a renewable biomass-based substrate, with C2, C4 and C6 short-chain fatty acids. The reaction provides isobornyl carboxylates, useful as fragrances, in virtually 100% selectivity and 80–90% yield. The reaction is equilibrium-controlled and occurs under mild conditions with a catalyst turnover number of u...

  13. Magnetic M x O y @N-C as heterogeneous catalysts for the catalytic oxidation of aniline solution with sulfate radicals

    Science.gov (United States)

    Qin, Xin; Shi, Penghui; Liu, Haolin; Fan, Jinchen; Min, Yulin; Xu, Qunjie; Yao, Weifeng

    2017-06-01

    Metal nanoparticles have been combined with magnet metal-organic frameworks (MOFs) to afford new materials that demonstrate an efficient catalytic degradation, high stability, and excellent reusability in areas of catalysis because of their exceptionally high surface areas and structural diversity. Magnetic M x O y @N-C (M = Fe, Co, Mn) nanocrystals were formed on nitrogen-doped carbon surface by using 8-hydroxyquinoline as a C/N precursor. The Co@N-C, MnO@N-C, and Fe/Fe2O3@N-C catalysts were characterized by X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), N2 adsorption/desorption, and X-ray photoelectron spectroscopy (XPS). The catalytic performances of catalysts were thoroughly investigated in the oxidation of aniline solution based on sulfate radicals (SO4 -.) toward Fenton-like reaction. Magnetic M x O y @N-C exhibits an unexpectedly high catalytic activity in the degradation of aniline in water. A high magnetic M x O y @N-C catalytic activity was observed after the evaluation by aniline degradation in water. Aniline degradation was found to follow the first-order kinetics, and as a result, various metals significantly affected the structures and performances of the catalysts, and their catalytic activity followed the order of Co > Mn > Fe. The nanoparticles displayed good magnetic separation under the magnetic field.

  14. Humic acid coated Fe{sub 3}O{sub 4} magnetic nanoparticles as highly efficient Fenton-like catalyst for complete mineralization of sulfathiazole

    Energy Technology Data Exchange (ETDEWEB)

    Niu Hongyun [State Key Laboratory of Environmental Chemistry and Ecotoxicology of Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Zhang Di [State Key Laboratory of Environmental Chemistry and Ecotoxicology of Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); College of Science, Northwest A and F University, Yangling, Shaanxi 712100 (China); Zhang Shengxiao [State Key Laboratory of Environmental Chemistry and Ecotoxicology of Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); School of Chemistry and Materials Science, Ludong University, Yantai 264025 (China); Zhang Xiaole [State Key Laboratory of Environmental Chemistry and Ecotoxicology of Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); College of Chemical Engineering and Biological Technology, Hebei Polytechnic University, Tangshan 063000, Hebei (China); Meng Zhaofu [College of Science, Northwest A and F University, Yangling, Shaanxi 712100 (China); Cai Yaqi, E-mail: caiyaqi@rcees.ac.cn [State Key Laboratory of Environmental Chemistry and Ecotoxicology of Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China)

    2011-06-15

    Humic acid coated Fe{sub 3}O{sub 4} magnetic nanoparticles (Fe{sub 3}O{sub 4}/HA) were prepared for the removal of sulfathiazole from aqueous media. Fe{sub 3}O{sub 4}/HA exhibited high activity to produce hydroxyl ({center_dot}OH) radicals through catalytic decomposition of H{sub 2}O{sub 2}. The degradation of sulfathiazole was strongly temperature-dependent and favored in acidic solution. The catalytic rate was increased with Fe{sub 3}O{sub 4}/HA dosage and H{sub 2}O{sub 2} concentration. When 3 g L{sup -1} of Fe{sub 3}O{sub 4}/HA and 0.39 M of H{sub 2}O{sub 2} were introduced to the aqueous solution, most sulfathiazole was degraded within 1 h, and >90% of total organic carbon (TOC) were removed in the reaction period (6 h). The major final products were identified as environmentally friendly ions or inorganic molecules (SO{sub 4}{sup 2-}, CO{sub 2}, and N{sub 2}). The corresponding degradation rate (k) of sulfathiazole and TOC was 0.034 and 0.0048 min{sup -1}, respectively. However, when 3 g L{sup -1} of bare Fe{sub 3}O{sub 4} were used as catalyst, only 54% of TOC was eliminated, and SO{sub 4}{sup 2-} was not detected within 6 h. The corresponding degradation rate for sulfathiazole and TOC was 0.01 and 0.0016 min{sup -1}, respectively. The high catalytic ability of Fe{sub 3}O{sub 4}/HA may be caused by the electron transfer among the complexed Fe(II)-HA or Fe(III)-HA, leading to rapid regeneration of Fe(II) species and production of {center_dot}OH radicals.

  15. Biodiesel synthesis via heterogeneous catalysis using modified strontium oxides as the catalysts.

    Science.gov (United States)

    Chen, Ching-Lung; Huang, Chien-Chang; Tran, Dang-Thuan; Chang, Jo-Shu

    2012-06-01

    In this work, alkaline earth metal oxides (i.e., MgO, CaO, and SrO) were used as catalysts for the transesterification of olive oil with methanol. The most efficient catalyst was further doped with either CaO or SiO(2) to improve its catalytic activity, which was evaluated by conducting transesterification at different reaction temperatures, different water content, and using different types of oils. Finally, repeated tests were conducted to evaluate the reusability of the doped catalyst. The results show that the conversion of refined olive oil to biodiesel was more than 80% in 15 min when SrO was applied, while using SrO doped SiO(2) (SrO/SiO(2)) further increased the conversion to 95% in 10 min. SrO/SiO(2) also featured good water and free fatty acids (FFAs) tolerance, as the conversion was still higher than 90% (in 20 min) when the water and FFAs contents were increased to 3.23 and 3.14 wt.%, respectively. Addition of hexane significantly improved the reusability of SrO/SiO(2) for transesterification, as the biodiesel production still reached nearly 80% after the catalyst was repeatedly used for four times. Copyright © 2012 Elsevier Ltd. All rights reserved.

  16. Toward computational screening in heterogeneous catalysis: Pareto-optimal methanation catalysts

    DEFF Research Database (Denmark)

    Andersson, Martin; Bligaard, Thomas; Kustov, Arkadii

    2006-01-01

    Finding the solids that are the best catalysts for a given reaction is a daunting task due to the large number of combinations and structures of multicomponent Surfaces. In addition, it is not only the reaction rate that needs to be optimized: the selectivity. durability. and cost Must also be ta...

  17. Incorporation of Molecular Catalysts in Metal-Organic Frameworks for Highly Efficient Heterogeneous Catalysis.

    Science.gov (United States)

    Wu, Chuan-De; Zhao, Min

    2017-04-01

    Porous metal-organic frameworks (MOFs) are built from periodically alternate organic moieties and metal ions/clusters. The unique features of the open framework structures, the high surface areas, the permanent porosity, and the appropriate hydrophilic and hydrophobic pore nature mean that MOF materials are a class of ideal host matrices for immobilization of molecular catalysts. The emerging porous materials can not only retain but are also able to enhance the catalytic functions of the single individuals. MOF catalysts have the following super characters: i) uniformly dispersed catalytic sites on the pore surfaces to improve the utility, ii) appropriate hydrophilic and hydrophobic pore nature to facilitate the recognition and transportation of reactant and product molecules, iii) a collaborative microenvironment to realize synergistic catalysis, and iv) simple separation and recovery for long-term usage. Accompanying the development of the synthetic strategies and the technologies for the characterization of MOF materials, MOF catalysis has undergone an upsurge, which has transcended the stage of opportunism. Here, the rational design and synthesis of MOF catalysts are discussed, along with the key factors of active sites, microenvironments, and transmission channels that lead to the distinct catalytic properties of MOF catalysts. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Porphyrin-Based Metal-Organic Frameworks as Heterogeneous Catalysts in Oxidation Reactions

    Directory of Open Access Journals (Sweden)

    Carla F. Pereira

    2016-10-01

    Full Text Available Porphyrin-based Metal-Organic Frameworks (Por-MOFs constitute a special branch of the wide MOF family that has proven its own value and high potential in different applications. In this mini-review the application of these materials as catalysts in oxidation reactions is highlighted.

  19. FeCl3.nano SiO2: An Efficient Heterogeneous Nano Catalyst for the ...

    African Journals Online (AJOL)

    NICO

    Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, 51167-Kashan, Iran. Received 28 May 2012, ... recycling of these catalysts.1 Recent advances in nanoscience and nanotechnology have led to a new ... used surface material supports for different chemical transfor- mations in organic chemistry.

  20. Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

    Science.gov (United States)

    Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

    2017-02-07

    A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

  1. Copper on Chitosan: A Recyclable Heterogeneous Catalyst for Azide-alkyne Cycloaddition Reactions in Water

    Science.gov (United States)

    Copper sulfate is immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with copper sulfate; the ensuing catalyst has been utilized for the azide-alkyne cycloaddition in aqueous media and it can be recycled and reused many time without loosing it...

  2. Cyclisation of citronellal over heterogeneous inorganic fluorides--highly chemo- and diastereoselective catalysts for (+/-)-isopulegol.

    Science.gov (United States)

    Coman, Simona M; Patil, Pratap; Wuttke, Stefan; Kemnitz, Erhard

    2009-01-28

    Based on a fluorolytic sol-gel synthesis, nanoscopic metal fluorides and partly hydroxylated metal fluorides were synthesized; varying the F : OH ratio inside these solids yielded catalysts with different combinations and variable strength Lewis and Brønsted acid sites, which demonstrated unexpected catalytic properties for the diastereoselective synthesis of (+/-)-isopulegol.

  3. Nanostructured Co3O4grown on nickel foam: An efficient and readily recyclable 3D catalyst for heterogeneous peroxymonosulfate activation.

    Science.gov (United States)

    Yuan, Ruixia; Hu, Lin; Yu, Peng; Wang, Huaiyuan; Wang, Zhaohui; Fang, Jingyun

    2018-05-01

    Cobalt-based heterogeneous catalyst has been recognized as one of most efficient activators for peroxymonosulfate (PMS) decomposition, but usually suffers from the poor stability and difficulty to recover and reuse. Here easily recyclable cobalt oxide (Co 3 O 4 ) nanowires and nanoflowers grown on nickel foam (NF) are fabricated by a hydrothermal and calcination method. The prepared 3D Co 3 O 4 /NF catalyst is characterized and applied as a heterogeneous catalyst for PMS activation to generate sulfate radicals for decomposition of Acid Orange 7 (AO7). The results show that the AO7 degradation rate increases with cobalt loading and PMS dosage, but decreases with the increase of solution pH. The Co 3 O 4 /NF catalyst using 2 mM Co(NO 3 ) 2 ·6H 2 O as cobalt source exhibits highest activity, and almost complete decolorization could be achieved within 30 min. The diverse effects of coexisting anions (SO 4 2- , HCO 3 - , NO 3 - and Cl - ) on AO7 degradation are observed and explained. After 10 consecutive runs, excellent catalytic reactivity of the catalyst remains while the level of leached cobalt during the catalyst usage is much lower than the maximum allowable concentration in drinking and natural water. More importantly, the macroscopic Co 3 O 4 /NF catalyst shows advantage of easy recycling after application compared to traditional catalysts. It is believed that the as-prepared Co 3 O 4 /NF is promising to be an effective and green heterogeneous catalyst for PMS activation to degrade organic pollutants for environmental application. Copyright © 2018 Elsevier Ltd. All rights reserved.

  4. Adsorption of Vanadium (V) from SCR Catalyst Leaching Solution and Application in Methyl Orange.

    Science.gov (United States)

    Sha, Xuelong; Ma, Wei; Meng, Fanqing; Wang, Ren; Fuping, Tian; Wei, Linsen

    2016-12-01

      In this study, we explored an effective and low-cost catalyst and its adsorption capacity and catalytic capacity for Methyl Orange Fenton oxidation degradation were investigated. The catalyst was directly prepared by reuse of magnetic iron oxide (Fe3O4) after saturated adsorption of vanadium (V) from waste SCR (Selective Catalytic Reduction) catalyst. The obtained catalyst was characterized by FTIR, XPS and the results showed that vanadium (V) adsorption process of Fe3O4 nanoparticles was non-redox reaction. The effects of pH, adsorption kinetics and equilibrium isotherms of adsorption were assessed. Adsorption of vanadium (V) ions by Fe3O4 nanoparticles could be well described by the Sips isotherm model which controlled by the mixed surface reaction and diffusion (MSRDC) adsorption kinetic model. The results show that vanadium (V) was mainly adsorbed on external surface of the Fe3O4 nanoparticles. The separation-recovering tungsten (VI) and vanadium (V) from waste SCR catalyst alkaline solution through pH adjustment was also investigated in this study. The results obtained from the experiments indicated that tungsten (VI) was selectively adsorbed from vanadium (V)/tungsten (VI) mixed solution in certain acidic condition by Fe3O4 nanoparticle to realize their recovery. Tungsten (V) with some impurity can be obtained by releasing from adsorbent, which can be confirmed by ICP-AES. The Methyl Orange degradation catalytic performance illustrated that the catalyst could improve Fenton reaction effectively at pH = 3.0 compare to Fe3O4 nanoparticles alone. Therefore, Fe3O4 nanoparticle adsorbed vanadium (V) has a potential to be employed as a heterogeneous Fenton-like catalyst in the present contribution, and its catalytic activity was mainly evaluated in terms of the decoloration efficiency of Methyl Orange.

  5. Theoretical Studies in Heterogenous Catalysis: Towards a Rational Design of Novel Catalysts for Hydrodesulfurization and Hydrogen Production

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez,J.A.; Liu, P.

    2008-10-01

    Traditionally, knowledge in heterogeneous catalysis has come through empirical research. Nowadays, there is a clear interest to change this since millions of dollars in products are generated every year in the chemical and petrochemical industries through catalytic processes. To obtain a fundamental knowledge of the factors that determine the activity of heterogeneous catalysts is a challenge for modern science since many of these systems are very complex in nature. In principle, when a molecule adsorbs on the surface of a heterogeneous catalyst, it can interact with a large number of bonding sites. It is known that the chemical properties of these bonding sites depend strongly on the chemical environment around them. Thus, there can be big variations in chemical reactivity when going from one region to another in the surface of a heterogeneous catalyst. A main objective is to understand how the structural and electronic properties of a surface affect the energetics for adsorption processes and the paths for dissociation and chemical reactions. In recent years, advances in instrumentation and experimental procedures have allowed a large series of detailed works on the surface chemistry of heterogeneous catalysts. In many cases, these experimental studies have shown interesting and unique phenomena. Theory is needed to unravel the basic interactions behind these phenomena and to provide a general framework for the interpretation of experimental results. Ideally, theoretical calculations based on density-functional theory have evolved to the point that one should be able to predict patterns in the activity of catalytic surfaces. As in the case of experimental techniques, no single theoretical approach is able to address the large diversity of phenomena occurring on a catalyst. Catalytic surfaces are usually modeled using either a finite cluster or a two-dimensionally periodic slab. Many articles have been published comparing the results of these two approaches. An

  6. CaFeAl mixed oxide derived heterogeneous catalysts for transesterification of soybean oil to biodiesel.

    Science.gov (United States)

    Lu, Yongsheng; Zhang, Zaiwu; Xu, Yunfeng; Liu, Qiang; Qian, Guangren

    2015-08-01

    CaAl layered double oxides (LDO) were prepared by co-precipitation and calcined at 750°C, and then applied to biodiesel production by transesterification reaction between methanol and soybean oil. Compared with characteristics of CaFe/LDO and CaAl/LDO, CaFeAl/LDO had the best performance based on prominent catalytic activity and stability, and achieved over 90% biodiesel yield, which stayed stable (over 85%) even after 8 cycles of reaction. The optimal catalytic reaction condition was 12:1M-ratio of methanol/oil, reaction temperatures of 60°C, 270rpm stirring rate, 60min reaction time, and 6% weight-ratio of catalyst/oil. In addition, the CaFeAl/LDO catalyst is insoluble in both methanol and methyl esters and can be easily separated for further reaction, turning it into an excellent alternative for biodiesel synthesis. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Heterogeneous electrochemical CO2 reduction using nonmetallic carbon-based catalysts: current status and future challenges

    Science.gov (United States)

    Ma, Tao; Fan, Qun; Tao, Hengcong; Han, Zishan; Jia, Mingwen; Gao, Yunnan; Ma, Wangjing; Sun, Zhenyu

    2017-11-01

    Electrochemical CO2 reduction (ECR) offers an important pathway for renewable energy storage and fuels production. It still remains a challenge in designing highly selective, energy-efficient, robust, and cost-effective electrocatalysts to facilitate this kinetically slow process. Metal-free carbon-based materials have features of low cost, good electrical conductivity, renewability, diverse structure, and tunability in surface chemistry. In particular, surface functionalization of carbon materials, for example by doping with heteroatoms, enables access to unique active site architectures for CO2 adsorption and activation, leading to interesting catalytic performances in ECR. We aim to provide a comprehensive review of this category of metal-free catalysts for ECR, providing discussions and/or comparisons among different nonmetallic catalysts, and also possible origin of catalytic activity. Fundamentals and some future challenges are also described.

  8. In Situ Ptychography of Heterogeneous Catalysts using Hard X-Rays

    DEFF Research Database (Denmark)

    Baier, Sina; Damsgaard, Christian Danvad; Scholz, Maria

    2016-01-01

    A new closed cell is presented for in situ X-ray ptychography which allows studies under gas flow and at elevated temperature. In order to gain complementary information by transmission and scanning electron microscopy, the cell makes use of a Protochips E-chipTM which contains a small, thin...... electron transparent window and allows heating. Two gold-based systems, 50 nm gold particles and nanoporous gold as a relevant catalyst sample, were used for studying the feasibility of the cell. Measurements showing a resolution around 40 nm have been achieved under a flow of synthetic air and during...... heating up to temperatures of 933 K. An elevated temperature exhibited little influence on image quality and resolution. With this study, the potential of in situ hard X-ray ptychography for investigating annealing processes of real catalyst samples is demonstrated. Furthermore, the possibility to use...

  9. Navigating Glycerol Conversion Roadmap and Heterogeneous Catalyst Selection Aided by Density Functional Theory: A Review

    Directory of Open Access Journals (Sweden)

    Bin Liu

    2018-01-01

    Full Text Available Glycerol has been utilized in an extremely diversified manner throughout human civilization—ranging from food, to various consumer products, to pharmaceuticals, and even explosives. Large surplus in glycerol supply thanks to biodiesel production and biomass processing has created a demand to further boost its utility. One growing area is to expand the use of glycerol as an alternative feedstock to supplement fuels and chemicals production. Various catalytic processes have been developed. This review summarizes catalytic materials for glycerol reforming, hydrodeoxygenation, and oxidation. In particular, rationale for catalyst selection and new catalyst design will be discussed aided by the knowledge of reaction mechanisms. The role of theoretical density functional theory (DFT in elucidating complex glycerol conversion chemistries is particularly emphasized.

  10. Electrode-Modified Zeolites - Electrode Microstructures Contained in and on a Heterogeneous Catalyst

    Science.gov (United States)

    1988-07-15

    character of metals at sizes where’ bulk metallic properties may not be exhibited. Furthermore, electrolyses are now allowed using loadings of catalysts which...added for any of the electrolyses . All electrolytic experiments were performed with the cell thermostatted at 0- 5 C. A DC power supply (Kepco Models...strongly in zeolite. The lack of electrolytic contribution from interior Pt sites in Pt-Y has also been seen for dispersion electrolyses in neat

  11. Study of catalytic reduction and photodegradation of methylene blue by heterogeneous catalyst

    Science.gov (United States)

    Sohrabnezhad, Sh.

    2011-10-01

    The photocatalytic degradation of methylene blue is investigated in aqueous solution containing CoS/nanoAl-MCM-41 photocatalyst under visible light. The catalyst is characterized by X-ray diffraction (XRD), UV-vis diffused reflectance spectra (UV-vis DRS) and transmission electron microscopy (TEM) techniques. The effect of CoS, nanoAl-MCM-41 support and different wt% of CoS over the support on the photocatalytic degradation and influence of parameters such as CoS loading, catalyst amount, pH and initial concentration of methylene blue on degradation are evaluated. Hypsochromic effects (i.e. blue shifts of spectral bands) resulting from N-demethylation of the dimethylamino group in methylene blue occurs in presence of CoS/nanoAl-MCM-41 under ambient condition. Meanwhile, the bleaching of methylene blue MB, by sulfide ion, in an aqueous solution is studied in the presence nanoAl-MCM-41 catalyst. In the presence of sulfide ions, MB is bleached to its colorless leuco (LMB) and MBH 2+ forms. In an acidified solution (pH bleaching process generates LMB and by changing pH between 2.0 and 7.0 bleaching of MB dye to MBH 2+ form is observed. Using nanoAl-MCM-41 with encapsulated CoS nanoparticles only causes demethylation of MB in aqueous solution.

  12. Comparison of different heterogeneous catalysts and different alcohols for the esterification reaction of oleic acid

    Energy Technology Data Exchange (ETDEWEB)

    J.M. Marchetti; A.F. Errazu [Planta Piloto de Ingenieria Quimica (UNS-CONICET), Bahia Blanca (Argentina)

    2008-11-15

    Oils with high amount of free fatty acid (FFA) are becoming one of the most promising alternatives to produced biodiesel; due, principally, to it low cost. However, because of the presence of FFA, the conventional basic homogenous catalyst should not be used with the aim to avoid the production of soaps. In this work, different catalysts, such as solid resins, zeolite and enzymes, as well as different alcohols: ethanol anhydrous, ethanol 96{sup o}, 1-propanol, 2-propanol and butanol, were tested for the direct esterification reaction of pure oleic acid. The influence of several variables, such as alcohol's carbon chain length, the presence of water, which has a negative effect on the final conversion shifting the final conversion to a lower level, and the location of the OH group were studied. The enzymatic catalyst, Lipozyme CALB, turned out to be the best one, achieving a final conversion of 98% after three days reaction. Short communication. 33 refs., 5 figs., 1 tab.

  13. O-Carboxymethyl Chitosan Supported Heterogeneous Palladium and Ni Catalysts for Heck Reaction

    Directory of Open Access Journals (Sweden)

    Dongjun Lv

    2017-01-01

    Full Text Available Two polymer catalysts (Pd-OCMCS and Ni-OCMCS with good reusability were synthesized by coordinating Pd and Ni onto O-carboxymethyl chitosan (OCMCS. The chemical structure and thermal stability of prepared catalysts were determined by Fourier transform infrared (FT-IR spectra, Energy Dispersive Spectrometer (EDSanalysis, X-ray diffraction (XRD, and thermogravimetric analyzer (TG-DTG, and the analysis results showed that the Pd and Ni ions coordinated onto the OCMCS and formed a ligand with the –COOH group, amino groups, and –OH group on the OCMCS, and the EDS and Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES analysis results showed that the loading amounts of Pd and Ni were approximately 8.3% and 8.9%, respectively. In the Heck reaction between aryl halides and n-butyl acrylate catalyzed by the prepared catalyst, the test results showed that the product yield followed the order of aryl iodide > aryl bromide > aryl chloride. Additionally, the product yield for the aryl iodide and aryl bromide could reach up to 99% and 96%, respectively. Moreover, the electron-withdrawing and electron-donating property of the group on the aryl also affected the product yield, and the product yield for aryl halides with electron-withdrawing group p-NO2, p-CH3CO, and p-CHO was higher than that with electron-donating group p-CH3.

  14. Photodegradation of Methyl Green by Nickel-Dimethylglyoxime/ZSM-5 Zeolite as a Heterogeneous Catalyst

    Directory of Open Access Journals (Sweden)

    Alireza Nezamzadeh-Ejhieh

    2013-01-01

    Full Text Available Ni-DMG/ZSM-5 zeolite was prepared by ion exchange and complexation procedures. FT-IR, XRD, SEM, TG, and DTG methods were used for characterization of the raw and modified samples. The prepared composite was used as a catalyst in the photodegradation process of an aqueous solution methyl green (MG dye under UV irradiation. The effect of key operating parameters such as catalyst dosage, temperature, the initial concentration of the dye, and pH of the samples was studied on the degradation extent of the dye. UV-Vis spectrophotometric measurements were performed for determination of the decolorization and mineralization extents. The optimal operation parameters were found as follows: , temperature of 60°C, 0.6 g L−1 of the catalyst, and 40 ppm of the dye concentration. The Ni-DMG particles out of zeolite framework did not show significant degradation efficiency. The degradation process obeys the first-order kinetic.

  15. Decolourization of methyl orange using iron- immobilize MKSF in UV assisted Fenton-like reaction

    Science.gov (United States)

    Abdullah, N. H.; Zubir, N. A.; Hassan, H.

    2017-09-01

    In this work, montmorillonite KSF clay was used to immobilize iron species as a potential heterogeneous UV assisted Fenton-like reaction. Iron-immobilized MKSF (Fe-MKSF) was synthesized via hydrothermal method in an autoclave. Fe-MKSF was tested on methyl orange (MO) removal by adsorption (5%) and hydrogen peroxide (H2O2) activation (63%) and these prominent margins proved Fe-MKSF performance was attributed by UV assisted Fenton-like reaction. Fe-MKSF show superior performance with 63% color removal within 180 mins reaction in comparison to iron oxide and pristine MKSF. The Fe-MKSF increased in the surface area from 91.1 to 101.9 m2/g and pore volume from 0.13 to 0.45 cm3/g compared to pristine MKSF. The SEM images of Fe-MKSF show iron aggregates indicating successful immobilizing process and the elemental weight percent of iron which increase from 6.12% to 55.38% in Fe-MKSF. These findings prove Fe-MKSF as a promising alternative catalyst in dye contaminated wastewater treatment.

  16. Ferrocene-modified chitosan as an efficient and green heterogeneous catalyst for sulfate-radical-based advanced oxidation process.

    Science.gov (United States)

    Lin, Kun-Yi Andrew; Lin, Jyun-Ting; Yang, Hongta

    2017-10-01

    While ferrocene (Fc) is a promising heterogeneous catalyst for activating persulfate (PS) to degrade organic contaminants, chemical reagent-grade Fc is nanoscale and direct usage of Fc leads to operational and recovery issues. In this study, chitosan (CS) is selected as a support to immobilize Fc as CS is abundant, and environmental benign fishery waste. The amine group of CS also allows the formation of covalent bond between Fc-based reagent (i.e., Fc-CHO) and CS to form Fc-modified CS (Fc-CS). This Fc-CS can be more advantageous than Fc because of its easier recovery by precipitation and filtration. To evaluate Fc-CS for PS activation, degradation of Amaranth (AMR) dye by PS is selected as a model test. The resulting Fc-CS exhibits a higher catalytic activity than pristine Fc possibly because Fc can be evenly dispersed on CS and CS can also exhibit affinity toward AMR. AMR can be also fully decomposed by Fc-CS activated PS. Through the Electron paramagnetic resonance (EPR) spectroscopic analysis, the AMR degradation can be attributed to both sulfate and hydroxyl radicals. Fc-CS had been also proven to activate PS for AMR degradation over multiple times without loss of catalytic activity. These features indicate that Fc-CS can be a promising catalyst and CS appears to be a naturally available and environmentally friendly waste-derived support for immobilizing Fc. The results and findings in this study are essential for CS-supported metal catalysts in environmental applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Kinetics of transesterification of palm oil and dimethyl carbonate for biodiesel production at the catalysis of heterogeneous base catalyst.

    Science.gov (United States)

    Zhang, Liping; Sheng, Boyang; Xin, Zhong; Liu, Qun; Sun, Shuzhen

    2010-11-01

    The transesterification of palm oil with dimethyl carbonate (DMC) for preparing biodiesel has been studied in solvent-free system at the catalysis of potassium hydroxide (KOH) as heterogeneous catalyst. Fatty acid methyl esters (FAMEs) were analyzed by GC with internal standard method. The effects of reaction conditions (molar ratio of DMC and palm oil, catalyst amount and time) on FAMEs yield were investigated. The highest FAMEs yield could reach 96.2% at refluxing temperature for 8h with molar ratio of DMC and oil 9:1 and 8.5% KOH (based on oil weight). Kinetics of the KOH-catalyzed transesterification of palm oil and DMC was researched over a temperature range of 65-75 degrees C. A pseudo first-order model was proposed. The activation energy (E(a)) was 79.1 kJ mo1(-1) and the pre-exponential factor (k(o)) was 1.26 x 10(9) min(-1) from Arrhenius equation. Further, a plausible reaction mechanism for the catalytic process with DMC as acyl acceptor was proposed. Copyright 2010 Elsevier Ltd. All rights reserved.

  18. Heterogeneous Catalysts for VOC Oxidation from Red Mud and Bagasse Ash Carbon

    Science.gov (United States)

    Pande, Gaurav

    A range of VOC oxidation catalysts have been prepared in this study from agricultural and industrial waste as the starting point. The aim is to prepare catalysts with non-noble metal oxides as the active catalytic component (iron in red mud). The same active component was also supported on activated carbon obtained from unburned carbon in bagasse ash. Red mud which is an aluminum industry waste and rich in different phases of iron as oxide and hydroxide is used as the source for the catalytically active species. It is our aim to enhance the catalytic performance of red mud which though high in iron concentration has a low surface area and may not have the properties of an ideal catalyst by itself. In one of the attempts to enhance the catalytic performance, we have tried to leach red mud for which we have explored a range of leaching acids for effecting the leaching most efficiently and then precipitated the iron from the leachate as its hydroxide by precipitating with alkali solution followed by drying and calcination to give high surface area metal oxide material. Extensive surface characterization and VOC oxidation catalytic testing were performed for these solids. In a step to further enhance the catalytic activity towards oxidation, copper was introduced by taking another industrial waste from the copper tubing industry viz. the pickling acid. Copper has a more favourable redox potential making it catalytically more effective than iron. To make the mixed metal oxide, red mud leachate was mixed with the pickling acid in a pre-decided ratio before precipitating with alkali solution followed by drying and calcination as was done with the red mud leachate. The results from these experiments are encouraging. The temperature programmed reduction (TPR) of the solids show that the precipitate of red mud leachates show hydrogen uptake peak at a lower temperature than for just the calcined red mud. This could be due to the greatly enhanced surface area of the prepared

  19. Synthesis and characterization of mangenese(III) porphyrin supported on imidazole modified chloromethylated MIL-101(Cr): A heterogeneous and reusable catalyst for oxidation of hydrocarbons with sodium periodate

    Energy Technology Data Exchange (ETDEWEB)

    Zadehahmadi, Farnaz; Tangestaninejad, Shahram, E-mail: stanges@sci.ui.ac.ir; Moghadam, Majid, E-mail: moghadamm@sci.ui.ac.ir; Mirkhani, Valiollah, E-mail: mirkhani@sci.ui.ac.ir; Mohammadpoor-Baltork, Iraj; Khosropour, Ahmad R.; Kardanpour, Reihaneh

    2014-10-15

    In the present work, chloromethylated MIL-101(Cr) modified with imidazole, Im-MIL-101, was applied as a support for immobilizing of tetraphenylporphyrinatomangenese(III) chloride. The imidazole-bound MIL-101, Im-MIL-101, not only used as support for immobilization of manganese porphyrin but also applied as a heterogeneous axial base. The Mn(TPP)Cl@Im-MIL-101 catalyst was characterized by UV–vis, FT-IR, X-ray diffraction (XRD), N{sub 2} adsorption, field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX), elemental analysis and inductively coupled plasma (ICP) methods. The catalytic activity of this new catalytic system was investigated in the alkene epoxidation and alkane hydroxylation using NaIO{sub 4} as an oxidant in CH{sub 3}CN/H{sub 2}O at room temperature. This heterogeneous catalyst is highly efficient, stable and reusable in the oxidation of hydrocarbons. - Highlights: • MIL-101 was modified by covalent post synthetic modification. • Mn(TPP)Cl was anchored to imidazole modified MIL-101 by covalent attachment. • A heterogeneous catalyst was prepared. • The catalyst was used for epoxidation of alkenes and hydroxylation of alkanes. • The catalyst was reusable.

  20. The Produce of Methyl Ester from Crude Palm Oil (CPO) Using Heterogene Catalyst Ash of Chicken Bone (CaO) using Ethanol as Solvent

    Science.gov (United States)

    Sinaga, M. S.; Fauzi, R.; Turnip, J. R.

    2017-03-01

    Methyl Ester (methyl ester) is generally made by trans esterification using heterogeneous base catalyst. To simplify the separation, the heterogeneous catalyst is used, such as CaO, which in this case was isolated from chicken bones made by softening chicken bones and do calcination process. Some other important variables other than the selection of the catalyst is the catalyst dosage, molar ratio of ethanol to the CPO and the reaction temperature. The best result from this observe is at the molar ratio of ethanol to the CPO is 17: 1, the reaction temperature is 70 ° C and 7% catalyst (w.t) with reaction time for 7 hours at 500 rpm as a constant variable, got 90,052 % purity, so that this result does not get the standard requirements of biodiesel, because of the purity of the biodiesel standard temporary must be achieve > 96.5 %. This study aims to produce methyl ester yield with the influence of the reaction temperature, percent of catalyst and molar ratio of ethanol and CPO. The most influential variable is the temperature of the reaction that gives a significant yield difference of methyl ester produced. It’s been proven by the increasing temperature used will also significantly increase the yield of methyl ester.

  1. Catalytic decolorization of Acid blue 29 dye by H2O2 and a heterogeneous catalyst

    Directory of Open Access Journals (Sweden)

    Ibrahim A. Salem

    2014-09-01

    Full Text Available The montmorillonite K10-Cu(IIethylenediamine (MMTK10-Cu(en2 catalyst has been prepared by intercalation of copper-ethylenediamine [Cu(en2]2+ complex onto the montmorillonite K10. The intercalation process is confirmed by scanning electron microscopy (SEM, fourier transforms infrared spectroscopy (FTIR, X-ray diffraction (XRD, and thermogravimetric analysis (TGA measurements. The decolorization of the Acid blue29 was conducted using MMTK10-Cu(en2 in the presence of hydrogen peroxide. The effect of reactants concentrations and the temperature on the decolorization efficiency was studied. It was found that the efficiency of decolorization process increases with increasing the concentration of H2O2 and the dye and the temperature. The results indicated that complete removal of AB29 was achieved in 15 min when the concentrations of H2O2 and AB29 were 0.4 and 5 × 10−5 M respectively and 0.1 g of the catalyst at 30 °C. The activation parameters of the decolorization process were determined. Two possible mechanisms were proposed.

  2. A Green Solventless Protocol for the Synthesis of β-Enaminones and β-Enamino Esters Using Silica Sulfuric Acid as a Highly Efficient, Heterogeneous and Reusable Catalyst

    Directory of Open Access Journals (Sweden)

    Alireza Hasaninejad

    2010-01-01

    Full Text Available Silica sulfuric acid is utilized as a green, highly efficient, heterogeneous and recyclable catalyst for the preparation of β-enaminones and β-enamino esters from amines and β-dicarbonyl compounds under solvent-free conditions at 80 °C. Using this method, the title compounds are produced in high to excellent yields and in short reaction times.

  3. K-10 and KSF clays as green and recyclable heterogeneous catalysts for the Cannizzaro reaction using DABCO under MWI and solvent-free conditions

    OpenAIRE

    Omid Marvi; Maryam Talakoubi

    2016-01-01

    Montmorillonite K-10 and KSF clays as recyclable and heterogeneous catalysts are used to catalyze the Cannizzaro reaction by 1,4-diazabicyclo[2.2.2]octane (DABCO) under microwave irradiation (MWI) and solvent-free conditions in excellent yields within seconds. The solid clays applied in the first cycle is recovered and reused in the subsequent reactions.

  4. Amine grafted silica supported CrAuPd alloy nanoparticles: superb heterogeneous catalysts for the room temperature dehydrogenation of formic acid.

    Science.gov (United States)

    Yurderi, Mehmet; Bulut, Ahmet; Caner, Nurdan; Celebi, Metin; Kaya, Murat; Zahmakiran, Mehmet

    2015-07-21

    Herein we show that a previously unappreciated combination of CrAuPd alloy nanoparticles and amine-grafted silica support facilitates the liberation of CO-free H2 from dehydrogenation of formic acid with record activity in the absence of any additives at room temperature. Furthermore, their excellent catalytic stability makes them isolable and reusable heterogeneous catalysts in the formic acid dehydrogenation.

  5. Preservation of glutamic acid-iron chelate into montmorillonite to efficiently degrade Reactive Blue 19 in a Fenton system under sunlight irradiation at neutral pH

    Science.gov (United States)

    Huang, Zhujian; Wu, Pingxiao; Gong, Beini; Yang, Shanshan; Li, Hailing; Zhu, Ziao; Cui, Lihua

    2016-05-01

    To further enhance the visible light responsive property and the chemical stability of Fe/clay mineral catalysts, glutamic acid-iron chelate intercalated montmorillonite (G-Fe-Mt) was developed. The physiochemical properties of G-Fe-Mt were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), etc. The results showed that glutamic acid-iron chelates were successfully intercalated into the gallery of montmorillonite and the intercalated glutamic acid-iron chelate molecules were well preserved. The product G-Fe-Mt displayed excellent catalytic performance in heterogeneous photo-Fenton reaction under sunlight irradiation at acidic and neutral pH values. The chelation and the visible light responsiveness of glutamic acid produce a synergistic effect leading to greatly enhanced sunlight-Fenton reaction catalyzed by the heterogeneous G-Fe-Mt under neutral pH. G-Fe-Mt is a promising catalyst for advanced oxidation processes.

  6. OSU-6: A Highly Efficient, Metal-Free, Heterogeneous Catalyst for the Click Synthesis of 5-Benzyl and 5-Aryl-1H-tetrazoles

    Directory of Open Access Journals (Sweden)

    Baskar Nammalwar

    2015-12-01

    Full Text Available OSU-6, an MCM-41 type hexagonal mesoporous silica with mild Brönsted acid properties, has been used as an efficient, metal-free, heterogeneous catalyst for the click synthesis of 5-benzyl and 5-aryl-1H-tetrazoles from nitriles in DMF at 90 °C. This catalyst offers advantages including ease of operation, milder conditions, high yields, and reusability. Studies are presented that demonstrate the robust nature of the catalyst under the optimized reaction conditions. OSU-6 promotes the 1,3-dipolar addition of azides to nitriles without significant degradation or clogging of the nanoporous structure. The catalyst can be reused up to five times without a significant reduction in yield, and it does not require treatment with acid between reactions.

  7. Synthesis of fatty acid methyl ester from palm oil (Elaeis guineensis) with Ky(MgCa)2xO3 as heterogeneous catalyst.

    Science.gov (United States)

    Olutoye, M A; Lee, S C; Hameed, B H

    2011-12-01

    Fatty acid methyl esters (FAME) were produced from palm oil using eggshell modified with magnesium and potassium nitrates to form a composite, low-cost heterogeneous catalyst for transesterification. The catalyst, prepared by the combination of impregnation/co-precipitation was calcined at 830 °C for 4 h. Transesterification was conducted at a constant temperature of 65 °C in a batch reactor. Design of experiment (DOE) was used to optimize the reaction parameters, and the conditions that gave highest yield of FAME (85.8%) was 5.35 wt.% catalyst loading at 4.5 h with 16:1 methanol/oil molar ratio. The results revealed that eggshell, a solid waste, can be utilized as low-cost catalyst after modification with magnesium and potassium nitrates for biodiesel production. Copyright © 2011 Elsevier Ltd. All rights reserved.

  8. Selective Heck Arylation of Cyclohexene with Homogeneous and Heterogeneous Palladium Catalysts

    Directory of Open Access Journals (Sweden)

    Ewa Mieczyńska

    2010-03-01

    Full Text Available Palladium catalysts containing Pd(II supported on Al2O3 and alumina-based mixed oxides, Al2O3-ZrO2, Al2O3-CeO2, and Al2O3-Fe2O3, are very effective in the Heck coupling of iodobenzene with cyclohexene in DMF solution. The best results, up to 81% of monoarylated products with a selectivity to 4-phenylcyclohexene (3 close to 90% were obtained with KOH as a base. The catalytic activity of palladium supported on alumina-based oxides was compared with that of homogeneous precursors, such as Pd(OAc2 and PdCl2(PhCN2, used in [Bu4N]Br as the reaction medium. Under such conditions homogeneous systems were more selective and produced up to 60% of monoarylated products with a selectivity to 3 close to 60%.

  9. Preparation and Characterization of Anadara Granosa Shells and CaCO3 as Heterogeneous Catalyst for Biodiesel Production

    National Research Council Canada - National Science Library

    Hadiyanto Hadiyanto; Sri Puji Lestari; Widayat Widayat

    2016-01-01

    .... The CaCO3 based catalyst gained high yield of biodiesel (94%) as compared to Anadara granoasa based catalyst (92%). The reusability study showed that these catalysts could be used until three times recycle with 40-60% yield of biodiesel. The CaO contents of catalyst decreased up to 90% after three times recycles.

  10. Fenton Process Coupled to Ultrasound and UV Light Irradiation for the Oxidation of a Model Pollutant

    Directory of Open Access Journals (Sweden)

    Karen E. Barrera-Salgado

    2016-01-01

    Full Text Available The Fenton process coupled to photosonolysis (UV light and Us, using Fe2O3 catalyst supported on Al2O3, was used to oxidize a model pollutant like acid green 50 textile dye (AG50. Dye degradation was followed by AG50 concentration decay analyses. It was observed that parameters like iron content on a fixed amount of catalyst supporting material, catalyst annealing temperature, initial dye concentration, and the solution pH influence the overall treatment efficiency. High removal efficiencies of the model pollutant are achieved. The stability and reusability tests of the Fe2O3 catalyst show that the catalyst can be used up to three cycles achieving high discoloration. Thus, this catalyst is highly efficient for the degradation of AG50 in the Fenton process.

  11. Solvent-Induced Reversal of Activities between Two Closely Related Heterogeneous Catalysts in the Aldol Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kandel, Kapil [Ames Laboratory; Althaus, Stacey M [Ames Laboratory; Peeraphatdit, Chorthip [Ames Laboratory; Kobayashi, Takeshi [Ames Laboratory; Trewyn, Brian G [Ames Laboratory; Pruski, Marek [Ames Laboratory; Slowing, Igor I [Ames Laboratory

    2013-01-11

    The relative rates of the aldol reaction catalyzed by supported primary and secondary amines can be inverted by 2 orders of magnitude, depending on the use of hexane or water as a solvent. Our analyses suggest that this dramatic shift in the catalytic behavior of the supported amines does not involve differences in reaction mechanism, but is caused by activation of imine to enamine equilibria and stabilization of iminium species. The effects of solvent polarity and acidity were found to be important to the performance of the catalytic reaction. This study highlights the critical role of solvent in multicomponent heterogeneous catalytic processes.

  12. MAu2GeS4-Chalcogel (M = Co, Ni): Heterogeneous Intra- and Intermolecular Hydroamination Catalysts

    KAUST Repository

    Davaasuren, Bambar

    2017-08-08

    High surface area macroporous chalcogenide aerogels (chalcogels) MAu2GeS4 (M = Co, Ni) were prepared from K2Au2GeS4 precursor and Co(OAc)2 or NiCl2 by one-pot sol-gel metathesis reactions in aqueous media. The MAu2GeS4-chalcogels were screened for catalytic intramolecular hydroamination of 4-pentyn-1-amine substrate at different temperatures. 87% and 58% conversion was achieved at 100 °C, using CoAu2GeS4- and NiAu2GeS4-chalcogels respectively, and the reaction kinetics follows the first order. It was established that the catalytic performance of the aerogels is associated with the M(2+) centers present in the structure. Intermolecular hydroamination of aniline with 1-R-4-ethynylbenzene (R = -H, -OCH3, -Br, -F) was carried out at 100 °C using CoAu2GeS4-chalcogel catalyst, due to its promising catalytic performance. The CoAu2GeS4-chalcogel regioselectively converted the pair of substrates to respective Markovnikov products, (E)-1-(4-R-phenyl)-N-phenylethan-1-imine, with 38% to 60% conversion.

  13. Synthesis of multi-functionalized benzofurans through the condensation of ninhydrin and phenols using SSA as a recyclable heterogeneous acid catalyst.

    Science.gov (United States)

    Kundu, Ashis; Pramanik, Animesh

    2016-08-01

    A simple and efficient one-pot methodology has been developed for the synthesis of biologically important multi-functionalized 3-(2[Formula: see text]-hydroxyaryl)-2-(2[Formula: see text]-carboxyphenyl)benzofurans using silica sulfuric acid (SSA) as a heterogeneous acid catalyst in DMF medium. The significant advantages of this methodology are the use of SSA as a recyclable solid acid catalyst, operational simplicity, easy availability of the starting materials, and good yield of the products with high atom-economy.

  14. Single molecule methods for the study of catalysis: from enzymes to heterogeneous catalysts.

    Science.gov (United States)

    Janssen, Kris P F; De Cremer, Gert; Neely, Robert K; Kubarev, Alexey V; Van Loon, Jordi; Martens, Johan A; De Vos, Dirk E; Roeffaers, Maarten B J; Hofkens, Johan

    2014-02-21

    Structural and temporal inhomogeneities can have a marked influence on the performance of inorganic and biocatalytic systems alike. While these subtle variations are hardly ever accessible through bulk or ensemble averaged activity screening, insights into the molecular mechanisms underlying these diverse phenomena are absolutely critical for the development of optimized or novel catalytic systems and processes. Fortunately, state-of-the-art fluorescence microscopy methods have allowed experimental access to this intriguing world at the nanoscale. In this tutorial review we will first provide a broad overview of key concepts and developments in the application of single molecule fluorescence spectroscopy to (bio)catalysis research. In the second part topics specific to both bio and heterogeneous catalysis will be reviewed in more detail.

  15. Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: A review on heterogeneous catalysts and applications.

    Science.gov (United States)

    Zhao, Qingxia; Mao, Qiming; Zhou, Yaoyu; Wei, Jianhong; Liu, Xiaocheng; Yang, Junying; Luo, Lin; Zhang, Jiachao; Chen, Hong; Chen, Hongbo; Tang, Lin

    2017-12-01

    In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. CoFe{sub 2}O{sub 4} magnetic nanoparticles as a highly active heterogeneous catalyst of oxone for the degradation of diclofenac in water

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Jing [State Key Laboratory of Pollution Control Reuse, Tongji University, Shanghai 200092 (China); Shao, Yisheng, E-mail: shaoyisheng2011@163.com [State Key Laboratory of Pollution Control Reuse, Tongji University, Shanghai 200092 (China); China Academy of Urban Planning and Design, Beijing 100037 (China); Gao, Naiyun; Tan, Chaoqun; Zhou, Shiqing; Hu, Xuhao [State Key Laboratory of Pollution Control Reuse, Tongji University, Shanghai 200092 (China)

    2013-11-15

    Highlights: • CoFe{sub 2}O{sub 4} MNPs tested as heterogeneous catalyst for the activation of oxone. • The catalytic performance was typically affected by several key operating parameters. • The catalyst exhibited good stability and easily recovered with excellent reusability. • Degradation pathway was proposed according to the results of LC-MS/MS analysis. -- Abstract: A magnetic nanoscaled catalyst cobalt ferrite (CoFe{sub 2}O{sub 4}) was successfully prepared and used for the activation of oxone to generate sulfate radicals for the degradation of diclofenac. The catalyst was characterized by transmission electron microscopy, X-ray diffractometry, Fourier transform infrared spectroscopy and vibrating sample magnetometer. The effects of calcination temperature, initial pH, catalyst and oxone dosage on the degradation efficiency were investigated. Results demonstrated that CoFe{sub 2}O{sub 4}-300 exhibited the best catalytic performance and almost complete removal of diclofenac was obtained in 15 min. The degradation efficiency increased with initial pH decreasing in the pH range of 5–9. The increase of catalyst and oxone dosage both had the positive effect on the degradation of diclofenac. Moreover, CoFe{sub 2}O{sub 4} could retain high degradation efficiency even after being reused for five cycles. Finally, the major diclofenac degradation intermediates were identified and the primary degradation pathways were proposed.

  17. Continuous biodiesel production in a fixed bed reactor packed with anion-exchange resin as heterogeneous catalyst.

    Science.gov (United States)

    Ren, Yanbiao; He, Benqiao; Yan, Feng; Wang, Hong; Cheng, Yu; Lin, Ligang; Feng, Yaohui; Li, Jianxin

    2012-06-01

    A continuous biodiesel production from the transesterification of soybean oil with methanol was investigated in a fixed bed reactor packed with D261 anion-exchange resin as a heterogeneous catalyst. The conversion to biodiesel achieved 95.2% within a residence time 56 min under the conditions: reaction temperature of 323.15K, n-hexane/soybean oil weight rate of 0.5, methanol/soybean oil molar ratio of 9:1 and feed flow rate of 1.2 ml/min. The resin can be regenerated in-situ and restored to the original activity to achieve continuous production after the resin deactivation. The product obtained was mainly composed of methyl esters. No glycerol in the product was detected due to the resin adsorbing glycerol in the fixed bed, which solved the issue of glycerol separation from biodiesel. It is believed that the fixed bed reactor with D261 has a potential commercial application in the transesterification of triglyceride. Copyright © 2011 Elsevier Ltd. All rights reserved.

  18. Transesterification of Coconut Oil Using Dimethyl Carbonate and TiO2/SiO2 Heterogeneous Catalyst

    Directory of Open Access Journals (Sweden)

    Kamisah D. Pandiangan

    2013-05-01

    Full Text Available In this study, transesterification of coconut oil with dimethyl carbonate (DMC for preparing biodiesel has been studied using TiO2/SiO2 as heterogeneous catalyst, with the main purpose to investigate the effect of molar ratio of DMC to oil. The product was analyzed by GC-MS to identify the fatty acid methyl esters (FAMEs composting the biodiesel. The significant role of the DMC to oil ratio was observed in this study, in which the oil conversion was found to increase with increasing molar ratio of DMC : Oil, with the highest percent of conversion of 88.44%. The GC-MS analysis revealed the presence of methyl esters in accordance with the composition of coconut oil commonly reported. Formation of FAMEs was verified by 1H-NMR spectroscopic analysis, which also suggested that some of the fatty acids remain unconverted into biodiesel. The biodiesel produced was found to have kinematic viscosity of 2.4 mm2/S at 40 °C, flash point of 103 °C, and cetane number of 54.

  19. Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

    Science.gov (United States)

    Albayati, Talib M.; Doyle, Aidan M.

    2015-02-01

    Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption-desorption porosimetry (Brunauer-Emmett-Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96-99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.

  20. Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Albayati, Talib M., E-mail: talib-albyati@yahoo.com [University of Technology, Department of Chemical Engineering (Iraq); Doyle, Aidan M., E-mail: a.m.doyle@mmu.ac.uk [Manchester Metropolitan University, Division of Chemistry and Environmental Science (United Kingdom)

    2015-02-15

    Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption–desorption porosimetry (Brunauer–Emmett–Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96–99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.

  1. Controllable Synthesis of Lindqvist Alkoxopolyoxovanadate Clusters as Heterogeneous Catalysts for Sulfoxidation of Sulfides.

    Science.gov (United States)

    Li, Ji-Kun; Dong, Jing; Wei, Chuan-Ping; Yang, Song; Chi, Ying-Nan; Xu, Yan-Qing; Hu, Chang-Wen

    2017-05-15

    Six alkoxohexavanadate-based Cu- or Co-POVs [Cu(dpa)(acac)(H2O)]2[V6O13(OMe)6] (1), [Cu(phen)(acac)(MeOH)]2[V6O13(OMe)6] (2), [Co(dpa)(acac)2]2[V6O13(OMe)6]·2MeOH (3), [Co(phen)(acac)2]2[V6O13(OMe)6] (4), [Cu(dpa)(acac)]2[VIV2VV4O12(OMe)7] (5), and [Cu(dpa)(acac)(MeOH)]2[VIV2VV4O11(OMe)8] (6) (POV = polyoxovanadate; dpa = 2,2'-dipyridine amine; phen = 1,10-phenanthroline; acac = acetylacetone anion) have been synthesized by controlling the reaction conditions and characterized by single-crystal X-ray diffraction and powder X-ray diffraction analyses, FT-IR spectroscopy, element analyses, and X-ray photoelectron spectroscopy. In compounds 1-4 and 6, Cu or Co complexes and alkoxohexavanadate anions are assembled through electrostatic interactions. Differently, in compound 5, seven-methoxo-substituted Lindqvist-type [V6O12(OMe)7]2- are bridged to Cu complex via terminal O atoms by coordination bonds. All compounds 1-6 exhibit excellent heterogeneous catalytic performance in oxidative desulfurization and CEES ((2-chloroethyl) ethyl sulfide, a sulfur mustard simulant) abatement with H2O2 as oxidant. Among them, the catalytic activity of 6 [conv. of DBT (dibenzothiophene) up to 100% in 6 h; conv. of CEES reached 100% and selectivity of CEESO ((2-chloroethyl) ethyl sulfoxide) up to 85% after 4 h] outperforms others and can be reused without losing its activity.

  2. Intensification of biodiesel production from soybean oil and waste cooking oil in the presence of heterogeneous catalyst using high speed homogenizer.

    Science.gov (United States)

    Joshi, Saurabh; Gogate, Parag R; Moreira, Paulo F; Giudici, Reinaldo

    2017-11-01

    In the present work, high speed homogenizer has been used for the intensification of biodiesel synthesis from soybean oil and waste cooking oil (WCO) used as a sustainable feedstock. High acid value waste cooking oil (27mg of KOH/g of oil) was first esterified with methanol using sulphuric acid as catalyst in two stages to bring the acid value to desired value of 1.5mg of KOH/g of oil. Transesterification of soybean oil (directly due to lower acid value) and esterified waste cooking oil was performed in the presence of heterogeneous catalyst (CaO) for the production of biodiesel. Various experiments were performed for understanding the effect of operating parameters viz. molar ratio, catalyst loading, reaction temperature and speed of rotation of the homogenizer. For soybean oil, the maximum biodiesel yield as 84% was obtained with catalyst loading of 3wt% and molar ratio of oil to methanol of 1:10 at 50°C with 12,000rpm as the speed of rotation in 30min. Similarly biodiesel yield of 88% was obtained from waste cooking oil under identical operating conditions except for the catalyst loading which was 1wt%. Significant increase in the rate of biodiesel production with yields from soybean oil as 84% (in 30min) and from WCO as 88% (30min) was established due to the use of high speed homogenizer as compared to the conventional stirring method (requiring 2-3h for obtaining similar biodiesel yield). The observed intensification was attributed to the turbulence caused at microscale and generation of fine emulsions due to the cavitational effects. Overall it can be concluded from this study that high speed homogenizer can be used as an alternate cavitating device to efficiently produce biodiesel in the presence of heterogeneous catalysts. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Formation of acetic acid by aqueous-phase oxidation of ethanol with air in the presence of a heterogeneous gold catalyst

    DEFF Research Database (Denmark)

    Christensen, Claus H.; Jørgensen, Betina; Hansen, Jeppe Rass

    2006-01-01

    Wine into vinegar: It is possible to selectively oxidize ethanol into acetic acid in aqueous solution with air as the oxidant and a heterogeneous gold catalyst (see TEM image of supported gold particles) at temperatures of about 423 K and O2 pressures of 0.6 MPa. This reaction proceeds readily...... in aqueous acidic media with yields of up to 90 % and CO2 as the only major by-product....

  4. Base-Catalyzed Depolymerization of Lignin with Heterogeneous Catalysts: Cooperative Research and Development Final Report, CRADA Number CRD-13-513

    Energy Technology Data Exchange (ETDEWEB)

    Beckham, Gregg T. [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2015-08-04

    We will synthesize and screen solid catalysts for the depolymerization of lignin to monomeric and oligomeric oxygenated species, which could be fractionated and integrated into refinery intermediate streams for selective upgrading, or catalytically upgraded to fuels and chemicals. This work will primarily focus on the synthesis and application of layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for depolymerization of lignin model compounds and softwood lignin. LDHs have been shown in our group to offer good supports and catalysts to promote base-catalyzed depolymerization of lignin model compounds and in preliminary experiments for the depolymerization of lignin from an Organosolv process. We will also include additional catalyst supports such as silica, alumina, and carbon as identified in ongoing and past efforts at NREL. This work will consist of two tasks. Overall, this work will be synergistic with ongoing efforts at NREL, funded by the DOE Biomass Program, on the development of catalysts for lignin depolymerization in the context of biochemical and thermochemical conversion of corn stover and other biomass feedstocks to advanced fuels and chemicals.

  5. Mesoporous Silica Supported Au Nanoparticles with Controlled Size as Efficient Heterogeneous Catalyst for Aerobic Oxidation of Alcohols

    Directory of Open Access Journals (Sweden)

    Xuefeng Chu

    2015-01-01

    Full Text Available A series of Au catalysts with different sizes were synthesized and employed on amine group functionalized ordered mesoporous silica solid supports as catalyst for the aerobic oxidation of various alcohols. The mesoporous silica of MCM-41 supported Au nanoparticles (Au-1 exhibited the smallest particle size at ~1.8 nm with superior catalytic activities owing to the confinement effect of the mesoporous channels. Au-1 catalyst is also very stable and reusable under aerobic condition. Therefore, this presented work would obviously provide us a platform for synthesizing more size-controlled metal catalysts to improve the catalytic performances.

  6. Heteropoly acid encapsulated into zeolite imidazolate framework (ZIF-67) cage as an efficient heterogeneous catalyst for Friedel–Crafts acylation

    Energy Technology Data Exchange (ETDEWEB)

    Ammar, Muhammad; Jiang, Sai; Ji, Shengfu, E-mail: jisf@mail.buct.edu.cn

    2016-01-15

    A new strategy has been developed for the encapsulation of the phosphotungstic heteropoly acid (H{sub 3}PW{sub 12}O{sub 40} denoted as PTA) into zeolite imidazolate framework (ZIF-67) cage and the PTA@ZIF-67(ec) catalysts with different PTA content were prepared. The structure of the catalysts was characterized by XRD, BET, SEM, FT-IR, ICP-AES and TG. The catalytic activity and recovery properties of the catalysts for the Friedel-Crafts acylation of anisole with benzoyl chloride were evaluated. The results showed that 14.6–31.7 wt% PTA were encapsulated in the ZIF-67 cage. The PTA@ZIF-67(ec) catalysts had good catalytic activity for Friedel-Crafts acylation. The conversion of anisole can reach ~100% and the selectivity of the production can reach ~94% over 26.5 wt% PTA@ZIF-67(ec) catalyst under the reaction condition of 120 °C and 6 h. After reaction, the catalyst can be easily separated from the reaction mixture by the centrifugation. The recovered catalyst can be reused five times and the selectivity can be kept over 90%. - Graphical abstract: The PTA@ZIF-67 catalysts with different PTA content were prepared by encapsulating the PTA into ZIF-67 cage and the as-synthesized catalysts exhibited good catalytic activity for the Friedel–Craft acylation of anisole with benzoyl chloride.

  7. Municipal Solid Waste Landfill Leachate Treatment by Fenton, Photo-Fenton and Fenton-Like Processes: Effect of some Variables

    Directory of Open Access Journals (Sweden)

    Maryam Bagheri Ardebilian

    2012-08-01

    Full Text Available Advanced oxidation processes like Fenton and photo-Fenton have been effectively applied to oxidize the persistent organic compounds in solid waste leachate and convert them to unharmful materials and products. However, there are limited data about application of Fenton-like process in leachate treatment. Therefore, this study was designed with the objective of treating municipal landfill leachate by Fenton, Fenton-like and photo–Fenton processes to determine the effect of different variables, by setting up a pilot system. The used leachate was collected from a municipal unsanitary landfill in Qaem-Shahr in the north of Iran. Fenton and Fenton-like processes were conducted by Jar-test method. Photo-Fenton process was performed in a glass photo-reactor. In all processes, H2O2 was usedas the oxidant. FeSO4.7H2O and FeCl3.6H2O were used as reagents. All parameters were measured based on standard methods. The results showed that the optimum concentration of H2O2 was equal to 5 g/L for the Fenton-like process and 3 g/L for the Fenton and photo-Fenton processes. The optimum ratio of H2O2: Fe+2/Fe+3 were equal to 8:1 in all processes. At optimum conditions, the amount of COD removal was 69.6%, 65.9% and 83.2% in Fenton, Fenton-like and photo–Fenton processes, respectively. In addition, optimum pH were 3, 5 and 3and the optimum contact time were 150, 90 and 120 minutes, for Fenton, Fenton-like and photo–Fenton processes, respectively. After all processes, the biodegradability (BOD5/COD ratio of the treated leachate was increased compared to that of the raw leachate and the highest increase in BOD5/COD ratio was observed in the photo-Fenton process. The efficiency of the Fenton-like process was overally less than Fenton and photo-Fenton processes, meanwhile the Fenton-like process was at higher pH and did not show problems.

  8. Municipal solid waste landfill leachate treatment by fenton, photo-fenton and fenton-like processes: Effect of some variables.

    Science.gov (United States)

    Zazouli, Mohammad Ali; Yousefi, Zabihollah; Eslami, Akbar; Ardebilian, Maryam Bagheri

    2012-08-02

    Advanced oxidation processes like Fenton and photo-Fenton have been effectively applied to oxidize the persistent organic compounds in solid waste leachate and convert them to unharmful materials and products. However, there are limited data about application of Fenton-like process in leachate treatment. Therefore, this study was designed with the objective of treating municipal landfill leachate by Fenton, Fenton-like and photo-Fenton processes to determine the effect of different variables, by setting up a pilot system. The used leachate was collected from a municipal unsanitary landfill in Qaem-Shahr in the north of Iran. Fenton and Fenton-like processes were conducted by Jar-test method. Photo-Fenton process was performed in a glass photo-reactor. In all processes, H2O2 was used as the oxidant. FeSO4.7H2O and FeCl3.6H2O were used as reagents. All parameters were measured based on standard methods. The results showed that the optimum concentration of H2O2 was equal to 5 g/L for the Fenton-like process and 3 g/L for the Fenton and photo-Fenton processes. The optimum ratio of H2O2: Fe+2/Fe+3 were equal to 8:1 in all processes. At optimum conditions, the amount of COD removal was 69.6%, 65.9% and 83.2% in Fenton, Fenton-like and photo-Fenton processes, respectively. In addition, optimum pH were 3, 5 and 3 and the optimum contact time were 150, 90 and 120 minutes, for Fenton, Fenton-like and photo-Fenton processes, respectively. After all processes, the biodegradability (BOD5/COD ratio) of the treated leachate was increased compared to that of the raw leachate and the highest increase in BOD5/COD ratio was observed in the photo-Fenton process. The efficiency of the Fenton-like process was overally less than Fenton and photo-Fenton processes, meanwhile the Fenton-like process was at higher pH and did not show problems.

  9. Municipal solid waste landfill leachate treatment by fenton, photo-fenton and fenton-like processes: Effect of some variables

    Directory of Open Access Journals (Sweden)

    Zazouli Mohammad

    2012-08-01

    Full Text Available Abstract Advanced oxidation processes like Fenton and photo-Fenton have been effectively applied to oxidize the persistent organic compounds in solid waste leachate and convert them to unharmful materials and products. However, there are limited data about application of Fenton-like process in leachate treatment. Therefore, this study was designed with the objective of treating municipal landfill leachate by Fenton, Fenton-like and photo–Fenton processes to determine the effect of different variables, by setting up a pilot system. The used leachate was collected from a municipal unsanitary landfill in Qaem-Shahr in the north of Iran. Fenton and Fenton-like processes were conducted by Jar-test method. Photo-Fenton process was performed in a glass photo-reactor. In all processes, H2O2 was used as the oxidant. FeSO4.7H2O and FeCl3.6H2O were used as reagents. All parameters were measured based on standard methods. The results showed that the optimum concentration of H2O2 was equal to 5 g/L for the Fenton-like process and 3 g/L for the Fenton and photo-Fenton processes. The optimum ratio of H2O2: Fe+2/Fe+3 were equal to 8:1 in all processes. At optimum conditions, the amount of COD removal was 69.6%, 65.9% and 83.2% in Fenton, Fenton-like and photo–Fenton processes, respectively. In addition, optimum pH were 3, 5 and 3 and the optimum contact time were 150, 90 and 120 minutes, for Fenton, Fenton-like and photo–Fenton processes, respectively. After all processes, the biodegradability (BOD5/COD ratio of the treated leachate was increased compared to that of the raw leachate and the highest increase in BOD5/COD ratio was observed in the photo-Fenton process. The efficiency of the Fenton-like process was overally less than Fenton and photo-Fenton processes, meanwhile the Fenton-like process was at higher pH and did not show problems.

  10. Hydroxide catalysts for lignin depolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Beckham, Gregg T.; Biddy, Mary J.; Chmely, Stephen C.; Sturgeon, Matthew

    2017-04-25

    Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

  11. Hydroxide catalysts for lignin depolymerization

    Science.gov (United States)

    Beckham, Gregg T; Biddy, Mary J.; Kruger, Jacob S.; Chmely, Stephen C.; Sturgeon, Matthew

    2017-10-17

    Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

  12. Use of iron and bio-oil wastes to produce highly dispersed Fe/C composites for the photo-Fenton reaction.

    Science.gov (United States)

    de Mendonça, Fernanda Gomes; Rosmaninho, Marcelo Gonçalves; da Fonseca, Philipe Xavier; Soares, Ricardo Reis; Ardisson, José Domingos; Tristão, Juliana Cristina; Lago, Rochel Montero

    2017-03-01

    This work describes the synthesis, characterization, and application of an active heterogeneous photo-Fenton system obtained from two different wastes, i.e., laterite (an iron mining waste) and the acid aqueous fraction (AAF) from bio-oil production. AAF with high acidity (ca. 3 molH+ L-1) and organic concentration (25 wt.%) obtained from biomass flash pyrolysis was used for the efficient extraction of Fe3+ from laterite waste. After extraction, the mixture Fe3+/AAF was dried and treated at different temperatures, i.e., 500, 650, and 800 °C, to obtain Fe/C reactive composites. Mössbauer, XRD, TG, elemental analyses, and SEM/EDS showed the presence of highly disperse Fe oxide nanoparticles at 500 and 650 °C and Fe0 particles in the material obtained at 800 °C with carbon contents varying from 74 to 80 %. The three composites were tested as heterogeneous catalysts in the photo-Fenton reaction for the oxidation of the model dye contaminant methylene blue, showing high activities at neutral pH.

  13. Municipal solid waste landfill leachate treatment by fenton, photo-fenton and fenton-like processes: Effect of some variables

    National Research Council Canada - National Science Library

    Zazouli, Mohammad Ali; Yousefi, Zabihollah; Eslami, Akbar; Ardebilian, Maryam Bagheri

    2012-01-01

    Advanced oxidation processes like Fenton and photo-Fenton have been effectively applied to oxidize the persistent organic compounds in solid waste leachate and convert them to unharmful materials and products...

  14. A heterogeneous catalyst, SiO2-ZnBr2: An efficient neat access for α ...

    Indian Academy of Sciences (India)

    high yield of the product. Recent synthetic specifics of our group on the new methodologies using Lewis acid catalysts26 have encouraged us to focus initially develop a new method, before going on to evaluation of medicinal chemistry, for achieving high yield of the α- aminophosphonates. In search for an effective catalyst.

  15. Effect of ethylenediamine-N,N'-disuccinic acid on Fenton and photo-Fenton processes using goethite as an iron source: optimization of parameters for bisphenol A degradation.

    Science.gov (United States)

    Huang, Wenyu; Brigante, Marcello; Wu, Feng; Hanna, Khalil; Mailhot, Gilles

    2013-01-01

    The main disadvantage of using iron mineral in Fenton-like reactions is that the decomposition rate of organic contaminants is slower than in classic Fenton reaction using ferrous ions at acidic pH. In order to overcome these drawbacks of the Fenton process, chelating agents have been used in the investigation of Fenton heterogeneous reaction with some Fe-bearing minerals. In this work, the effect of new iron complexing agent, ethylenediamine-N,N'-disuccinic acid (EDDS), on heterogeneous Fenton and photo-Fenton system using goethite as an iron source was tested at circumneutral pH. Batch experiments including adsorption of EDDS and bisphenol A (BPA) on goethite, H(2)O(2) decomposition, dissolved iron measurement, and BPA degradation were conducted. The effects of pH, H(2)O(2) concentration, EDDS concentration, and goethite dose were studied, and the production of hydroxyl radical ((•)OH) was detected. The addition of EDDS inhibited the heterogeneous Fenton degradation of BPA but also the formation of (•)OH. The presence of EDDS decreases the reactivity of goethite toward H(2)O(2) because EDDS adsorbs strongly onto the goethite surface and alters catalytic sites. However, the addition of EDDS can improve the heterogeneous photo-Fenton degradation of BPA through the propagation into homogeneous reaction and formation of photochemically efficient Fe-EDDS complex. The overall effect of EDDS is dependent on the H(2)O(2) and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O (2) (•-) to generate Fe(II) species from Fe(III) reduction. Low concentrations of H(2)O(2) (0.1 mM) and EDDS (0.1 mM) were required as optimal conditions for complete BPA removal. These findings regarding the capability of EDDS/goethite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.

  16. Contribution of stimulations for the optimization of quantitative electron probe micro analysis of heterogeneous catalysts; Apport de la simulation dans l'optimisation de l'analyse quantitative par microsonde electronique de catalyseurs heterogenes

    Energy Technology Data Exchange (ETDEWEB)

    Sorbier, L.

    2001-11-01

    Electron Probe Micro Analysis (EPMA) is frequently used to measure the local concentration of active elements in heterogeneous catalysts. However, when classical procedures are used, a significant deficit is observed both in local total concentration and mean total concentrations. A Monte Carlo program simulating measured intensities (characteristic lines and continuous background) has been written using PENELOPE routines. We have included in this program models taking into account the different physical phenomena likely to lead to the observed signal loss (insulating properties, roughness, porosity, energy loss at interfaces). Simulation results have shown that an important roughness (Ra>200 nm) was the only parameter apt to lead to a significant total signal loss. This led us to inquire into another origin to explain the signal loss observed on meso-porous samples. Measurements conducted on a meso-porous alumina confirmed that measuring aluminum, oxygen and carbon leads to a correct total of concentrations. Signal loss is thus explained by the contamination of the sample during its preparation, the components of the embedding resin diffusing into the porosity and reacting with the reactive surface of the catalyst support. In the case of macroporous catalysts, local roughness effect is very important. The simulations have shown the efficiency of the Peak to Background method to correct these local roughness effects. Measurements conducted on reforming and hydro-treating catalysts have led to a correct total concentration and confirmed the contribution of the Peak to Background method to achieve local quantitative measurement. (author)

  17. Anchorage of Au3+into Modified Isoreticular Metal-Organic Framework-3 as a Heterogeneous Catalyst for the Synthesis of Propargylamines.

    Science.gov (United States)

    Liu, Lili; Tai, Xishi; Zhou, Xiaojing; Xin, Chunling; Yan, Yongmei

    2017-10-05

    Postsynthetic modification of metal-organic framework is a general and practical approach to access MOF-based catalysts bearing multiple active sites. The isoreticular metal-organic framework-3 (IRMOF-3) was modified with lactic acid through condensation reaction of the carboxyl group of lactic acid and amino group present in IRMOF-3 frameworks. Au 3+ was subsequently anchored onto the metal-organic framework IRMOF-3 using postsynthetic modification. The synthezized IRMOF-3-LA-Au (LA = lactic acid) was characterized by powder X-ray diffraction, N 2 adsorption-desorption, infrared spectroscopy, liquid-state nuclear magnetic resonance, thermogravimetric analysis, H 2 -temperature programmed reduction, transmission electro microscopy, and inductively coupled plasma-optical emission spectrometry. IRMOF-3-LA-Au acted as an efficient heterogeneous catalyst in the synthesis of propargylamines by three-component coupling reaction of aldehyde, alkyne, and amine. Moreover, the catalyst is applicable to various substituted substrates, including aromatic and aliphatic aldehydes, alkyl- and aryl-substituted terminal alkynes, and alicyclic amines. In addition, the catalyst can be easily separated from the mixture and can be reused for four consecutive cycles.

  18. Synthesis of Metal-organic Frameworks Based on Zr4+ and Benzene 1,3,5-Tricarboxylate Linker as Heterogeneous Catalyst in the Esterification Reaction of Palmitic Acid

    Science.gov (United States)

    Larasati, I.; Winarni, D.; Putri, F. R.; Hanif, Q. A.; Lestari, W. W.

    2017-07-01

    The conversion of the biomass into biodiesels via catalytic esterification and trans-esterification became an interesting topic due to the depletion of fossil-based energy. Homogenous catalysts such as HCl, H2SO4 and NaOH commonly used as catalyst, however, the use of this kind of catalyst causes more problems, such as the difficulties on the separation from the product and the pollution effect on the environment. Heterogeneous catalysts, such as Metal-Organic Frameworks (MOFs) give an alternative promising way to substitute these limitations due to their strong catalytic site, porosity, high specific surface area, and easy-separation and reusable properties. Herein, we reported the synthesis of MOFs based on zirconium(IV) and H3BTC linker (H3BTC = benzene-1,3,5-tricarboxylic acid) by solvothermal and reflux method. Solvothermal reaction at 120 °C was found to be the optimum method, that was indicated by most crystalline product compared to the simulated pattern in XRD analysis. The formation of the framework was characterized by FTIR analysis, which showed a significant shift from 1722 cm-1 to 1620 cm-1. The synthesized Zr(IV)-BTC was thermally stable up to 322°C as shown by TG/DTA analysis. This high thermal stability was related to the high oxidation state of Zr(IV), which give a significant covalent character to the Zr-O bond.

  19. Nanoparticle-assisted photo-Fenton reaction for photo-decomposition of humic acid

    Science.gov (United States)

    Banik, Jhuma; Basumallick, Srijita

    2017-11-01

    We report here the synthesis of CuO-doped ZnO composite nanomaterials (NMs) by chemical route and demonstrated for the first time that these NMs are efficient catalysts for H2O2-assisted photo-decomposition (photo-Fenton type catalyst) of humic acid, a natural pollutant of surface water by solar irradiation. This has been explained by faster electron transfer to OH radical at the p-n hetero-junction of this composite catalyst. Application of this composite catalyst in decomposing humus substances of local pond water by solar energy has been demonstrated.

  20. Inorganic-organic hybrid silica based tin complex as a novel, highly efficient and recyclable heterogeneous catalyst for the one-pot preparation of spirooxindoles in water.

    Science.gov (United States)

    Ghahremanzadeh, Ramin; Rashid, Zahra; Zarnani, Amir-Hassan; Naeimi, Hossein

    2014-11-14

    In the present study, a tin complex immobilized on silica gel as a novel, green, highly efficient and heterogeneous reusable catalyst was synthesized by grafting 2-amino benzamide onto the silica gel surface as a result of the reaction between isatoic anhydride and 3-aminopropyl-functionalized silica gel, followed by complexing with tin chloride. The resulting organic-inorganic hybrid material was evaluated in the one-pot three-component synthesis of spiro[indoline-pyrazolo[4',3':5,6]pyrido[2,3-d]pyrimidine]trione derivatives in water via the condensation reaction of isatins, barbituric acids, and 1H-pyrazol-5-amines. All the reactions were completed in short reaction times and all the products were obtained in high to excellent yields with high purity. In addition, the synthesized novel catalyst could be separated from the reaction mixture by simple filtration and can be reused up to seven runs without significant loss in activity.

  1. Fe–Co/sulfonated polystyrene as an efficient and selective catalyst in heterogeneous Baeyer–Villiger oxidation reaction of cyclic ketones

    Directory of Open Access Journals (Sweden)

    Yingting Wang

    2018-02-01

    Full Text Available A highly efficient catalyst Fe–Co/sulfonated polystyrene (Fe–Co/SPS was introduced and synthesized, which catalyzed BV oxidation of ketones with aqueous hydrogen peroxide to give the corresponding lactones in high yield and selectivity. Solid acid catalyst of Fe–Co/SPS has been prepared by using the 98-wt% sulfuric acid as the sulfonating agent and CoCl2 combined FeCl3 as sources of metal ions. Various physical–chemical characterizations including FT-IR, XRD, SEM and TGA, revealed that bimetallic ions Fe3+–Co2+ species in the sulfonated polystyrene framework were responsible for the catalytic activities. The BV reaction catalyzed by Fe–Co/SPS highlighted the special effects between metal ions and protonic acids as well as solvent-free heterogeneous catalytic oxidation with excellent conversion.

  2. Ultrasound assisted two-stage biodiesel synthesis from non-edible Schleichera triguga oil using heterogeneous catalyst: Kinetics and thermodynamic analysis.

    Science.gov (United States)

    Sarve, Antaram N; Varma, Mahesh N; Sonawane, Shriram S

    2016-03-01

    Present work deals with the ultrasound-assisted biodiesel production from low cost, substantial acid value kusum (Schleichera triguga) oil using a two-step method of esterification in presence of acid (H2SO4) catalyst followed by transesterification using a basic heterogeneous barium hydroxide (Ba(OH)2) catalyst. The initial acid value of kusum oil was reduced from 21.65 to 0.84 mg of KOH/g of oil, by acid catalyzed esterification with 4:1 methanol to oil molar ratio, catalyst concentration 1% (v/v), ultrasonic irradiation time 20 min at 40 °C. Then, Ba(OH)2 concentration of 3% (w/w), methanol to oil molar ratio of 9:1, ultrasonic irradiation time of 80 min, and temperature of 50 °C was found to be the optimum conditions for transesterification step and triglyceride conversion of 96.8% (wt) was achieved. This paper also examined the kinetics as well as the evaluation of thermodynamic parameters for both esterification and transesterification reactions. The lower value of activation energy and higher values of kinetic constants indicated a fast rate of reaction, which could be attributed to the physical effect of emulsification, in which the microturbulence generated due to radial motion of bubbles, creates an intimate mixing of the immiscible reactants causing the increase in the interfacial area, giving faster reaction kinetics. The positive values of Gibbs-free energy (ΔG), enthalpy (ΔH) and negative value of entropy (ΔS) revealed that both the esterification and transesterification were non-spontaneous, endothermic and endergonic reactions. Therefore, the present work has not only established the escalation obtained due to ultrasonication but also exemplified the two-step approach for synthesis of biodiesel from non-edible kusum oil based on the use of heterogeneous catalyst for the transesterification step. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Biodiesel production via transesterification of palm olein using waste mud crab (Scylla serrata) shell as a heterogeneous catalyst.

    Science.gov (United States)

    Boey, Peng-Lim; Maniam, Gaanty Pragas; Hamid, Shafida Abd

    2009-12-01

    A recent rise in crab aquaculture activities has intensified the generation of waste shells. In the present study, the waste shells were utilized as a source of calcium oxide to transesterify palm olein into methyl esters (biodiesel). Characterization results revealed that the main component of the shell is calcium carbonate which transformed into calcium oxide when activated above 700 degrees C for 2 h. Parametric studies have been investigated and optimal conditions were found to be methanol/oil mass ratio, 0.5:1; catalyst amount, 5 wt.%; reaction temperature, 65 degrees C; and a stirring rate of 500 rpm. The waste catalyst performs equally well as laboratory CaO, thus creating another low-cost catalyst source for producing biodiesel. Reusability results confirmed that the prepared catalyst is able to be reemployed up to 11 times. Statistical analysis has been performed using a Central Composite Design to evaluate the contribution and performance of the parameters on biodiesel purity.

  4. Development of new heterogeneous catalysts for the decomposition of methanol into hydrogen and carbon monoxide applying high throughput methods; Entwicklung neuer heterogener Katalysatoren zur Spaltung von Methanol in Wasserstoff und Kohlenmonoxid mittels Hochdurchsatz-Methoden

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, Torsten

    2008-07-11

    The topic of this thesis has been the development of new heterogeneous catalysts for the decomposition of methanol into hydrogen and carbon monoxide. As an important constraint here, the content of noble metals of the catalysts should be as low as possible. High-throughput-methods were applied in some of the syntheses and experiments to accelerate the development, as, for example, the use of liquid based sol-gel syntheses and the examination of catalyst libraries by spatial resolution gas chromatography. This screening technique allowed to test up to 207 different substances during one single experiment. Then, different combinatorial strategies were applied. First, these methods led to a highly active and stable catalyst in the ternary system of Cu-Ni-Zn, which showed high conversion and selectivity comparable to an industrial reference catalyst. Its activity during an 18 hour long term run was constant in contrast to the reference. Second, an additional approach starting from a broader variety of elements led to a Ce- Ru- and to a Cr-Ru-catalyst. Both of them were highly active in short term experiments, but lost their outstanding performances during long term runs. (orig.) [German] Die vorliegende Arbeit befasste sich mit der Entwicklung neuer heterogener Katalysatoren fuer die Spaltung von Methanol zu Wasserstoff und Kohlenmonoxid, die einen moeglichst geringen Gehalt an Edelmetallen aufweisen sollten. Um diesen Prozess zu beschleunigen, wurden in einem Teil der Synthesen und Experimente Hochdurchsatzmethoden verwendet. Neben der Roboter gestuetzten Sol-Gel-Synthese umfasste dies die Untersuchung von Katalysatorbibliotheken mittels ortsaufgeloester Gaschromatographie, die es ermoeglichte, in einem Experiment bis zu 207 verschiedene Substanzen auf ihre katalytische Aktivitaet zu testen. Unter Anwendung verschiedener kombinatorischer Strategien wurde zunaechst ein sehr aktiver und stabiler Katalysator im ternaeren Cu-Ni-Zn-System entdeckt. Neben Umsaetzen und

  5. Conversion of corn stalk into furfural using a novel heterogeneous strong acid catalyst in γ-valerolactone.

    Science.gov (United States)

    Xu, Zhiping; Li, Wenzhi; Du, Zhijie; Wu, Hao; Jameel, Hasan; Chang, Hou-Min; Ma, Longlong

    2015-12-01

    A novel solid acid catalyst was prepared by the copolymerization of p-toluenesulfonic acid and paraformaldehyde and then characterized by FT-IR, TG/DTG, HRTEM and N2-BET. Furfural was successfully produced by the dehydration of xylose and xylan using the novel catalyst in γ-valerolactone. This investigation focused on effects of various reaction conditions including solvent, acid catalyst, reaction temperature, residence time, water concentration, xylose loading and catalyst dosage on the dehydration of xylose to furfural. It was found that the solid catalyst displayed extremely high activity for furfural production. 80.4% furfural yield with 98.8% xylose conversion was achieved at 170°C for 10 min. The catalyst could be recycled at least five times without significant loss of activity. Furthermore, 83.5% furfural yield and 19.5% HMF yield were obtained from raw corn stalk under more severe conditions (190°C for 100 min). Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Treating leachate by Fenton oxidation

    Directory of Open Access Journals (Sweden)

    Roger Iván Méndez Novelo

    2010-05-01

    Full Text Available Leachates are formed from liquids, mainly rainwater, percolating through solid wastes during stabilisation. Their composition is variable and highly toxic; leachate treatment is therefore a complex task. Leachates represent a high risk to health due to the Yucatan Peninsula’s highly permeable soil. The results are presented from applying the Fenton process to treating leachate from the sanitary Merida landfill, Yucatan, Mexico. The Fenton process consists of treating the contaminant load with an H2O2 and FeSO4 combination in acidic conditions. Optimal reaction time, pH value, Fenton reagent dose, post treatment coagulation – flocculation doses and increased biodegradability index were all determined. Optimal oxidation conditions and doses were 202+ minute contact time, 4 pH, 600 mg/L H2O2 concentration and 1,000 mg/L Fe. Average organic matter removal rate, measured as CODS and TOC, were 78% and 87% respectively. The biodegradability index increased from 0.07 to 0.11 during the Fenton process and up to 0.13 when the Fenton process was followed by coagulation-flocculation.

  7. Versatile and sustainable synthesis of cyclic imides from dicarboxylic acids and amines by Nb2O5 as a base-tolerant heterogeneous Lewis acid catalyst.

    Science.gov (United States)

    Ali, Md Ayub; Siddiki, S M A Hakim; Kon, Kenichi; Hasegawa, Junya; Shimizu, Ken-Ichi

    2014-10-27

    Catalytic condensation of dicarboxylics acid and amines without excess amount of activating reagents is the most atom-efficient but unprecedented synthetic method of cyclic imides. Here we present the first general catalytic method, proceeding selectively and efficiently in the presence of a commercial Nb2 O5 as a reusable and base-tolerant heterogeneous Lewis acid catalyst. The method is effective for the direct synthesis of pharmaceutically or industrially important cyclic imides, such as phensuximide, N-hydroxyphthalimide (NHPI), and unsubstituted cyclic imides from dicarboxylic acid or anhydrides with amines, hydroxylamine, or ammonia. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Removal of Acid Red 33 from Aqueous Solution by Fenton and Photo Fenton Processes

    Directory of Open Access Journals (Sweden)

    Aref Shokri

    2017-04-01

    Full Text Available In this project decolorization and mineralization of synthetic wastewater containing acid red 33 (AR33 was investigated by Fenton and photo Fenton processes in a batch photo reactor. A comparative assessment using Fenton and photo Fenton processes was performed after initial optimization studies such as varying pH, the concentration of pollutant, peroxide and iron. The color removal and mineralization efficiency of AR33 were calculated by Spectrophotometric and chemical oxygen demand (COD tests. The degradation efficiency in photo Fenton process (98.5% in 10 min of reaction was higher than Fenton ones (97.5% in 30 min. After 60 min of reaction, the removal of COD in photo Fenton and Fenton processes was 71% and 37.5%, respectively. Therefore, photo Fenton was the most effective process in partial mineralization of AR33. Kinetic constants were evaluated using pseudo first order equations to obtain the rate constant, K.

  9. Heterogeneous Catalysis Applied To Advanced Oxidation Processes (AOPs) For Degradation of Organic Pollutants

    Science.gov (United States)

    Cotto-Maldonado, Maria del Carmen

    Water is an essencial resource for humankind and biomes. Actually, the pollution of the water resources, specially the contamination of the fresh water is great concern in our society. Develop of new and more efficient method for degradation of pollutant in water increase the research in this area, especially in the AOPs. During this investigation a comparison between different AOPs methods (photocatalysis, sono-Fenton and photo-Fenton) to determine the most efficient process of them was done. To reach our goal, different catalysts, namely TiO2 nanowires, TiO2 CNTs, ZnO nanoparticles, Fe2O3 nanowires and magnetite nanoparticles were synthesized and characterized by different techniques including FE-SEM, TGA, specific surface area (BET), XRD, Raman spectroscopy, XPS and magnetic susceptibility. Commercial and synthesized catalysts were used in photocatalysis, sono-Fenton and photo-Fenton processes for the degradation of model organic compounds (Methylene Blue, Rhodamine B, Methyl Orange, Gential Violet, Methyl Violet and p-aminobenzoic acid). According with the experimental results, no significant differences were observed between the photo-Fenton and sono-Fenton processes when the same catalysts were used. For the photocatalytic process, the more effective catalyst was TiO2NWs and for the sono-Fenton and photo-Fenton processes, the more effective catalyst was FeCl2.

  10. Egg-shaped core/shell α-Mn2O3@α-MnO2 as heterogeneous catalysts for decomposition of phenolics in aqueous solutions.

    Science.gov (United States)

    Saputra, Edy; Zhang, Huayang; Liu, Qiaoran; Sun, Hongqi; Wang, Shaobin

    2016-09-01

    Novel uniform ellipsoid α-Mn2O3@α-MnO2 core/shell (McMs) nanocomposites were prepared via a hydrothermal process with a shape-control protocol followed by calcination at different temperatures. The properties of the composites were characterized by a number of techniques such as thermogravimetric analysis (TGA), X-ray diffraction (XRD), N2 adsorption, and scanning electron microscopy (SEM). The core/shell materials were much effective in heterogeneous oxone(®) activation to generate sulfate and hydroxyl radicals for degradation of aqueous phenol. The McMs composites demonstrated catalytic activity for 100% phenol decomposition in short duration varying between 20 and 120 min, much higher than that of homogeneous Mn(2+) system with 95% phenol degradation in 120 min. They also showed a higher activity than single-phase α-Mn2O3 or α-MnO2. The catalytic activity of phenol degradation depends on temperature, oxone(®) concentration, phenol concentration, and catalyst loading. The catalysts also showed a stable activity in several cycles. Kinetic study demonstrated that phenol degradation reactions follow a first order reaction on McMs catalysts giving activation energies at 32.1-68.8 kJ/mol. With the detection of radicals by electron paramagnetic resonance (EPR), the generation mechanism was proposed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Heterogeneous Single-Atom Catalyst for Visible-Light-Driven High-Turnover CO2Reduction: The Role of Electron Transfer.

    Science.gov (United States)

    Gao, Chao; Chen, Shuangming; Wang, Ying; Wang, Jiawen; Zheng, Xusheng; Zhu, Junfa; Song, Li; Zhang, Wenkai; Xiong, Yujie

    2018-02-14

    Visible-light-driven conversion of CO 2 into chemical fuels is an intriguing approach to address the energy and environmental challenges. In principle, light harvesting and catalytic reactions can be both optimized by combining the merits of homogeneous and heterogeneous photocatalysts; however, the efficiency of charge transfer between light absorbers and catalytic sites is often too low to limit the overall photocatalytic performance. In this communication, it is reported that the single-atom Co sites coordinated on the partially oxidized graphene nanosheets can serve as a highly active and durable heterogeneous catalyst for CO 2 conversion, wherein the graphene bridges homogeneous light absorbers with single-atom catalytic sites for the efficient transfer of photoexcited electrons. As a result, the turnover number for CO production reaches a high value of 678 with an unprecedented turnover frequency of 3.77 min -1 , superior to those obtained with the state-of-the-art heterogeneous photocatalysts. This work provides fresh insights into the design of catalytic sites toward photocatalytic CO 2 conversion from the angle of single-atom catalysis and highlights the role of charge kinetics in bridging the gap between heterogeneous and homogeneous photocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Contributions to a rational design of heterogeneous catalysts: from experimentation to numerical simulation; Contributions a une conception rationnelle des catalyseurs heterogenes: de l'experimentation a la simulation numerique

    Energy Technology Data Exchange (ETDEWEB)

    Toulhoat, H.

    2002-03-01

    I present through this dissertation a synthesis of my contributions to the field of heterogeneous catalysis, along two decades of research undertaken as a scientist at Institut Francais du Petrole. I started my itinerary on the 'floor', with the task of developing industrial hydro-treating catalysts, then I had the nice opportunity to lead advanced research on various subjects. However, I have been devoting myself for the past ten years to the encounter between catalysis and theoretical chemistry. The presentation of my work follows therefore a guideline starting with preparation and ending at modelization of the catalytic solid, after having gone through its characterization and the assessment of its activity. Modelization is thus founded on a consistent set of experimental informations. This guideline is applied to the four main themes to which this work is confined: hydro-treating catalysts, hydro-de-metallation catalysts, thio-resistance of noble metals, and solid acids. In summary, I believe I have contributed significantly, on the one hand to strong conceptual and technical advances in the area of ab initio simulation of elementary phenomena in heterogeneous catalysis, with the elaboration of original knowledge on catalysis by sulfides, metals and acids, as well as the genesis of alumina carriers, and on the other hand to a new approach of periodic trends in catalysis: this can be considered as a re-visitation of the principle of Sabatier, leading to a predictive tool for catalytic activity of solids. In a near future it will be possible to say if practical results validate this conceptual tool, and justify or not the ambitious title I gave to my work. (author)

  13. Effective degradation of rhodamine B by electro-Fenton process, using ferromagnetic nanoparticles loaded on modified graphite felt electrode as reusable catalyst: in neutral pH condition and without external aeration.

    Science.gov (United States)

    Tian, Jiangnan; Zhao, Jixiang; Olajuyin, Ayobami Matthew; Sharshar, Moustafa Mohamed; Mu, Tingzhen; Yang, Maohua; Xing, Jianmin

    2016-08-01

    Polytetrafluoroethylene/ferromagnetic nanoparticle/carbon black (PTFE/MNP/CB)-modified graphite felt (GF) was successfully applied as cathode for the mineralization of rhodamine B (RhB) in electro-Fenton (EF) process. The modified cathode showed high decolorization efficiency for RhB solution even in neutral pH condition and without external aeration, achieving nearly complete decolorization and 89.52 % total organic carbon (TOC) removal after 270-min oxidation with the MNP load 1.2 g at 50 A/m(2). Moreover, the operational parameters (current density, MNP load, initial pH, and airflow rate) were optimized. After that, adsorption isotherm was also conducted to compare the absorption quantity of CB and carbon nanotube (CNT). Then, the surface morphologies of MNPs were characterized by transmission electron microscope (TEM), energy-dispersive X-ray detector (EDX), and Fourier transform infrared spectroscopy (FTIR); and the modified cathode was characterized by SEM and contact angle. Finally, the stability and reusability of modified cathode were tested. Result uncovered that the PTFE/MNP/CB-modified cathode has the potential for industrial application and the solution after treatment was easily biodegradable.

  14. Effects of Supported ( n BuCp) 2 ZrCl 2 Catalyst Active-Center Distribution on Ethylene–1-Hexene Copolymer Backbone Heterogeneity and Thermal Behaviors

    KAUST Repository

    Atiqullah, Muhammad

    2013-07-10

    Two catalysts, denoted as catalyst 1 [silica/MAO/(nBuCp) 2ZrCl2] and catalyst 2 [silica/nBuSnCl 3/MAO/(nBuCp)2ZrCl2] were synthesized and subsequently used to prepare, without separate feeding of methylaluminoxane (MAO), ethylene homopolymer 1 and homopolymer 2, respectively, and ethylene-1-hexene copolymer 1 and copolymer 2, respectively. Gel permeation chromatography (GPC), Crystaf, differential scanning calorimetry (DSC) [conventional and successive self-nucleation and annealing (SSA)], and 13C nuclear magnetic resonance (NMR) polymer characterization results were used, as appropriate, to model the catalyst active-center distribution, ethylene sequence (equilibrium crystal) distribution, and lamellar thickness distribution (both continuous and discrete). Five different types of active centers were predicted in each catalyst, as corroborated by the SSA experiments and complemented by an extended X-ray absorption fine structure (EXAFS) report published in the literature. 13C NMR spectroscopy also supported this active-center multiplicity. Models combined with experiments effectively illustrated how and why the active-center distribution and the variance in the design of the supported MAO anion, having different electronic and steric effects and coordination environments, influence the concerned copolymerization mechanism and polymer properties, including inter- and intrachain compositional heterogeneity and thermal behaviors. Copolymerization occurred according to the first-order Markovian terminal model, producing fairly random copolymers with minor skewedness toward blocky character. For each copolymer, the theoretical most probable ethylene sequences, nE MPDSC-GT and n E MPNMR-Flory, as well as the weight-average lamellar thicknesses, Lwav DSC-GT and Lwav SSA DSC, were found to be comparable. To the best of our knowledge, such a match has not previously been reported. The percentage crystallinities of the homo- and copolymers increased linearly as a function of

  15. Esterification of oil adsorbed on palm decanter cake into methyl ester using sulfonated rice husk ash as heterogeneous acid catalyst

    Science.gov (United States)

    Hindryawati, Noor; Erwin, Maniam, Gaanty Pragas

    2017-02-01

    Palm Decanter cake (PDC) which is categorized as the waste from palm oil mill has been found to contain residual crude palm oil. The oil adsorbed on the PDC (PDC-oil) can be extracted and potentially used as feedstock for biodiesel production. Feedstock from waste like PDC-oil is burdened with high free fatty acids (FFAs) which make the feedstock difficult to be converted into biodiesel using basic catalyst. Therefore, in this study, a solid acid, RHA-SO3H catalyst was synthesized by sulfonating rice husk ash (RHA) with concentrated sulfuric acid. The RHA-SO3H prepared was characterized with TGA, FTIR, BET, XRD, FE-SEM, and Hammett indicators (methyl red, bromophenol blue, and crystal violet). PDC was found to have about 11.3 wt. % oil recovered after 1 hour extraction using ultrasound method. The presence of sulfonate group was observed in IR spectrum, and the surface area of RHA-SO3H was reduced to 37 m2.g-1 after impregnation of sulfonate group. The RHA-SO3H catalyst showed that it can work for both esterification of free fatty acid which is present in PDC-oil, and transesterification of triglycerides into methyl ester. The results showed highest methyl ester content of 70.2 wt.% at optimal conditions, which was 6 wt.% catalyst amount, methanol to oil molar ratio of 17:1 for 5 hours at 120 °C.

  16. Low-grade oils and fats: effect of several impurities on biodiesel production over sulfonic acid heterogeneous catalysts.

    Science.gov (United States)

    Morales, Gabriel; Bautista, L Fernando; Melero, Juan A; Iglesias, Jose; Sánchez-Vázquez, Rebeca

    2011-10-01

    Different lipidic wastes and low-grade oils and fats have been characterized and evaluated as feedstocks for the acid-catalyzed production of FAME. The characterization of these materials has revealed significant contents of free fatty acids, Na, K, Ca, Mg, P, unsaponifiable matter and humidity. Arenesulfonic acid-functionalized SBA-15 silica catalyst has provided yields to FAME close to 80% in the simultaneous esterification-transesterification of the different feedstocks, regardless of their nature and properties, using methanol under the following reaction conditions: 160 °C, 2 h, methanol to oil molar ratio of 30, 8 wt.% catalyst loading, and 2000 rpm stirring rate. Nevertheless, reutilization of the catalyst is compromised by high levels of impurities, especially because of deactivation by strong interaction of unsaponifiable matter with the catalytic sites. The conditioning of these materials by aqueous washing in the presence of cationic-exchange resin Amberlyst-15, followed by a drying step, resulted in a lower deactivation of the catalyst. Copyright © 2011 Elsevier Ltd. All rights reserved.

  17. B2O3/Al2O3 as a new, highly efficient and reusable heterogeneous catalyst for the selective synthesis of β-enamino ketones and esters under solvent-free conditions

    OpenAIRE

    Chen,Jiu-Xi; Zhang,Chang-Fu; Gao,Wen-Xia; Jin,Hui-Le; Ding,Jin-Chang; Wu,Hua-Yue

    2010-01-01

    Boron oxide adsorbed on alumina (B2O3/Al2O3 ) has been found to be a new and highly efficient heterogeneous catalyst for the synthesis of β-enamino ketones and esters by the enamination of various primary and secondary amines with β-dicarbonyl compounds under solvent-free conditions. The important features of this methodology are broad substrate scope, high yield, no requirement of metal catalysts, high regio- and chemoselectivity and environmental friendliness. In addition, the cat...

  18. Evaluation of Fenton's Reagent and Activated Persulfate for Treatment of a Pharmaceutical Waste Mixture in Groundwater

    DEFF Research Database (Denmark)

    Bennedsen, Lars Rønn; Søgaard, Erik Gydesen; Kakarla, Prasad

    -going bench tests evaluating treatment of site groundwater and soil using modified Fenton's reagent and activated persulfate. These tests are investigating oxidant stability, oxidation efficiency, metals mobilization and, for the persulfate, different activating agents, including NaOH, chelated iron......, and modified Fenton's reagent. The stability of the oxidants will be determined under simulated aquifer conditions, with and without catalyst or activating agents. Once an optimal activation technique has been determined, oxidation efficiency towards the complex mix of contaminants will be measured in terms...... is to identify the fate of mercury and cyanide consequent to the application of Fenton's reagent and activated persulfate.  Batch and continuous-flow column reactors will be used to measure mobilization of the mercury, cyanide and other metals both within the aqueous and vapor phases.   The collective chemical...

  19. SIMULTANEOUS DEGRADATION OF SOME PHTHALATE ESTERS UNDER FENTON AND PHOTO-FENTON OXIDATION PROCESSES

    National Research Council Canada - National Science Library

    BELDEAN-GALEA M.S; COZMA A.M; DIODIU R

    2015-01-01

    In this study the assessment of the degradation efficiency of five phthalates, DEP, BBP, DEHP, DINP and DIDP, found in a mixture in a liquid phase, using the Fenton and Photo Fenton oxidation processes, was conducted...

  20. β-cyclodextrin-polyurethane polymer: A neutral and eco-friendly heterogeneous catalyst for the one-pot synthesis of 1,4-dihydropyridine and polyhydroquinolien derivatives via Hantzsch reaction under solvent-free conditions

    Directory of Open Access Journals (Sweden)

    Kiasat Ali Reza

    2014-01-01

    Full Text Available An efficient synthesis of 1,4-dihydropyridine & polyhydroquinolien derivatives using b-Cyclodextrin-polyurethane polymer (β-CDPU as a stationary microvessel and neutral heterogeneous catalyst via a four component coupling of aldehydes, β-ketoester (2 mol and ammonium acetate under solvent-free conditions is described. Compared with the classical Hantzsch reaction, this new method has the advantages of good yield, short reaction time and methodological simplicity. β-CDPU was proved to be an efficient heterogeneous catalyst which could be easily handled and removed from the reaction mixture by simple filtration, and also recovered and reused without loss of reactivity.

  1. Evaluation of the mercaptobenzothiazole degradation by combined adsorption process and Fenton reaction using iron mining residue.

    Science.gov (United States)

    Martins, Adriana Lau da Silva; Teixeira, Luís Alberto César; da Fonseca, Fabiana Valéria; Yokoyama, Lídia

    2017-08-01

    The present study investigated the degradation of mercaptobenzothiazole (MBT), evaluating homogeneous and heterogeneous systems. An iron mineral residue from the desliming step of iron mining was used as a source in the Fenton-like reaction (advanced oxidation process). A granulometric analysis of the residue was performed and yielded fractions with high hematite (Fe2O3) and low quartz content in sieves from 74 to below 44 mm. In this particle size range, the hematite content from 58.9% to 67.4% and the Brunauer-Emmett-Teller area from 0.1345 to 1.3137 m(2) g(-1) were obtained. The zeta potential curves as a function of pH were obtained for the residue, the MBT solution and mixtures thereof. The adsorption of MBT in the residue and its degradation through the Fenton-like reaction were investigated. Adsorption tests and the Fenton-like reaction were carried out, where the MBT species and the residue are oppositely charged, yielding, respectively, 10% MBT adsorption on the surface of the residue and 100% MBT degradation by the Fenton-like reaction at pH 3, hydrogen peroxide concentration of 25 mg L(-1), residue concentration of 3 g L(-1), 200 rpm and 25°C, from a 100 mg L(-1) MBT solution. MBT degradation was found to occur mainly by the heterogeneous Fenton-like process.

  2. Evidence for the Active Phase of Heterogeneous Catalysts through In Situ Reaction Product Imaging and Multiscale Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Matera, S.; Blomberg, S.; Hoffmann, M. J.; Zetterberg, J.; Gustafson, J.; Lundgren, E.; Reuter, K.

    2015-06-17

    We use multiscale modeling to analyze laser-induced fluorescence (LIF) measurements of the CO oxidation reaction over Pd(100) at near-ambient reaction conditions. Integrating density functional theory-based kinetic Monte Carlo simulations of the active catalyst into fluid-dynamical simulations of the mass transport inside the reactor chamber, we calculate the reaction product concentration directly above the catalyst surface. Comparing corresponding data calculated for different surface models against the measured LIF signals, we can discriminate the one that predominantly actuates the experimentally measured catalytic activity. For the probed CO oxidation reaction conditions, the experimental activity is due to pristine Pd(100) possibly coexisting with other (oxidic) domains on the surface.

  3. ZnO-Nanorods as an Efficient Heterogeneous Catalyst for the Synthesis of Thiazole Derivatives in Water.

    Science.gov (United States)

    Shams-Najafi, Sayyed Jalal; Gholizadeh, Mostafa; Ahmadpour, Ali; Rostami-Charati, Faramarz

    2017-01-01

    Aims & Scope: Thiazole derivatives are produced using one-pot multicomponent reactions of acid chlorides, potassium thiocyanate, amino acids, alkyl bromides and ZnO nanorods (NR-ZnO) as the catalyst in water at ambient temperature. These reactions were no't performed without using NR-ZnO as the catalyst. Nanorods of ZnO have been prepared by reflux procedure using sodium dodecylsulfate (SDS). Nanorods of ZnO showed a considerable improvement in the yield of the product and displayed significant reusable activity. In these reactions, all chemicals were prepared from Fluka (Buchs, Switzerland). Nanorods of ZnO were synthesized in the laboratory according to literature report. By using an electrothermal 9100 apparatus, melting points of synthesized compounds were determined. Heraeus CHN-O-Rapid analyzer was employed for elemental analyses for C, H, and N. FINNIGANMAT 8430 spectrometer operating at an ionization potential of 70 eV was used for mass spectra. Shimadzu IR-460 spectrometer was employed for IR spectra. BRUKER DRX-500 AVANCE spectrometer at 500.1 and 125.8 MHz was used for 1H, and 13C NMR spectra for solutions in CDCl3 with TMS as internal standard or 85% H3PO4 as external standard, respectively. We describe a facile and green synthetic method for the synthesis of thiazole derivatives 5 from acid chlorides, potassium thiocyanate, alkyl bromides and amino acids using NR-ZnO- as the catalyst in water at room temperature. In conclusion, we describe an efficient, green procedure and high yielding synthesis of thiazole derivatives using acid chlorides, potassium thiocyanate, alkyl bromides and amino acids in the presence of NR-ZnO as the catalyst in water at room temperature. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  4. BBD Optimization of K-ZnO Catalyst Modification Process for Heterogeneous Transesterification of Rice Bran Oil to Biodiesel

    Science.gov (United States)

    Kabo, K. S.; Yacob, A. R.; Bakar, W. A. W. A.; Buang, N. A.; Bello, A. M.; Ruskam, A.

    2016-07-01

    Environmentally benign zinc oxide (ZnO) was modified with 0-15% (wt.) potassium through wet impregnation and used in transesterification of rice bran oil (RBO) to form biodiesel. The catalyst was characterized by X-Ray powder Diffraction (XRD), its basic sites determined by back titration and Response Surface Methodology (RSM) Box-Behnken Design (BBD) was used to optimize the modification process variables on the basic sites of the catalyst. The transesterification product, biodiesel was analyzed by Nuclear Magnetic Resonance (NMR) spectroscopy. The result reveals K-modified ZnO with highly increased basic sites. Quadratic model with high regression R2 = 0.9995 was obtained from the ANOVA of modification process, optimization at maximum basic sites criterion gave optimum modification conditions of K-loading = 8.5% (wt.), calcination temperature = 480 oC and time = 4 hours with response and basic sites = 8.14 mmol/g which is in close agreement with the experimental value of 7.64 mmol/g. The catalyst was used and a value of 95.53% biodiesel conversion was obtained and effect of potassium leaching was not significant in the process

  5. Fenton and solar photo-Fenton processes for the removal of ...

    African Journals Online (AJOL)

    2011-10-10

    Oct 10, 2011 ... However, in the solar photo-Fenton process, the degradation rate increased significantly. ... the solar photo-Fenton process needs 50% less time than that used in the Fenton process which translates to a 50% gain of. H2O2. Keywords: ..... HABER F and WEISS J (1934) The catalytic decomposition of hydro-.

  6. AN ADVANCED OXIDATION PROCESS : FENTON PROCESS

    Directory of Open Access Journals (Sweden)

    Engin GÜRTEKİN

    2008-03-01

    Full Text Available Biological wastewater treatment is not effective treatment method if raw wastewater contains toxic and refractory organics. Advanced oxidation processes are applied before or after biological treatment for the detoxification and reclamation of this kind of wastewaters. The advanced oxidation processes are based on the formation of powerful hydroxyl radicals. Among advanced oxidation processes Fenton process is one of the most promising methods. Because application of Fenton process is simple and cost effective and also reaction occurs in a short time period. Fenton process is applied for many different proposes. In this study, Fenton process was evaluated as an advanced oxidation process in wastewater treatment.

  7. Nano Pd(0) supported on cellulose: a highly efficient and recyclable heterogeneous catalyst for the Suzuki coupling and aerobic oxidation of benzyl alcohols under liquid phase catalysis.

    Science.gov (United States)

    Jamwal, Navjot; Sodhi, Ravinderpal Kour; Gupta, Princy; Paul, Satya

    2011-12-01

    Nano palladium(0) supported on cellulose was found to be highly efficient recyclable heterogeneous catalyst for the Suzuki coupling between aryl bromides and phenyl boronic acid in water and aerobic oxidation of benzyl alcohols using air as the source of molecular oxygen in acetonitrile. The Cell-Pd(0) was prepared by stirring commercially available cellulose with Pd(OAc)(2) in ethanol at 25°C followed by reduction with hydrazine hydrate, leading finally to nano Pd(0) particles uniformly distributed on surface of cellulose. This catalytic system provides biaryls and polyaryls in excellent yields with very high turn over numbers via Suzuki coupling; and benzaldehyde derivatives in high yields and selectivity by oxidation in air. Cell-Pd(0) was characterized by X-ray diffraction techniques (XRD), thermal analysis (TGA), scanning electron microscope (SEM) and transmission electron microscope (TEM). Copyright © 2011 Elsevier B.V. All rights reserved.

  8. Chitosan supported Zn(II) mixed ligand complexes as heterogeneous catalysts for one-pot synthesis of amides from ketones via Beckmann rearrangement

    Science.gov (United States)

    Anuradha; Kumari, Shweta; Layek, Samaresh; Pathak, Devendra D.

    2017-02-01

    Chitosan supported Zn(II) mixed ligand complexes have been synthesized and characterized by FT-IR, UV-Vis, TGA, XRD, FESEM, EDX, AAS and Elemental Analysis. These complexes have been found to be efficient and recyclable heterogeneous catalysts for the one-pot synthesis of amides via Beckmann rearrangement. All three complexes can be easily filtered out from the reaction medium and reused up to five times without significant loss of catalytic activity. The reported protocol is economical and novel in the sense that amides can be easily synthesized in only one-step. All products were obtained as white to off-white crystalline solids and fully characterized by 1H NMR, FT-IR and Mass Spectra.

  9. Catalyst system comprising a first catalyst system tethered to a supported catalyst

    Science.gov (United States)

    Angelici, Robert J.; Gao, Hanrong

    1998-08-04

    The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilation, olefin oxidation, isomerization, hydrocyanation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical.

  10. Surface heterogeneity of zirconia-supported V{sub 2}O{sub 5} catalysts. The link between structure and catalytic properties in oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Adamski, A.; Sojka, Z.; Dyrek, K.; Che, M.; Wendt, G.; Albrecht, S.

    1999-08-31

    Undoped and alkali-doped zirconia-supported vanadia catalysts for the oxidative dehydrogenation of propane were prepared by impregnation and characterized by various techniques. The chemical state of surface and bulk vanadium was investigated as a function of the calcination temperature, V{sub 2}O{sub 5} loading, and the nature and content of alkali-metal additives. It is found that on the surface vanadium is present in the form of isolated vanadyl species or oligomeric vanadates, or as nanocrystalline V{sub 2}O{sub 5} and that V{sup 5+} and V{sup 4+} ions coexist in octahedral and tetrahedral coordination, while within the bulk of zirconia matrix, V{sup 4+} ions are stabilized in a V{sub x}Zr{sub 1{minus}x}O{sub 2} solid solution. Presence of the alkali-metal additives and water changes the dispersion of surface vanadium species favoring, in both cases, formation of mononuclear vanadyl surface complexes. Surface heterogeneity plays a vital role for the catalytic performance of V{sub 2}O{sub 5}/ZrO{sub 2} catalysts in oxidative dehydrogenation of propane. Catalytic properties are related to the nature of VO{sub x} surface species and correlates well with their reducibility. The maximum of catalytic activity was observed for catalysts with vanadia content between 3 and 5 mol %, for which octahedral polyvanadate surface species are dominant. It is proposed that the catalytic activity is affected by the nucleophilicity of bridging oxygen in V-O-V entities, modified by the adjacent alkali cations.

  11. Effective heterogeneous transition metal glycerolates catalysts for one-step biodiesel production from low grade non-refined Jatropha oil and crude aqueous bioethanol

    Science.gov (United States)

    Lau, Pak-Chung; Kwong, Tsz-Lung; Yung, Ka-Fu

    2016-03-01

    The utilization of bioethanol as the alcohol source for biodiesel production is more environmentally advantageous over methanol owing to its lower toxicity, lower flammability and its sustainable supply from renewable agricultural resources. However, as the presence of water in crude bioethanol is the critical factor limiting the biodiesel production process, the energy-intensive and costly purification of bioethanol is necessary for biodiesel application. Manganese glycerolate (MnGly) is reported the first time here as a robust heterogeneous catalyst that exhibited over 90% conversion by using aqueous ethanol containing 80 wt.% of water in the production of fatty acid ethyl ester (FAEE). The employment of 95 wt.% ethanol with respect to water could achieve 99.7% feedstock conversion in 6 hours under the optimal reaction conditions: reaction temperature (150 °C), feedstock-to-ethanol molar ratio (1:20) and catalyst loading (6 wt.%). Commercially available low grade crude bioethanol with the presence of impurities like sugars were applied which demonstrated remarkable catalytic activity in 24 hours. The high water tolerance of MnGly towards biodiesel production could eventually simplify the purification of bioethanol that consumes less energy and production cost.

  12. Ceria-Based Mixed Oxide Supported Nano-Gold as an Efficient and Durable Heterogeneous Catalyst for Oxidative Dehydrogenation of Amines to Imines Using Molecular Oxygen

    Directory of Open Access Journals (Sweden)

    Bashir Ahmad Dar

    2012-06-01

    Full Text Available The present work is intended to determine the catalytic activity of Mixed Oxide supported gold for aerobic oxidative dehydrogenation of amines to imines using Ceria as a main constituent of the each support. The model catalysts Au/CeO2:TiO2 Au/CeO2:SiO2, Au/CeO2:ZrO2 and Au/CeO2:Al2Os were prepared by deposition co-precipitation method and deposition of gold was determined by EDEX analysis. The supported nano-gold catalyzes the dehydrogenation of secondary amines to imines without loss of activity. On recycling good amount of product yield is obtained. Oxidation of secondary amines to imines is carried at 100˚C and almost 90 % conversion was obtained with >99% selectivity. © 2012 BCREC UNDIP. All rights reservedReceived: 26th December 2011; Revised: 7th June 2012; Accepted: 13rd June 2012[How to Cite: B.A. Dar, M. Sharma, B. Singh. (2012. Ceria-Based Mixed Oxide Supported Nano-Gold as an Efficient and Durable Heterogeneous Catalyst for Oxidative Dehydrogenation of Amines to Imines Using Molecular Oxygen. Bulletin of Chemical Reaction Engineering & Catalysis, 7(1: 79-84.  doi:10.9767/bcrec.7.1.1257.79-84][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1257.79-84 ] | View in 

  13. Novel schemes for production of biodiesel and value-added co-products from microalgal oil using heterogeneous catalysts

    Science.gov (United States)

    Dong, Tao

    Microalgae are promising sources of biofuels primarily because of their higher potential productivity compared to terrestrial biofuel crops. However, the production of liquid fuels from microalgae suffers from a lack of viable methods of extraction, conversion and fractionation of various components of the algal biomass. In this dissertation study, a rapid method was developed to accurately evaluate the biodiesel potential of microalgae biomass. The major advantage of this method is in situ fatty acid methyl ester (FAME) preparation directly from wet fresh microalgal and yeast biomass, without prior solvent extraction or dehydration. FAMEs were prepared by a sequential alkaline hydrolysis and acidic esterification process. This method can be used even with high amount of water in the biomass and is applicable to a vast range of microalgae and yeast species. A two-step in situ process was also investigated in this study to obtain a high FAME yield from microalgae biomass that had high free fatty acids (FFA) content. This process has the potential to reduce the production cost of microalgae-derived FAME and be more environmental compatible due to the higher FAME yield with reduced catalyst consumption. A cost-effective bio-char based catalyst was tested for the two-step biodiesel production. The results indicated that the bio-char catalyst was superior to commercial Amberly-15. A scalable chlorophyll remove process was also developed as a part of the system. The research resulted in a practical and cost-effective approach for producing biodiesel from crude microalgal oil. An integrated approach was explored in the fourth part of the study to produce biodiesel and fractionate high-value polyunsaturated fatty acid (PUFA). Zeolites were employed as the catalyst for selective esterification of fatty acids according to their chain length and degree of saturation. Low-value short chain FFA could be largely converted into FAME, while PUFA would remain unreacted due to

  14. HETEROGENEOUS PHOTOCATALYTIC DEGRADATION OF PHENOL IN AQUEOUS SUSPENSION OF PERIWINKLE SHELL ASH CATALYST IN THE PRESENCE OF UV FROM SUNLIGHT

    Directory of Open Access Journals (Sweden)

    OSARUMWENSE, J. O.

    2015-12-01

    Full Text Available The batch photocatalytic degradation of phenol in aqueous solution wasinvestigated using periwinkle shell ash (PSA as photocatalyst. Chemical characterisation of the PSA revealed that the major oxides present were calcium oxide (CaO, silica (SiO2 and aluminium oxide (Al2O3 which accounted for 41.3, 33.2 and 9.2% of the weight of PSA characterised. The major elements in PSA were iron (19.2% and zinc (16.5%. FTIR results revealed absorption peaks of 3626.59 cm−1, 1797.58 cm−1, 1561.43 cm−1 and 1374.34 cm−1 in the infrared spectrum of PSA corresponding to O–H, C= O, C= C and C–H bonds respectively. Increasing the initial phenol concentration resulted in a decrease in the degradation efficiency of PSA. Lower catalyst loadings favoured the degradation process. Maximum degradation efficiency was obtained when the initial phenol concentration and catalyst loading were set as 50 g/L and 5 g/L respectively. The kinetics of the degradation process was well described by the pseudo first order equation while the diffusion mechanism was well represented by the intra particle diffusion model (R2>0.90. The adsorption equilibrium data fitted well to the Langmuir isotherm equation with an R2 value of 0.997.

  15. Catalytic supercritical water gasification of primary paper sludge using a homogeneous and heterogeneous catalyst: Experimental vs thermodynamic equilibrium results.

    Science.gov (United States)

    Louw, Jeanne; Schwarz, Cara E; Burger, Andries J

    2016-02-01

    H2, CH4, CO and CO2 yields were measured during supercritical water gasification (SCWG) of primary paper waste sludge (PWS) at 450°C. Comparing these yields with calculated thermodynamic equilibrium values offer an improved understanding of conditions required to produce near-equilibrium yields. Experiments were conducted at different catalyst loads (0-1g/gPWS) and different reaction times (15-120min) in a batch reactor, using either K2CO3 or Ni/Al2O3-SiO2 as catalyst. K2CO3 up to 1g/gPWS increased the H2 yield significantly to 7.5mol/kgPWS. However, these yields and composition were far from equilibrium values, with carbon efficiency (CE) and energy recovery (ER) of only 29% and 20%, respectively. Addition of 0.5-1g/gPWS Ni/Al2O3-SiO2 resulted in high H2 and CH4 yields (6.8 and 14.8mol/kgPWS), CE of 84-90%, ER of 83% and a gas composition relatively close to the equilibrium values (at hold times of 60-120min). Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Fenton-Like Catalysis and Oxidation/Adsorption Performances of Acetaminophen and Arsenic Pollutants in Water on a Multimetal Cu-Zn-Fe-LDH.

    Science.gov (United States)

    Lu, Hongtao; Zhu, Zhiliang; Zhang, Hua; Zhu, Jianyao; Qiu, Yanling; Zhu, Linyan; Küppers, Stephan

    2016-09-28

    Acetaminophen can increase the risk of arsenic-mediated hepatic oxidative damage; therefore, the decontamination of water polluted with coexisting acetaminophen and arsenic gives rise to new challenges for the purification of drinking water. In this work, a three-metal layered double hydroxide, namely, Cu-Zn-Fe-LDH, was synthesized and applied as a heterogeneous Fenton-like oxidation catalyst and adsorbent to simultaneously remove acetaminophen (Paracetamol, PR) and arsenic. The results showed that the degradation of acetaminophen was accelerated with decreasing pH or increasing H2O2 concentrations. Under the conditions of a catalyst dosage of 0.5 g·L(-1) and a H2O2 concentration of 30 mmol·L(-1), the acetaminophen in a water sample was completely degraded within 24 h by a Fenton-like reaction. The synthesized Cu-Zn-Fe-LDH also exhibited a high efficiency for arsenate removal from aqueous solutions, with a calculated maximum adsorption capacity of 126.13 mg·g(-1). In the presence of hydrogen peroxide, the more toxic arsenite can be gradually oxidized into arsenate and adsorbed at the same time by Cu-Zn-Fe-LDH. For simulated water samples with coexisting arsenic and acetaminophen pollutants, after treatment with Cu-Zn-Fe-LDH and H2O2, the residual arsenic concentration in water was less than 10 μg·L(-1), and acetaminophen was not detected in the solution. These results indicate that the obtained Cu-Zn-Fe-LDH is an efficient material for the decontamination of combined acetaminophen and arsenic pollution.

  17. Design of a novel immobilized solid acid coating and its application in Fenton-like oxidation of phenol

    Science.gov (United States)

    Wang, Jiankang; Jiang, Zhaohua; Wang, Yajing; Xia, Qixing; Yao, Zhongping

    2017-07-01

    A novel immobilized solid acid coating on Q235 carbon steel was successfully prepared via plasma electrolytic oxidation. Sulfate functionalized Fe3O4/FeAl2O4 was confirmed by XRD, TEM and XPS analysis and surface acidic property was verified by NH3-TPD measurement. Fenton-like degradation performance was evaluated by employing phenol as target pollutant. Fast phenol degradation under the wide range of pH (pH 6-9) was accomplished within only 11 min. Without sulfate functionalization, phenol could hardly be degraded by Fenton-like oxidation which meant that after sulfate functionalization the existence of acidic microenvironment on the catalyst surface not only provided an optimal circumstance for enhanced Fenton-like reaction, but also avoided adjusting pH of the treated wastewater. A reasonable Fenton-like degradation mechanism was proposed. This paper offered a novel design thought for synthesizing excellent Fenton-like coating catalyst under circumneutral pH.

  18. Degradation of Reactive Black 5 dye by CWPO using Fe/mining sand under photo-Fenton process

    Science.gov (United States)

    Amri, Nurulhuda; Nasuha, Norhaslinda; Halim, Siti Fatimah Abdul; Ngah, Khairuddin

    2015-05-01

    This present study was conducted to investigate the effectiveness of catalytic wet peroxide oxidation (CWPO) process using photo-Fenton method and the used of mining sand as support catalyst as well as to determine the optimum parameters and effect of catalyst wt%, pH, H2O2 concentration, initial dye concentration and catalyst dosage on RB 5 degradation. The Fe/mining sand was prepared by impregnation technique and a solar degradation of RB 5 carried out by mean photo-Fenton reaction promoted by solar energy. The dye degradation was monitored during the experimental runs through UV/Vis spectrophotometer. In this process, the reaction condition were optimized at 0.4 of catalyst wt%, pH 2, 4 mM of H2O2 concentration and 0.5 g of catalyst dosage which achieved degradation efficiency at 100% for the three experiments except catalyst dosage which achieved 97.54% respectively within 180 min. The degradation of RB 5 also decreased with the increasing of dye concentration with 10 mg/L achieved the optimum degradation of 99.93%. The results demonstrated that photo-Fenton method could effectively degrade RB 5 and reduce the operating cost by conducting the experiment at optimum conditions.

  19. Ultrasound promoted rapid and green synthesis of thiiranes from epoxides in water catalyzed by chitosan-silica sulfate nano hybrid (CSSNH) as a green, novel and highly proficient heterogeneous nano catalyst.

    Science.gov (United States)

    Behrouz, Somayeh; Soltani Rad, Mohammad Navid; Piltan, Mohammad Amin

    2018-01-01

    The synthesis and characterization of chitosan-silica sulfate nano hybrid (CSSNH) as a novel, green and highly efficient heterogeneous nano catalyst is described. The catalytic activity of this new biopolymeric nano catalyst was investigated in the ultrasonic assisted green synthesis of structurally diverse thiiranes from epoxides using thiourea in water at room temperature. CSSNH was characterized using some different microscopic and spectroscopic techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N2 adsorption isotherm, Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA). The green nature, cheapness, efficiency, ease of preparation, handling and reusability of this new catalyst makes this catalyst to be useful for green industrial processes. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Heterogeneous photocatalysis on construction materials: effect of catalyst properties on the efficiency for degrading NOx and self cleaning

    Directory of Open Access Journals (Sweden)

    Bengtsson, N.

    2014-05-01

    Full Text Available This paper analyzes the effect of some properties of different catalysts on the photocatalytic activity. The efficiency has been determined for two different processes: NOx abatement and self-cleaning for Rhodamine B and tobacco extract being, the TiO2 based photocatalyst, supported as coatings on white mortar. Eight different catalysts were tested, seven commercial ones and one home-made catalyst with improved visible light absorption properties. Additionally, some of them were submitted to exposition to water and/or calcinations to alter their physical properties. A kinetic approach was used to evaluate the photocatalytic activity, being the first reaction constant (for NO and just empirical constants (for self-cleaning the parameters used for the comparison of the different materials. As a result, the efficiency, even for ranking, is dependent on the type of contaminant used in the experiment. In general, NO oxidation and tobacco followed similar trends while no clear relations were found for Rhodamine B.En este trabajo se analiza el efecto de las propiedades de distintos catalizadores en la actividad fotocatalítica de degradación de NOx y autolimpieza, para Rodamina B y extracto de tabaco. Se han ensayado ocho fotocatalizadores, basados en TiO2 y soportados sobre mortero blanco; siete de ellos comerciales y uno sintetizado en el laboratorio con absorción mejorada en el visible. Adicionalmente, las propiedades físicas de algunos de ellos se alteraron mediante tratamientos con agua y/o por calcinación. La actividad fotocatalítica se ha evaluado mediante aproximación cinética, siendo la constante de reacción de primer orden (para NO y constantes empíricas de ajuste (para autolimpieza los parámetros de comparación entre materiales. Como resultado, la eficiencia depende del contaminante utilizado en el experimento de evaluación. En general, en este estudio, oxidación de NO y de extracto de tabaco presentan tendencias similares

  1. Homogeneous and heterogeneous photoredox-catalyzed hydroxymethylation of ketones and keto esters: catalyst screening, chemoselectivity and dilution effects

    Directory of Open Access Journals (Sweden)

    Axel G. Griesbeck

    2014-05-01

    Full Text Available The homogeneous titanium- and dye-catalyzed as well as the heterogeneous semiconductor particle-catalyzed photohydroxymethylation of ketones by methanol were investigated in order to evaluate the most active photocatalyst system. Dialkoxytitanium dichlorides are the most efficient species for chemoselective hydroxymethylation of acetophenone as well as other aromatic and aliphatic ketones. Pinacol coupling is the dominant process for semiconductor catalysis and ketone reduction dominates the Ti(OiPr4/methanol or isopropanol systems. Application of dilution effects on the TiO2 catalysis leads to an increase in hydroxymethylation at the expense of the pinacol coupling.

  2. Oxidative degradation of sulfathiazole by Fenton and photo-Fenton reactions.

    Science.gov (United States)

    Velásquez, Marizú; Santander, I Paola; Contreras, David R; Yáñez, Jorge; Zaror, Claudio; Salazar, Ricardo A; Pérez-Moya, Montserrat; Mansilla, Héctor D

    2014-01-01

    This article presents experimental results on 47 μmol L(-1) sulfathiazole (STZ) degradation by Fenton and photo-Fenton reactions using multivariate analysis. The optimal experimental conditions for reactions were obtained by Response Surface Methodology (RSM). In the case of the Fenton reactions there were 192 μmol L(-1) ferrous ions (Fe(II)) and 1856 μmol L(-1) hydrogen peroxide (H2O2), as compared with 157 μmol L(-1) (Fe(II)) and 1219 μmol L(-1) (H2O2) for photo-Fenton reactions. Under these conditions, around 90% of STZ degradation were achieved after 8 minutes treatment by Fenton and photo-Fenton reactions, respectively. Moreover, a marked difference was observed in the total organic carbon (TOC) removal after 60-min treatment, achieving 30% and 75% for the Fenton and photo-Fenton reactions, respectively. Acetic, maleic, succinic and oxamic acids could be identified as main Fenton oxidation intermediates. A similar pattern was found in the case of photo-Fenton reaction, including the presence of oxalic acid and ammonia at short periods of irradiation with UV-A. The calculated values of Average Oxidation State (AOS) corroborate the formation of oxidized products from the initial steps of the reaction.

  3. Solvent effects by ionic liquid-water mixtures on the heterogeneous hydrolysis of lignocellulosic biomass with solid catalysts

    Science.gov (United States)

    Prosser, Jacob H.

    Ionic liquids are novel solvents proposed as alternatives for the liquid phase catalysis of lignocellulosic biomass because these can molecularly dissolve lignocellulose to high concentrations. However, solvent effects caused by ionic liquids for this application, such as how they shift the kinetics and equilibrium of lignocellulose conversion relative to other solvents, as well as if these change the nature of catalysts used and inhibit catalytic activity or unfavorably alter catalytic selectivity have not been rigorously considered. Additionally, many issues associated with the use of ionic liquids as solvents in lignocellulose conversion arise. Firstly, most ionic liquids readily undergo liquid phase thermal degradation at moderately low temperatures relevant for catalysis. Secondly, solvothermal degradation of solid catalytic materials by ILs can occur and is something not widely evaluated. Furthermore, the catalytic nature of many commonly used catalysts is altered through ion exchange between ionizable surface groups and ionic liquid ions. To understand how hydrophilic imidazolium-based ionic liquids influence the hydrolysis of lignocellulose, I examine with the aid of spectroscopic ellipsometry, UV-Vis spectrophotometry, high performance liquid chromatography, reflectance-small angle x-ray scattering, and powder x-ray diffraction the: (1) thermal degradation of a 1,2,3-trialkylimidzaolium ionic liquid; (2) solvothermal stability of mesoporous silica and gamma-alumina catalytsts; (3) behavior of the hydrolysis reaction of a lignin model compound in 1,2,3-trialkylimidzaolium ionic liquid-water mixtures; and (4) this same reaction catalyzed by gamma-alumina. From my investigations, I discover that: (1) water is able to diminish the thermal degradation of imidazolium ionic liquids when its composition is above about 35 mol% in these mixtures, an effect I propose is from two different mechanisms; (2) mesoporous silica and gamma-alumina are solvothermally stable

  4. Introducing saccharic acid as an efficient iron chelate to enhance photo-Fenton degradation of organic contaminants.

    Science.gov (United States)

    Subramanian, Gokulakrishnan; Madras, Giridhar

    2016-11-01

    The identification of iron chelates that can enhance photo-Fenton degradation is of great interest in the field of advanced oxidation process. Saccharic acid (SA) is a polyhydroxy carboxylic acid and completely non-toxic. Importantly, it can effectively bind Fe(III) as well as induce photoreduction of Fe(III). Despite having these interesting properties, the effect of SA on photo-Fenton degradation has not been studied. Herein, we demonstrate the first assessment of SA as an iron chelate in photo-Fenton process using methylene blue (MB) as a model organic contaminant. Our results demonstrate that SA has the ability to (i) enhance the photo-Fenton degradation of MB by about 11 times at pH 4.5 (ii) intensify photochemical reduction of Fe(III) to Fe(II) by about 17 times and (iii) accelerate the rate of consumption of H2O2 in photo-Fenton process by about 5 times (iv) increase the TOC reduction by about 2 times and (v) improve the photo-Fenton degradation of MB in the presence of a variety of common inorganic ions and organic matter. The influential properties of SA on photo-Fenton degradation is attributed to the efficient photochemical reduction of Fe(III) via LMCT (ligand to metal charge transfer reaction) to Fe(II), which then activated H2O2 to generate OH and accelerated photo-Fenton degradation efficiency. Moreover, the effect of operational parameters such as oxidant: contaminant (H2O2: MB) ratio, catalyst: contaminant (Fe(III)SA: MB) ratio, Fe(III): SA stoichiometry and pH on the degradation of MB by photo-Fenton in the presence of SA is demonstrated. Importantly, SA assisted photo-Fenton caused effective degradation of MB and 4-Chlorophenol under natural sunlight irradiation in natural water matrix. The findings strongly support SA as a deserving iron chelate to enhance photo-Fenton degradation. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Synthesis of bio-additives: transesterification of ethyl acetate with glycerol using homogeneous or heterogeneous acid catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Meireles, Bruno A.; Pereira, Vera Lucia P., E-mail: patrocinio@nppn.ufrj.br [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Centro de Ciencias da Saude. Nucleo de Pesquisas de Produtos Naturais

    2013-01-15

    A new catalytic route with potential practical interest to sustainable production of bioadditives from glycerol is described. Ethyl acetate was transesterified with glycerol, in the ratio glycerol:EtOAc 1:10, at 25 or 90 deg C using 0.1 equiv.of H{sub 2}SO{sub 4} or TsOH, as homogeneous catalysts. H{sub 2}SO{sub 4} led to the total glycerol consumption in 2 h. In the equilibrium, attained in 9 h, 100% yield of a diacetin:triacetin (55:45) mixture was formed. Using Amberlyst Registered-Sign 15 dry and Amberlyst Registered-Sign 16 wet in 1:30 glycerol:EtOAc ratio and reflux at 90 Degree-Sign C the total glycerol consumption was achieved in 2 and 10h, respectively. The lower reactivity of Amberlyst-16 wet was explained in terms of deactivation of acid sites and decrease in glycerol diffusion to the inner resin pores, both factors caused by adsorbed water. The kinetics of glycerol transformation and product distribution in the equilibrium in relation to the H{sub 2}SO{sub 4}, Amberlyst-15 (dry) and Amberlyst-16 (wet) catalyzed reactions were measured. (author)

  6. Química organometálica de superfície aplicada à preparação de catalisadores heterogêneos bem definidos Surface organometallic chemistry applied to the preparation of well defined heterogeneous catalysts

    Directory of Open Access Journals (Sweden)

    Silvana I. Wolke

    2002-11-01

    Full Text Available The study of the reactions of organometallic complexes with the surfaces of inorganic oxides, zeolites and metals constitutes the basis of Surface Organometallic Chemistry (SOMC. The basic rules of organometallic chemistry are often valid when applied to surfaces and well-defined surface organometallic complexes can be obtained. These complexes can be used as heterogeneous catalysts or, by controlled reactions, can be transformed in other species useful for a given catalytic reaction. In some cases, these catalysts exhibit higher activity and/or selectivity than their analogous molecular complexes.

  7. MOF-derived magnetic carbonaceous nanocomposite as a heterogeneous catalyst to activate oxone for decolorization of Rhodamine B in water.

    Science.gov (United States)

    Lin, Kun-Yi Andrew; Chang, Hsuan-Ang; Chen, Ru-Chieh

    2015-07-01

    Metal Organic Frameworks (MOFs) represents one of the most interesting and versatile materials nowadays. As interests to explore MOFs' functionality and potential continue to grow, using MOFs as a platform/template to develop other functional materials has received a great attention recently. Among these MOF-derived materials, MOF-derived carbonaceous materials are particularly attractive owing to its simple preparation and dual characteristics from carbon and metals. Herein, we propose to prepare a cobalt-based magnetic carbonaceous nanocomposite (MCN) by one-step carbonization of the cobalt-containing MOF, ZIF-67. Because of cobalt oxide (i.e., Co3O4) in MCN, MCN not only exhibits magnetic controllability but also catalytic activity to activate Oxone. To investigate and optimize this MCN-activated Oxone process, the decolorization of a cationic dye, Rhodamine B (Rh.B) in water is selected as a model reaction. This MCN-activated Oxone process was found to be the most effective when the ratio of Oxone/MCN was 5/1. While the high temperatures significantly improved the decolorization efficiency, the high initial pH was unfavorable for the Rh.B decolorization by this catalytic Oxone process. UV irradiation and ultrasonication were both found to enhance this MCN-activated Oxone process. The recyclability test revealed that MCN can be continuously used with constant and effective catalytic activity. These features enable MCN to be a promising and interesting catalyst for the wet chemical oxidation such as the Oxone oxidation process. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. TUNGSTOPHOSPHORIC ACID HETEROGENIZED ONTO NH4ZSM5 AS AN EFFICIENT AND RECYCLABLE CATALYST FOR THE PHOTOCATALYTIC DEGRADATION OF DYES

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    Candelaria Leal Marchena

    2015-05-01

    Full Text Available Materials based on tungstophosphoric acid (TPA immobilized on NH4ZSM5 zeolite were prepared by wet impregnation of the zeolite matrix with TPA aqueous solutions. Their concentration was varied in order to obtain TPA contents of 5%, 10%, 20%, and 30% w/w in the solid. The materials were characterized by N2 adsorption-desorption isotherms, XRD, FT-IR, 31P MAS-NMR, TGA-DSC, DRS-UV-Vis, and the acidic behavior was studied by potentiometric titration with n-butylamine. The BET surface area (SBET decreased when the TPA content was raised as a result of zeolite pore blocking. The X-ray diffraction patterns of the solids modified with TPA only presented the characteristic peaks of NH4ZSM5 zeolites, and an additional set of peaks assigned to the presence of (NH43PW12O40. According to the Fourier transform infrared and 31P magic angle spinning-nuclear magnetic resonance spectra, the main species present in the samples was the [PW12O40]3- anion, which was partially transformed into the [P2W21O71]6- anion during the synthesis and drying steps. The thermal stability of the NH4ZSM5TPA materials was similar to that of their parent zeolites. Moreover, the samples with the highest TPA content exhibited band gap energy values similar to those reported for TiO2. The immobilization of TPA on NH4ZSM5 zeolite allowed the obtention of catalysts with high photocatalytic activity in the degradation of methyl orange dye (MO in water, at 25 ºC. These can be reused at least three times without any significant decrease in degree of degradation.

  9. Fundamentos e aplicações ambientais dos processos fenton e foto-fenton Fundaments and environmental applications of fenton and photo-fenton processes

    Directory of Open Access Journals (Sweden)

    Raquel F. Pupo Nogueira

    2007-04-01

    Full Text Available Wastewater and soil treatment processes based on Fenton's reagent have gained great attention in recent years due to its high oxidation power. This review describes the fundaments of the Fenton and photo-Fenton processes and discusses the main aspects related to the degradation of organic contaminants in water such as the complexation of iron, the use of solar light as the source of irradiation and the most important reactor types used. An overview of the main applications of the process to a variety of industrial wastewater and soil remediations is presented.

  10. Degradação de poluentes emergentes por processos Fenton e foto-Fenton

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    Marco A. Benedetti Durigan

    2012-01-01

    Full Text Available A continuous photochemical treatment system was developed for aiming the treatment of aqueous solutions containing relevant micro-pollutants (microcystin-LR, sulfamethoxazole and 17-b estradiol. The continuous photo-Fenton process provided high degradation efficiency. However, contact time between samples and the irradiated region is short relative to total treatment time, indicating that observed changes are predominantly due to the Fenton process. Higher degradation efficiency was observed in systems operated using two treatment cycles, the first involving a batch Fenton process and the second a continuous photo-Fenton treatment.

  11. Experimental and theoretical analysis of asymmetric induction in heterogeneous catalysis: diastereoselective hydrogenation of chiral alpha-hydroxyketones over Pt catalyst.

    Science.gov (United States)

    Busygin, Igor; Taskinen, Antti; Nieminen, Ville; Toukoniitty, Esa; Stillger, Thomas; Leino, Reko; Murzin, Dmitry Yu

    2009-04-01

    Assessing the origin of asymmetric induction in heterogeneously catalyzed hydrogenation is a challenging task. In this work, hydrogenation of a chiral compound, (R)-1-hydroxy-1-phenyl-2-propanone [(R)-PAC], in toluene over cinchonidine modified and unmodified Pt/Al(2)O(3) was studied. To reveal the detailed reaction mechanism and the origin of stereoselectivity in the Pt-catalyzed hydrogenation of the CO double bond, the structures and energies of several adsorption modes of (R)-PAC as well as whole reaction paths for hydrogenation were investigated on Pt(111) by density functional theory (DFT). In agreement with experimental results, the theoretically obtained potential energy profiles for the studied hydrogenation mechanisms implied that (1R,2S)-1-phenyl-1,2-propanediol is formed in excess with respect to the other diastereomeric product diol, (1R,2R)-1-phenyl-1,2-propanediol. Generally, if the elementary hydrogen addition step was thermodynamically more favorable on one of the two diastereotopic faces, it was also kinetically preferred on the same face, and vice versa. Pairwise addition of hydrogen was the most energetically favorable mechanism. Adsorption and hydrogenation of other structurally similar chiral alpha-hydroxyketones, (R)-3-hydroxy-2-butanone and (R)-2-hydroxy-1-cyclohexanone, were also studied computationally on Pt(111). The results showed that cluster model DFT calculations can be used to assess (dia)stereoselectivity in metal-catalyzed hydrogenation of even such complex organic molecules as studied here.

  12. Facile synthesis of magnetic ZnFe2O4-reduced graphene oxide hybrid and its photo-Fenton-like behavior under visible iradiation.

    Science.gov (United States)

    Yao, Yunjin; Qin, Jiacheng; Cai, Yunmu; Wei, Fengyu; Lu, Fang; Wang, Shaobin

    2014-06-01

    A magnetic ZnFe2O4-reduced graphene oxide (rGO) hybrid was successfully developed as a heterogeneous catalyst for photo-Fenton-like decolorization of various dyes using peroxymonosulfate (PMS) as an oxidant under visible light irradiation. Through an in situ chemical deposition and reduction, ZnFe2O4 nanoparticles (NPs) with an average size of 23.7 nm were anchored uniformly on rGO sheets to form a ZnFe2O4-rGO hybrid. The catalytic activities in oxidative decomposition of organic dyes were evaluated. The reaction kinetics, effect of ion species and strength, catalytic stability, degradation mechanism, as well as the roles of ZnFe2O4 and graphene were also studied. ZnFe2O4-rGO showed to be a promising photocatalyst with magnetism for the oxidative degradation of aqueous organic pollutants and simple separation. The combination of ZnFe2O4 NPs with graphene sheets leads to a much higher catalytic activity than pure ZnFe2O4. Graphene acted as not only a support and stabilizer for ZnFe2O4 to prevent them from aggregation, largely improving the charge separation in the hybrid material, but also a catalyst for activating PMS to produce sulfate radicals at the same time. The ZnFe2O4-rGO hybrid exhibited stable performance without losing activity after five successive runs.

  13. Fighting Fenton Chemistry: A Highly Active Iron(III) Tetracarbene Complex in Epoxidation Catalysis.

    Science.gov (United States)

    Kück, Jens W; Anneser, Markus R; Hofmann, Benjamin; Pöthig, Alexander; Cokoja, Mirza; Kühn, Fritz E

    2015-12-07

    Organometallic Fe complexes with exceptionally high activities in homogeneous epoxidation catalysis are reported. The compounds display Fe(II) and Fe(III) oxidation states and bear a tetracarbene ligand. The more active catalyst exhibits activities up to 183 000 turnovers per hour at room temperature and turnover numbers of up to 4300 at -30 °C. For the Fe(III) complex, a decreased Fenton-type reactivity is observed compared with Fe(II) catalysts reported previously as indicated by a substantially lower H2 O2 decomposition and higher (initial) turnover frequencies. The dependence of the catalyst performance on the catalyst loading, substrate, water addition, and the oxidant is investigated. Under all applied conditions, the advantageous nature of the use of the Fe(III) complex is evident. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Recent Overview of Solar Photocatalysis and Solar Photo-Fenton Processes for Wastewater Treatment

    Directory of Open Access Journals (Sweden)

    A. G. Gutierrez-Mata

    2017-01-01

    Full Text Available This literature research, although not exhaustive, gives perspective to solar-driven photocatalysis, such as solar photo-Fenton and TiO2 solar photocatalysis, reported in the literature for the degradation of aqueous organic pollutants. Parameters that influence the degradation and mineralization of organics like catalyst preparation, type and load of catalyst, catalyst phase, pH, applied potential, and type of organic pollutant are addressed. Such parameters may also affect the photoactivity of the catalysts used in the studied solar processes. Solar irradiation is a renewable, abundant, and pollution-free energy source for low-cost commercial applications. Therefore, these solar processes represent an environmentally friendly alternative mainly because the use of electricity can be decreased/avoided.

  15. Catalytic Synthesis of 3-Methyl-1-phenyl-1H-benzo[g]pyrazolo[3,4-b]quinoline-5,10-dione Derivatives Using Cerium Oxide Nanoparticles as Heterogeneous Catalyst in Green Conditions

    Directory of Open Access Journals (Sweden)

    Ali Gharib

    2013-01-01

    Full Text Available We have developed a new methodology for the synthesis of 3-methyl-1-phenyl-1H-benzo[g]pyrazolo[3,4-b]quinoline-5,10-dione derivatives in excellent yields. A new green chemistry protocol with the reusability of the nanoparticle as catalyst has been developed for the synthesis of 3-methyl-1-phenyl-1H-benzo[g]pyrazolo[3,4-b]quinoline-5,10-dione derivatives via one-pot reaction of 3-methyl-1-phenyl-1H-pyrazol-5-amine, arylaldehydes, and 2-hydroxynaphthalene-1,4-dione in water as green solvent and using cerium oxide nanoparticles (CONPs as heterogeneous catalyst. The present methodology affords several advantages such as simple procedure, excellent yields, and short reaction time. The catalyst is inexpensive, stable, easily recycled, and reused for several cycles with consistent activity.

  16. A combined process of adsorption and Fenton-like oxidation for furfural removal using zero-valent iron residue.

    Science.gov (United States)

    Li, Furong; Bao, Jianguo; Zhang, Tian C; Lei, Yutian

    2015-01-01

    In this study, the feasibility of using a combined adsorption and Fenton-like oxidation process (with zero-valent iron (ZVI) residue from heat wraps as an absorbent and catalyst) to remove furfural in the solution was evaluated. The influencing parameters (e.g. pH, H2O2 concentration, initial furfural concentration) and the reusability of ZVI residue (to replace the iron powder) were estimated. The ZVI residue was found to have much better adsorption effect on furfural at pH 2.0 compared with pH 6.7. For Fenton-like reaction alone with ZVI residue, the highest furfural removal of 97.5% was observed at the concentration of 0.176 mol/L H2O2, and all of the samples had >80% removal efficiency at different initial furfural concentrations of 2, 10, 20, 30 and 40 mmol/L. However, with a combined adsorption and Fenton-like oxidation, the removal efficiency of furfural was nearly 100% for all treatments. The ZVI residue used for furfural removal was much better than that of iron powder in the Fenton-like reaction at a seven-cycle experiment. This study suggests the combined process of adsorption and Fenton-like oxidation using ZVI residue is effective for the treatment of furfural in the liquid.

  17. A Bio-Electro-Fenton System Employing the Composite FePc/CNT/SS316 Cathode

    Directory of Open Access Journals (Sweden)

    Yi-Ta Wang

    2017-02-01

    Full Text Available Bio-electro-Fenton microbial fuel cells generate energy through the decomposition of organic matter by microorganisms. The generated electricity drives a Fenton reaction in a cathode chamber, which can be used for the decolorization of dye wastewater. Most of the previous works added expensive platinum catalyst to improve the electrical property of the system. In this research, aligned carbon nanotubes (CNTs were generated on the surface of SS316 stainless steel by chemical vapor deposition, and an iron phthalocyanine (FePc catalyst was added to fabricate a compound (FePc/CNT/SS316 that was applied to the cathode electrode of the fuel cell system. This was expected to improve the overall electricity generation efficiency and extent of decolorization of the system. The results showed that the maximum current density of the system with the modified electrode was 3206.30 mA/m2, and the maximum power was 726.55 mW/m2, which were increased by 937 and 2594 times, respectively, compared to the current and power densities of a system where only the SS316 stainless steel electrode was used. In addition, the decolorization of RB5 dye reached 84.6% within 12 h. Measurements of the electrical properties of bio-electro-Fenton microbial fuel cells and dye decolorization experiments with the FePc/CNT/SS316 electrode showed good results.

  18. Sono-incorporation of CuO nanoparticles on the surface and into the mesoporous hexatitanate layers: Enhanced Fenton-like activity in degradation of orange-G at its neutral pH

    Science.gov (United States)

    Sehati, S.; Entezari, M. H.

    2017-03-01

    In this work, for the first time, CuO/Ti6O13 mesoporous nanocomposite was synthesized by direct intercalation of CuO nanoparticles into hexatitanate layers in the presence of ultrasound. In fact mesoporous potassium hexatitanate with high pore size (44.94 nm) was used as a support. CuO nanoparticles were grown into the titanate pores which caused formation of ultra small CuO with uniform size and high surface area. In fact, titanate is considered as a substrate for better dispersion and nucleation of the CuO nanoparticles which prevented the agglomeration and overgrowth of guest molecules. The prepared sample was characterized by XRD, FE-SEM, TEM, UV-vis spectra, N2 adsorption-desorption, Raman spectra and FT-IR techniques. The product was used as a heterogeneous Fenton-like catalyst for the degradation of Orang G (OG). The effect of important parameters, including pH, H2O2 addition rate and catalyst loading on the decolorization of OG were investigated. Based on the results, CuO/Ti6O13 catalyst exhibited high catalytic activity for OG degradation in aqueous solution at neutral pH of the dye. Moreover, breaking of H2O2 during the catalytic reaction was monitored by spectroscopic method. The results confirmed the decomposition of H2O2 to produce rad OH which is the main active species for the degradation of OG.

  19. Photo-Fenton and Fenton Oxidation of Recalcitrant Wastewater from the Wooden Floor Industry.

    Science.gov (United States)

    Hansson, Henrik; Kaczala, Fabio; Marques, Marcia; Hogland, William

    2015-06-01

    There is a need for development of on-site wastewater treatment technologies suitable to "dry-process" industries, such as the wooden floor sector. Due to the nature of their activities, these industries generate low volumes of highly polluted and recalcitrant wastewaters due to washing and cleaning surfaces and machinery. Advanced oxidation processes such as Fenton and photo-Fenton are potentially feasible options for the treatment of wastewaters with not easily biodegradable pollutants. The wastewater from a wooden floor industry with initial COD value of 4956 mg/L and TOC value of 2730 mg/L was treated with Fenton (Fe/H2O2) and photo-Fenton (Fe/H2O2/UV) applying a 2-level full-factorial experimental design. The highest removals of COD and TOC (79% and 62% respectively) were achieved when photo-Fenton was applied. In conclusion, Fenton and photo-Fenton are promising treatment options for these highly recalcitrant wastewaters, photo-Fenton being a more promising option according to the results.

  20. Degradation of 4-methylbenzylidene camphor (4-MBC Using Fenton, UV Light Irradiation and Photo-Fenton

    Directory of Open Access Journals (Sweden)

    Ji Chunmei

    2017-01-01

    Full Text Available As one of the most commonly employed UV-filters, 4-methylbenzylidene camphor (4-MBC has been shown to accumulate in the environment and have endocrine disrupting activity. 4-MBC cannot be degraded completely by common methods in wastewater treatment plants. To prevent the environmental problems caused by 4-MBC from being more serious, finding effective method to degrade 4-MBC is essential. In this research, Fenton reaction and photo-Fenton was employed to degrade the 4-MBC. Orthogonal experimental design was employed to evaluate the influence of factors (Fe2+, H2O2, pH and reaction time on the degradation of 4-MBC. The degradation rate reached to 66.01% in Fenton process and 96.71% in photo-Fenton process. UV light irradiation was also employed to degrade 4-MBC. After being irradiated by mercury lamp (300W 90 min, the concentration of the 4-MBC reduced 85.4%, but most of them translated to the isomeride. Compared with the Fenton, photo-Fenton and UV light irradiation processes, we deduces that photo-Fenton can get the better degradation efficiency of 4-MBC, and, Fenton reagents and light irradiation are synergistic.

  1. Treatment of sugarcane vinasse by combination of coagulation/flocculation and Fenton's oxidation.

    Science.gov (United States)

    Guerreiro, Lígia F; Rodrigues, Carmen S D; Duda, Rose M; de Oliveira, Roberto A; Boaventura, Rui A R; Madeira, Luis M

    2016-10-01

    The efficiency of individual and integrated processes applied to organic matter reduction and biodegradability improvement of a biodigested sugarcane vinasse wastewater was assessed. Strategies considered were Fenton's oxidation (Strategy 1), coagulation/flocculation (Strategy 2) and the combination of both processes (coagulation/flocculation followed by Fenton's reaction) - Strategy 3. It was found that Fenton's oxidation per se allowed reducing the organic matter, increasing the wastewater biodegradability and a non-toxic effluent was generated; however the cost of treatment was very high (86.6 R$/m(3) - 21.2 €/m(3)). Under optimized conditions, coagulation/flocculation provided a slight increase in effluent's biodegradability, toxicity towards Vibrio fischeri was also eliminated and moderate removals of total organic carbon - TOC - (30.5%), biological oxygen demand - BOD5 - (27.9%) and chemical oxygen demand - COD - (43.6%) were achieved; however, the operating costs are much smaller. The use of dissolved iron resulting from coagulation/flocculation (270 mg/L) as catalyst in the second stage - Fenton's oxidation - was shown to be an innovative and economically attractive strategy. Under optimal conditions overall removals of 51.6% for TOC, 45.7% for BOD5 and 69.2% for COD were achieved, and a biodegradable (BOD5:COD ratio = 0.54) and non-toxic effluent was obtained. In order to increase the efficiency of the process but using less hydrogen peroxide, the Fenton's oxidation was performed by gradually adding the oxidant. This procedure allowed to obtain the highest organic matter removal efficiency (as compared with the addition of all hydrogen peroxide at the beginning of the reaction). This way it was possible to minimize the reagent consumption and, consequently, reduce the treatment cost. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. A novel structural Fenton-like nanocatalyst with highly improved catalytic performance for generalized preparation of iron oxide@organic dye polymer core-shell nanospheres.

    Science.gov (United States)

    Zhao, Guanghui; Peng, Xiaomen; Li, Hongping; Wang, Jianzhi; Zhou, Lincheng; Zhao, Tianqi; Huang, Zhihao; Jiang, Haifei

    2015-05-01

    FexOy@FexOy/C nanoparticles with a soap-bubble-like shell have been synthesized, and the materials exhibit excellent Fenton catalytic performance. More importantly, FexOy@FexOy/C nanoparticles as catalysts and precursors could catalyze organic dye molecules to form iron oxide@organic dye polymer core-shell nanospheres.

  3. Oligomerization of Ethylene to Produce Linear α-Olefins Using Heterogeneous Catalyst Prepared by Immobilization of α-Diiminenickel(II Complex into Fluorotetrasilicic Mica Interlayer

    Directory of Open Access Journals (Sweden)

    Hideki Kurokawa

    2013-02-01

    Full Text Available Heterogeneous catalysts for production of linear α-olefins from ethylene were prepared by the direct reaction of the α-diimine ligand [L: R-N=C(R'-C(R'=N-R; R' = Me and R = 2,6-Me2Ph (L5, 2,5-Me2Ph (L1, 2-MePh (L2, or Ph (L3; R' = 1,8-naphth-diyl and R = Ph (L4] and Ni2+ ion-exchanged fluorotetrasilicic mica. Only high molecular weight polyethylene was obtained in the reaction using the L5/Ni2+-Mica procatalyst activated by AlEt3 (TEA as an activator, whereas the TEA-activated L1- and L2/Ni2+-Mica procatalysts afforded a mixture of a large amount of low-molecular weight polyethylene and a small amount of oligomers having 4-22 carbons. The procatalyst consisting of Ni2+-Mica and the L3 ligand that possesses non-substituted phenyl groups on the iminonitrogen atoms effectively promoted the oligomerization of ethylene after its activation with TEA, resulting in the fact that the ethylene oligomers were produced with a moderate catalytic activity (101 g-ethylene g-cat−1 h−1 at 0.7 MPa-ethylene in the presence of TEA. When the backbone was varied from the butane moiety (L3 to acenaphthene (L4, the solid product dramatically increased. The weight percentage of the oligomers in the total products increased with the increasing reaction temperature; however, an insignificant increase in the oligomers was observed when the ethylene pressure was decreased.

  4. Continuous generation of hydroxyl radicals for highly efficient elimination of chlorophenols and phenols catalyzed by heterogeneous Fenton-like catalysts yolk/shell Pd@Fe3O4@metal organic frameworks.

    Science.gov (United States)

    Niu, Hongyun; Zheng, Yang; Wang, Saihua; Zhao, Lixia; Yang, Shipeng; Cai, Yaqi

    2018-03-15

    Core/shell Fe 3 O 4 -decorated Pd nanoparticles (NPs) hybrids (Pd@Fe 3 O 4 ) are prepared through a "green", and one-pot chemical process. The Pd@Fe 3 O 4 hybrids consisted of faceted quasi-spherical Pd nanoparticles (NPs) cores (∼20 nm) surrounded by close-packed Fe 3 O 4 NPs (∼7 nm). To improve the stability and avoid aggregation of Pd@Fe 3 O 4 hybrids in water, hollow Fe-metal organic frameworks (Fe-MOFs) were applied to enwrap Pd@Fe 3 O 4 to obtain yolk/shell structured composites. Sub-10 nm Fe 3 O 4 and Pd NPs close to each other were distributed evenly in the MOFs shell of Pd@Fe 3 O 4 @MOFs. The yolk/shell Pd@Fe 3 O 4 @MOFs can catalyze the oxidative degradation of chlorophenols and phenols by hydroxyl radicals (OH) decomposed from H 2 O 2 . With low molar ratio of H 2 O 2 /pollutants, the pollutants are degraded and mineralized efficiently and rapidly. The outstanding catalytic efficiency of Pd@Fe 3 O 4 @MOFs is contributed by the fast and continuous generation of OH radicals in Pd@Fe 3 O 4 @MOFs suspension which is detected with the electron spin resonance spin-trap technique and a continuous-flow chemiluminescence system. Lack of consumption of hydroperoxyl radicals/superoxide radicals (HO 2 /O 2 - ) in the Pd@Fe 3 O 4 @MOFs-H 2 O 2 system might suggest that the production of OH radicals results from the electron transferring from Pd to Fe 3 O 4 component both in the inner Pd@Fe 3 O 4 and MOF shell, which facilitates fast Fe(III)/Fe(II) redox cycle. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Kinetics and reaction pathways of formaldehyde degradation using the UV-fenton method.

    Science.gov (United States)

    Liu, Xiangxuan; Liang, Jiantao; Wang, Xuanjun

    2011-05-01

    This study was based on the purpose of investigating the reaction rules of formaldehyde (HCHO) as an intermediate product in the degradation of many other organic wastewaters. The process conditions of UV-Fenton method for the degradation of the low concentrations of HCHO were studied in a batch photochemical reactor. The results showed that, when the original HCHO concentration was 30 mg/L, at an operating temperature of 23 degrees C, pH = 3, an H202 dosage of 68 mg/L, and an H2O2-to-Fe2+ mole ratio (H2O2:Fe2+) of 5, 91.89% of the HCHO was removed after 30 minutes. The degradation of HCHO in the UV-Fenton system was basically in accordance with the exponential decay. The kinetic study results showed that the reaction orders of HCHO, Fe2+, and H2O2 in the system were 1.054, 0.510, and 0.728, respectively, and the activation energy (Ea) was 9.85 kJ/mol. The comparison of UV/H2O2, Fenton, and UV-Fenton systems for the degradation of HCHO, and the results of iron catalyst tests showed that the mechanism of UV-Fenton on the degradation of HCHO was through a synergistic effect of Fe2+ and UV light to catalyze the decomposition of H2O2. The introduction of UV irradiation to the Fenton system largely increased the degradation rate of HCHO, mainly as a result of the accelerating effect on the formation of the Fe2+/Fe3+ cycle. The reaction products were analyzed by gas chromatography-mass spectrometry and a chemical oxygen demand (COD) analyzer. The effluent gases also were analyzed by gas chromatography. Based on those results, the reaction pathways of HCHO in the UV-Fenton system were proposed. The qualitative and quantitative analysis of the reaction products and the COD showed that the main intermediate product of the reaction was formic acid, and the further oxidation of it was the rate-limiting step for the degradation of HCHO.

  6. Catalysts for Environmental Remediation

    DEFF Research Database (Denmark)

    Abrams, B. L.; Vesborg, Peter Christian Kjærgaard

    2013-01-01

    The properties of catalysts used in environmental remediation are described here through specific examples in heterogeneous catalysis and photocatalysis. In the area of heterogeneous catalysis, selective catalytic reduction (SCR) of NOx was used as an example reaction with vanadia and tungsta...

  7. Commercial- and whitewashing-grade limestone as a heterogeneous catalyst for synthesis of fatty acid methyl esters from used frying oil (UFO)

    Energy Technology Data Exchange (ETDEWEB)

    Agrawal, Shweta; Singh, Bhaskar; Sharma, Yogesh C. [Banaras Hindu University, Department of Applied Chemistry, Institute of Technology, Varanasi (India); Frometa, Amado Enrique N. [Universidad Tecnologica de Izucar de Matamoros, Puebla (Mexico)

    2012-12-15

    Commercial-grade limestone used in whitewashing which is a low-cost material has been used as a catalyst for the synthesis of fatty acid methyl esters. The catalyst was characterized by differential thermal analysis/thermogravimetric analysis, X-ray diffraction, and Fourier transform infrared spectroscopy for the study of its physicochemical nature. The catalyst was calcined at 900 C for 2.5 h for the decomposition of calcium carbonate to calcium oxide. The catalyst was further activated by dissolving 1.5 wt% of catalyst in 30 ml methanol (7.5:1, methanol to used frying oil molar ratio) and stirred at 25 C for 1 h on a magnetic stirrer. The transesterification reaction was performed using calcium oxide as a catalyst and then with the ''activated calcium oxide.'' The conversion obtained was 94.4 % with calcium oxide and was found to be lower for the ''activated calcium oxide'' (i.e., 87.36 %). The conversion increased to 96.8 % on increasing the catalyst amount to 2.0 wt% in 5 h. A high yield (>95 %) of fatty acid methyl esters was observed when either calcium oxide or ''activated calcium oxide'' was taken as catalyst. The catalytic activity of calcium oxide obtained from low-grade limestone has been found to be comparable with the laboratory-grade CaO. (orig.)

  8. Ionophore silica-coated magnetite nanoparticles as a recyclable heterogeneous catalyst for one-pot green synthesis of 2,4,5-trisubstituted imidazoles.

    Science.gov (United States)

    Naeimi, Hossein; Aghaseyedkarimi, Dorsa

    2016-01-21

    Novel multi-SO3H functionalized strong Brønsted acidic ionic liquid coated magnetite nanoparticles have been prepared and applied as catalyst for the synthesis of 2,4,5-trisubstituted imidazoles. The results showed that a novel catalyst was very efficient for the reaction and could be magnetically separated and reused at least 6 times with less reduction in its catalytic activity. Operational simplicity, low cost of the catalyst used, high yields, environmental friendliness, wide applicability, reusability and easy recovery of the catalyst using an external magnet are the most important features of this methodology. The catalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), X-Ray diffraction analysis (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray analysis (EDX), dynamic laser scattering (DLS) and vibrating sample magnetometry (VSM).

  9. Landfill Leachates Treatment by /UV, /, Modified Fenton, and Modified Photo-Fenton Methods

    Directory of Open Access Journals (Sweden)

    Jeremi Naumczyk

    2012-01-01

    Full Text Available Advanced oxidation processes (AOPs such as H2O2/UV, O3/H2O2, modified Fenton, and modified photo-Fenton processes have been investigated in terms of the treatment of landfill leachate with ratio of BOD5/COD in the range of 0.22 to 0.24. The modification of Fenton and photo-Fenton processes consisted in the inclusion of precipitation and separation of humic substances at pH 3. Due to the precipitation, the value of COD decreased by 39% and BOD5 by 7.1%. The modification of the processes allowed us to improve the efficiency and to decrease the doses of reagents necessary to continue the process. Modified photo-Fenton process proved to be the most effective (92.7% COD removal of all processes investigated. Additionally, modified-Fenton process was much more effective than the other two processes when compared up to 120 min, while after longer times it gave the least satisfactory results. After 30 min of modified-Fenton process BOD5/COD ratio increased to 0.43. The parameter referred to as “efficiency of oxidants” was used to estimate the efficiency of all the processes—its value varied from 178 to 239%. Various substances including phthalates, hydrocarbons, silanes, and siloxanes were identified in raw and treated leachate.

  10. Enhancement of olive mill wastewater biodegradation by homogeneous and heterogeneous photocatalytic oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Badawy, M.I.; Gohary, F.El. [Water Pollution Research Department, National Research Centre (NRC), Dokki, Cairo 11312 (Egypt); Ghaly, M.Y., E-mail: ghalynrc@yahoo.com [Chemical Engineering and Pilot Plant Department, National Research Centre (NRC), Dokki, Cairo (Egypt); Ali, M.E.M. [Water Pollution Research Department, National Research Centre (NRC), Dokki, Cairo 11312 (Egypt)

    2009-09-30

    Olive mills wastewater (OMW) is characterized by its high organic content and refractory compounds. In this study, an advanced technology for the treatment of the recalcitrant contaminants of OMW has been investigated. The technique used was either photo-Fenton as homogeneous photocatalytic oxidation or UV/semi-conductor catalyst (such as TiO{sub 2}, ZrO{sub 2} and FAZA) as heterogeneous photocatalytic oxidation for treatment of OMW. For both the processes, the effect of irradiation time, amounts of photocatalysts and semi-conductors, and initial concentration of hydrogen peroxide has been studied. At the optimum conditions, photo-Fenton process achieved COD, TOC, lignin (total phenolic compounds) and total suspended solids (TSSs) removal values of 87%, 84%, 97.44% and 98.31%, respectively. The corresponding values for UV/TiO{sub 2} were 68.8%, 67.3%, 40.19% and 48.9%, respectively, after 80 min irradiation time. The biodegradability expressed by BOD{sub 5}/COD ratio for treated wastewater was ranged from 0.66 to 0.8 compared to 0.19 for raw wastewater indicating enhancement of biodegradation.

  11. Removal of synthetic dyes by Fenton process using activated carbon-supported [Fe.sub.2][O.sub.3] obtained from rose remnants/Remocion de colorantes sinteticos mediante el proceso Fenton heterogeneo usando [Fe.sub.2][O.sub.3] soportado en carbon activado obtenido a partir de residuos de rosas

    National Research Council Canada - National Science Library

    Garcia, Julian Camilo; Castellanos, Maria Paula; Uscategui, Angela; Fernandez, Jorge; Pedroza, Aura Marina; Daza, Carlos Enrique

    2012-01-01

    [Fe.sub.2][O.sub.3]-catalysts (0-10% m/m of Fe) supported on activated carbon obtained from rose remnants were used to study the removal of dyes reactive black 5 and crystal violet by the Fenton reaction...

  12. Green synthesis of the Pd nanoparticles supported on reduced graphene oxide using barberry fruit extract and its application as a recyclable and heterogeneous catalyst for the reduction of nitroarenes.

    Science.gov (United States)

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Alizadeh, Mohammad; Bagherzadeh, Mojtaba

    2016-03-15

    Through this manuscript the green synthesis of palladium nanoparticles supported on reduced graphene oxide (Pd NPs/RGO) under the mild conditions through reduction of the graphene oxide and Pd(2+) ions using barberry fruit extract as reducing and stabilizing agent is reported. The as-prepared Pd NPs/RGO was characterized by UV-vis spectroscopy, X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS). The Pd NPs/RGO could be used as an efficient and heterogeneous catalyst for reduction of nitroarenes using sodium borohydride in an environmental friendly medium. Excellent yields of products were obtained with a wide range of substrates and the catalyst was recycled multiple times without any significant loss of its catalytic activity. Copyright © 2015 Elsevier Inc. All rights reserved.

  13. Acetaminophen degradation by electro-Fenton and photoelectro-Fenton using a double cathode electrochemical cell

    Energy Technology Data Exchange (ETDEWEB)

    Luna, Mark Daniel G. de [Department of Chemical Engineering, University of the Philippines, 1011 Diliman, Quezon City (Philippines); Environmental Engineering Graduate Program, University of the Philippines, 1011 Diliman, Quezon City (Philippines); Veciana, Mersabel L. [Environmental Engineering Graduate Program, University of the Philippines, 1011 Diliman, Quezon City (Philippines); Su, Chia-Chi [Department of Environmental Resources Management, Chia Nan University of Pharmacy and Science, Tainan 717, Taiwan (China); Lu, Ming-Chun, E-mail: mmclu@mail.chan.edu.tw [Department of Environmental Resources Management, Chia Nan University of Pharmacy and Science, Tainan 717, Taiwan (China)

    2012-05-30

    Highlights: Black-Right-Pointing-Pointer The electro-Fenton reactor using a double cathode electrochemical cell was applied. Black-Right-Pointing-Pointer The initial Fe{sup 2+} concentration was the most significant parameter for the acetaminophen degradation. Black-Right-Pointing-Pointer Thirteen intermediates were identified and a degradation pathway was proposed. - Abstract: Acetaminophen is a widely used drug worldwide and is one of the most frequently detected in bodies of water making it a high priority trace pollutant. This study investigated the applicability of the electro-Fenton and photoelectro-Fenton processes using a double cathode electrochemical cell in the treatment of acetaminophen containing wastewater. The Box-Behnken design was used to determine the effects of initial Fe{sup 2+} and H{sub 2}O{sub 2} concentrations and applied current density. Results showed that all parameters positively affected the degradation efficiency of acetaminophen with the initial Fe{sup 2+} concentration being the most significant parameter for both processes. The acetaminophen removal efficiency for electro-Fenton was 98% and chemical oxygen demand (COD) removal of 43% while a 97% acetaminophen removal and 42% COD removal were observed for the photoelectro-Fenton method operated at optimum conditions. The electro-Fenton process was only able to obtain 19% total organic carbon (TOC) removal while the photoelectro-Fenton process obtained 20%. Due to negligible difference between the treatment efficiencies of the two processes, the electro-Fenton method was proven to be more economically advantageous. The models obtained from the study were applicable to a wide range of acetaminophen concentrations and can be used in scale-ups. Thirteen different types of intermediates were identified and a degradation pathway was proposed.

  14. Heterogeneous Fenton oxidation of ofloxacin drug by iron alginate support.

    Science.gov (United States)

    Titouhi, Hana; Belgaied, Jamel-Eddine

    2016-08-01

    A new catalytic wet peroxide oxidation of ofloxacin antibiotic is presented in this work. The removal was achieved using a biodegradable sodium alginate-iron material. Several parameters were studied such as iron content, drying duration of the catalytic support, temperature, solid amount and initial drug concentration. The process showed a strong oxidative ability; at optimum conditions, a nearly complete removal of the drug (around 98%) has been reached after three h of treatment. A relatively low decrease of support activity (around 10%) has been observed after three successive oxidation runs and a low iron leaching has been detected (1.2% of the incorporated quantity). The removal of the substrate has been also examined in the absence of hydrogen peroxide in order to discriminate between the contributions of simple adsorption and oxidation processes in the drug disappearance. We also discussed the influence of the studied experimental parameters on the removal kinetic.

  15. Cosmetic wastewater treatment using the Fenton, Photo-Fenton and H2O2/UV processes.

    Science.gov (United States)

    Marcinowski, Piotr P; Bogacki, Jan P; Naumczyk, Jeremi H

    2014-01-01

    Advanced Oxidation Processes (AOPs), such as the Fenton, photo-Fenton and H2O2/UV processes, have been investigated for the treatment of cosmetic wastewaters that were previously coagulated by FeCl3. The Photo-Fenton process at pH 3.0 with 1000/100 mg L(-1) H2O2/Fe(2+) was the most effective (74.0% Chemical Oxygen Demand (COD) removal). The Fenton process with 1200/500 mg L(-1) H2O2/Fe(2+) achieved a COD removal of 72.0%, and the H2O2/UV process achieved a COD removal of 47.0%. Spreading the H2O2 doses over time to obtain optimal conditions did not improve COD removal. The kinetics of the Fenton and photo-Fenton processes may be described by the following equation: d[COD]/dt = -a[COD] t(m) (t represents time and a and m are constants). The rate of COD removal by the H2O2/UV process may be described by a second-order reaction equation. Head Space, Solid-Phase MicroExtraction, Gas Chromatography and Mass Spectrometry (HS-SPME-GC-MS) were used to identify 48 substances in precoagulated wastewater. Among these substances, 26 were fragrances. Under optimal AOP conditions, over 99% of the identified substances were removed in 120 min.

  16. Removal of Carmoisine edible dye by Fenton and photo Fenton processes using Taguchi orthogonal array design

    Directory of Open Access Journals (Sweden)

    Mahmood R. Sohrabi

    2017-05-01

    Full Text Available This research was designed to investigate the removal of Carmoisine from aqueous solutions by advanced oxidation processes including Fenton and photo Fenton systems. The progress of oxidation of Carmoisine dye was monitored by UV–Vis spectrophotometer. The effect of operating parameters affecting removal efficiency such as H2O2, Fe2+ and dye concentrations as well as pH was studied and optimized using Taguchi fractional factorial design during removal of Carmoisine from 50 mL of solutions. Optimal conditions were achieved as 0.015 mmol Fe2+, 0.15 mmol H2O2, 20 mg/L initial dye concentration and pH = 3.5, for the Fenton process and 0.0125 mmol Fe2+, 0.3 mmol H2O2, 20 mg/L initial dye concentration and pH = 3.5 for the photo Fenton process. Also, removal yields were achieved as 92.7% for the Fenton and 95.1% for the photo Fenton processes in optimal conditions. The result of this study showed high efficient removal of Carmoisine by advanced oxidation processes that introduced it as a cheap, versatile and efficient method for removal of this pollutant.

  17. Controlled synthesis of Bi25FeO40 with different morphologies: growth mechanism and enhanced photo-Fenton catalytic properties.

    Science.gov (United States)

    Ji, Wenda; Li, Mingmeng; Zhang, Gaoke; Wang, Pei

    2017-08-15

    Bi25FeO40 microtetrahedra, microcubes and microspheres were successfully synthesized by a simple hydrothermal process and by adding different additive agents. The formation mechanism of Bi25FeO40 microcrystals was proposed; the additive agents had important influences on the morphology and facet exposure of the products. The catalytic activity of these materials was evaluated by the degradation of RhB in a heterogeneous photo-Fenton process. The Bi25FeO40 microcubes showed enhanced photo-Fenton catalytic activity, which can be attributed to an exposed {001} facet with the active O atoms. The hydroxyl radicals are the main active group in the heterogeneous photo-Fenton catalytic degradation. This study may provide a new method to design and synthesize novel nanoscale and microscope functional materials.

  18. Mineralization of aromatics in water by sunlight-assisted electro-fenton technology in a pilot reactor.

    Science.gov (United States)

    Casado, Juan; Fornaguera, Jordi; Galán, María Isabel

    2005-03-15

    The viability of the degradation of aqueous solutions of aniline, nitrobenzene, and 4-chlorophenol by the so-called Photoelectro-Fenton process in a pilot reactor is reported. The Electro-Fenton process stage, based on the flow of oxygen through a gas diffusion cathode to produce H2O2, allows mineralization of about a half of the TOC content in ca. 1 h, because anodic oxidation is coupled with Fenton reaction in the presence of Fe2+ catalyst. An intensity of 20 A was applied in a flow cell comprising a Ti/Pt anode and a carbon-PTFE cathode. After electrolysis, samples of the effluent were exposed to sunlight, and almost complete mineralization was reached after ca. 50 min. Effect of parameters such as electrolysis time, pH, initial concentration, and solar or UVA irradiation on the process efficiencies and the running costs are studied. The Photoelectro-Fenton process using sunlight effectively diminishes these costs. The analogous behavior of the three aromatics suggests similar degradation pathways, regardless of the different groups attached to the ring.

  19. ZnS nanoparticles as an efficient and reusable heterogeneous catalyst for synthesis of 1-substituted-1 H-tetrazoles under solvent-free conditions

    Science.gov (United States)

    Naeimi, Hossein; Kiani, Fatemeh; Moradian, Mohsen

    2014-09-01

    An efficient and green protocol for the synthesis of 1-substituted-1 H-tetrazoles through cyclization reaction of various primary amines, sodium azide, and triethyl orthoformate was described. In this method, a series of tetrazole derivatives was synthesized by using ZnS nanoparticles as an effective, recoverable, and reusable catalyst under solvent-free conditions. This strategy is a magnificent improvement for the synthesis of these heterocycles due to the non-acidic, clean, and solvent-free conditions via a solid recyclable catalyst. The catalyst was separated by simple filtration and reused seven times without significant loss of activity. The ZnS nanoparticles with high surface area and fine monodisperse particles were prepared using the simple microwave-assisted method without using any surfactant. The ZnS nanoparticle catalyst is a good candidate to replace brønsted acids and metal salts or other catalyst for the preparation of 1-substituted-1 H-tetrazoles in high yields and has potential values for industrial applications.

  20. Enhancement of anaerobic digestibility of waste activated sludge using photo-Fenton pretreatment.

    Science.gov (United States)

    Heng, Gan Chin; Isa, Mohamed Hasnain; Lim, Jun-Wei; Ho, Yeek-Chia; Zinatizadeh, Ali Akbar Lorestani

    2017-12-01

    Biological treatments, such as activated sludge process, are common methods to treat municipal and industrial wastewaters. However, they produce huge amounts of waste activated sludge (WAS). The excess sludge treatment and disposal are a challenge for wastewater treatment plants due to economic, environmental, and regulatory factors. In this study, photo-Fenton pretreatment (oxidation using hydrogen peroxide and iron catalyst aided with UV light) was optimized using response surface methodology (RSM) and central composite design (CCD) to determine the effects of three operating parameters (H2O2 dosage, H2O2/Fe2+ molar ratio, and irradiation time) on disintegration and dewaterability of WAS. MLVSS removal, capillary suction time (CST) reduction, sCOD, and EPS were obtained as 70%, 25%, 12,000 mg/L, and 500 mg/L, respectively, at the optimal conditions, i.e., 725 g H2O2/kg TS, H2O2/Fe2+ molar ratio 80, and irradiation time 40 min. Two batch-fed completely mixed mesophilic anaerobic digesters were then operated at 15-day solid retention time (SRT) and 37 ± 0.5 °C to compare the digestibility of untreated and photo-Fenton pretreated sludge in terms of volatile solids (VS) reduction, COD removal, and biogas production at steady-state operations. Photo-Fenton pretreatment followed by anaerobic digestion of WAS was very effective and yielded 75.7% total VS reduction, 81.5% COD removal, and 0.29-0.31 m3/kg VSfed·d biogas production rate, compared to 40.7% total VS solid reduction, 54.7% COD removal, and 0.12-0.17 m3/kg VSfed·d biogas production rate for control. Thus, photo-Fenton can be a useful pretreatment step in sludge management.

  1. Photo-Fenton oxidation with immobilized iron of a dye of the textile industry; Oxidacion foto-Fenton con hierro inmovilizado de un colorante de la industria textil

    Energy Technology Data Exchange (ETDEWEB)

    Riaza Frutos, A.; Manzano Quinones, M. A.; Quiroga Alonso, J. M.

    2006-07-01

    The oxidation of a representative dye of the textile industry (Orange II) has been studied. The primary degradation and mineralization are easy to follow through spectrophotometric and TOC measures, respectively. It was used the photo-Fenton process under conditions of heterogeneous catalysis with the iron ions (III) fixed in a perfluorinated membrane that resists to the oxidation process. The main variables it has been studied the main variable that influence in the process to the object of establishing the best operation conditions. Likewise, it has been carried out the mineralization and kinetic study under the optimal conditions. (Author) 26 refs.

  2. Ultrasound-promoted one-pot three component synthesis of tetrazoles catalyzed by zinc sulfide nanoparticles as a recyclable heterogeneous catalyst.

    Science.gov (United States)

    Naeimi, Hossein; Kiani, Fatemeh

    2015-11-01

    Ultrasound irradiation was applied for the appropriate and rapid synthesis of 1-substituted tetrazoles through cyclization reaction of various primary amines, sodium azide and triethyl orthoformate. This reaction was effectively catalyzed by ZnS nanoparticles as an efficient, recoverable and reusable catalyst. Compared with conventional methods, this method has the considerable advantages such as shorter reaction times, easier work-up, purer products with high yields and mild conditions. The ZnS nanoparticles catalyst is an excellent instance to replace Brønsted acids for the preparation of 1-substituted tetrazole derivatives in very short reaction times with excellent yields. The catalyst can be recovered and reused several times without significant loss of its catalytic activity. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. DeNOx active iron sites in iron loaded ZSM-5 - a multitechnique analysis of a complex heterogeneous catalyst based on Mössbauer spectroscopy

    Science.gov (United States)

    Padmalekha, K. G.; Huang, H.; Ellmers, I.; Pérez Vélez, R.; van Leusen, J.; Brückner, A.; Grünert, W.; Schünemann, V.

    2017-11-01

    Iron loaded zeolites like Fe-ZSM-5 are potent candidates for the catalytic abatement of nitrogen oxides from car exhaust, e.g. from Diesel engines. Recent problems in this field show that there is an urgent need in further improvement of such catalysts, for which a full analysis of Fe species present in them under different conditions is highly desirable. We have studied Fe-ZSM-5 catalysts prepared via solid-state ion exchange by using field dependent Mössbauer spectroscopy at low temperature in order to identify the different iron species present in this type of catalyst in the fresh state and after use in catalysis. Mössbauer spectroscopy proved to be the key technique for a full understanding of species structures, but due to the complexity of structures, guidance by parallel EPR experiments and control by SQUID magnetometry were essential to prove reliability of derived species distributions.

  4. Degradation of atenolol via heterogeneous activation of persulfate by using BiOCl@Fe3O4catalyst under simulated solar light irradiation.

    Science.gov (United States)

    Shi, Yahong; Chen, Hongche; Wu, Yanlin; Dong, Wenbo

    2018-01-01

    Efficient oxidative degradation of pharmaceutical pollutants in aquatic environments is of great importance. This study used magnetic BiOCl@Fe 3 O 4 catalyst to activate persulfate (PS) under simulated solar light irradiation. This degradation system was evaluated using atenolol (ATL) as target pollutant. Four reactive species were identified in the sunlight/BiOCl@Fe 3 O 4 /PS system. The decreasing order of the contribution of each reactive species on ATL degradation was as follows: h +  ≈ HO ·  > O 2 ·-  > SO 4 ·- . pH significantly influenced ATL degradation, and an acidic condition favored the reaction. High degradation efficiencies were obtained at pH 2.3-5.5. ATL degradation rate increased with increased catalyst and PS contents. Moreover, ATL mineralization was higher in the sunlight/BiOCl@Fe 3 O 4 /PS system than in the sunlight/BiOCl@Fe 3 O 4 or sunlight/PS system. Nine possible intermediate products were identified through LC-MS analysis, and a degradation pathway for ATL was proposed. The BiOCl@Fe 3 O 4 nanomagnetic composite catalyst was synthesized in this work. This catalyst was easily separated and recovered from a treated solution by using a magnet, and it demonstrated a high catalytic activity. Increased amount of the BiOCl@Fe 3 O 4 catalyst obviously accelerated the efficiency of ATL degradation, and the reusability of the catalyst allowed the addition of a large dosage of BiOCl@Fe 3 O 4 to improve the degradation efficiency.

  5. Oxidation catalyst

    Science.gov (United States)

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

    The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

  6. Mitoxantrone removal by electrochemical method: A comparison of homogenous and heterogenous catalytic reactions

    Directory of Open Access Journals (Sweden)

    Abbas Jafarizad

    2017-08-01

    Full Text Available Background: Mitoxantrone (MXT is a drug for cancer therapy and a hazardous pharmaceutical to the environment which must be removed from contaminated waste streams. In this work, the removal of MXT by the electro-Fenton process over heterogeneous and homogenous catalysts is reported. Methods: The effects of the operational conditions (reaction medium pH, catalyst concentration and utilized current intensity were studied. The applied electrodes were carbon cloth (CC without any processing (homogenous process, graphene oxide (GO coated carbon cloth (GO/CC (homogenous process and Fe3O4@GO nanocomposite coated carbon cloth (Fe3O4@GO/CC (heterogeneous process. The characteristic properties of the electrodes were determined by atomic force microscopy (AFM, field emission scanning electron microscopy (FE-SEM and cathode polarization. MXT concentrations were determined by using ultraviolet-visible (UV-Vis spectrophotometer. Results: In a homogenous reaction, the high concentration of Fe catalyst (>0.2 mM decreased the MXT degradation rate. The results showed that the Fe3O4@GO/CC electrode included the most contact surface. The optimum operational conditions were pH 3.0 and current intensity of 450 mA which resulted in the highest removal efficiency (96.9% over Fe3O4@GO/CC electrode in the heterogeneous process compared with the other two electrodes in a homogenous process. The kinetics of the MXT degradation was obtained as a pseudo-first order reaction. Conclusion: The results confirmed the high potential of the developed method to purify contaminated wastewaters by MXT.

  7. Degradation of flumequine by the Fenton and photo-Fenton processes: Evaluation of residual antimicrobial activity

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues-Silva, Caio; Maniero, Milena Guedes [School of Civil Engineering, Architecture and Urbanism, University of Campinas — UNICAMP, P.O. Box 6021, CEP 13083-852, Campinas, SP (Brazil); Rath, Susanne [Chemistry Institute, University of Campinas — UNICAMP, P.O. Box 6154, CEP 13084-971, Campinas, SP (Brazil); Guimarães, José Roberto, E-mail: jorober@fec.unicamp.br [School of Civil Engineering, Architecture and Urbanism, University of Campinas — UNICAMP, P.O. Box 6021, CEP 13083-852, Campinas, SP (Brazil)

    2013-02-15

    Flumequine is a broad-spectrum antimicrobial agent of the quinolone class, and it is widely used as a veterinary drug in food-producing animals. The presence of flumequine in the environment may contribute to the development of drug resistant bacterial strains. In this study, water samples fortified with flumequine (500 μg L{sup −1}) were degraded using the Fenton and photo-Fenton processes. The maximum degradation efficiency for flumequine by the Fenton process was approximately 40% (0.5 mmol L{sup −1} Fe(II), 2.0 mmol L{sup −1} H{sub 2}O{sub 2} and 15 min). By applying UV radiation (photo-Fenton process), the efficiency reached more than 94% in 60 min when 0.25 mmol L{sup −1} Fe(II) and 10.0 mmol L{sup −1} H{sub 2}O{sub 2} were used. Under these conditions, the Fenton process was able to reduce the biological activity, whereas the photo-Fenton process eliminated almost all of the antimicrobial activity because it was not detected. Four byproducts with an m/z of 244, 238, 220 and 202 were identified by mass spectrometry, and a degradation pathway for flumequine was proposed. The byproducts were derived from decarboxylation and defluorination reactions and from modifications in the alkylamino chain of the fluoroquinolone. - Highlights: ► Photo-Fenton process achieved the maximum performance, degrading 94% of flumequine. ► As the flumequine concentration decreased, antimicrobial activity also decreased. ► Four byproducts with m/z of 244, 238, 220 and 202 were identified. ► A degradation pathway for flumequine was proposed.

  8. Development plus kinetic and mechanistic studies of a prototype supported-nanoparticle heterogeneous catalyst formation system in contact with solution: Ir(1,5-COD)Cl/gamma-Al2O3 and its reduction by H2 to Ir(0)n/gamma-Al2O3.

    Science.gov (United States)

    Mondloch, Joseph E; Wang, Qi; Frenkel, Anatoly I; Finke, Richard G

    2010-07-21

    An important question and hence goal in catalysis is how best to transfer the synthetic and mechanistic insights gained from the modern revolution in nanoparticle synthesis, characterization, and catalysis to prepare the next generation of improved, supported-nanoparticle heterogeneous catalysts. It is precisely this question and to-date somewhat elusive goal which are addressed by the present work. More specifically, the global hypothesis investigated herein is that the use of speciation-controlled, well-characterized, solid oxide supported-organometallic precatalysts in contact with solution will lead to the next generation of better composition, size- and shape-controlled, as well as highly active and reproducible, supported-nanoparticle heterogeneous catalysts-ones that can also be understood kinetically and mechanistically. Developed herein are eight criteria defining a prototype system for supported-nanoparticle heterogeneous catalyst formation in contact with solution. The initial prototype system explored is the precatalyst, Ir(1,5-COD)Cl/gamma-Al(2)O(3) (characterized via ICP, CO adsorption, IR, and XAFS spectroscopies), and the well-defined product, Ir(0)(n)/gamma-Al(2)O(3) (characterized by reaction stoichiometry, TEM, and XAFS). The Ir(0)(n)/gamma-Al(2)O(3) system proved to be a highly active and long-lived catalyst in the simple test reaction of cyclohexene hydrogenation and in comparison to two literature Ir(0)(n)/Al(2)O(3) heterogeneous catalysts examined under identical conditions. High activity (2.2-4.8-fold higher than that of the literature Ir(0)(n)/Al(2)O(3) catalysts tested under the same conditions) and good lifetime (> or = 220,000 total turnovers of cyclohexene hydrogenation) are observed, in part by design since only acetone solvent, cyclohexene, and H(2) are possible ligands in the resultant "weakly ligated/labile-ligand" supported nanoclusters. Significantly, the Ir(1,5-COD)Cl/gamma-Al(2)O(3) + H(2) --> Ir(0)(n)/gamma-Al(2)O(3

  9. Ultrasound assisted biodiesel production from sesame (Sesamum indicum L.) oil using barium hydroxide as a heterogeneous catalyst: Comparative assessment of prediction abilities between response surface methodology (RSM) and artificial neural network (ANN).

    Science.gov (United States)

    Sarve, Antaram; Sonawane, Shriram S; Varma, Mahesh N

    2015-09-01

    The present study estimates the prediction capability of response surface methodology (RSM) and artificial neural network (ANN) models for biodiesel synthesis from sesame (Sesamum indicum L.) oil under ultrasonication (20 kHz and 1.2 kW) using barium hydroxide as a basic heterogeneous catalyst. RSM based on a five level, four factor central composite design, was employed to obtain the best possible combination of catalyst concentration, methanol to oil molar ratio, temperature and reaction time for maximum FAME content. Experimental data were evaluated by applying RSM integrating with desirability function approach. The importance of each independent variable on the response was investigated by using sensitivity analysis. The optimum conditions were found to be catalyst concentration (1.79 wt%), methanol to oil molar ratio (6.69:1), temperature (31.92°C), and reaction time (40.30 min). For these conditions, experimental FAME content of 98.6% was obtained, which was in reasonable agreement with predicted one. The sensitivity analysis confirmed that catalyst concentration was the main factors affecting the FAME content with the relative importance of 36.93%. The lower values of correlation coefficient (R(2)=0.781), root mean square error (RMSE=4.81), standard error of prediction (SEP=6.03) and relative percent deviation (RPD=4.92) for ANN compared to those R(2) (0.596), RMSE (6.79), SEP (8.54) and RPD (6.48) for RSM proved better prediction capability of ANN in predicting the FAME content. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Insights into the asymmetric heterogeneous catalysis in porous organic polymers: constructing a TADDOL-embedded chiral catalyst for studying the structure-activity relationship.

    Science.gov (United States)

    An, Wan-Kai; Han, Man-Yi; Wang, Chang-An; Yu, Si-Min; Zhang, Yuan; Bai, Shi; Wang, Wei

    2014-08-25

    Construction of porous organic polymers (POPs) as asymmetric catalysts remains as an important but challenging task. Herein, we exploit the "bottom-up" strategy to facilely synthesize an α,α,α',α'-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL)-based chiral porous polymer (TADDOL-CPP) for highly efficient asymmetric catalysis. Constructed through the covalent linkages among the three-dimensional rigid monomers, TADDOL-CPP possesses hierarchical porous structure, high Brunauer-Emmett-Teller (BET) surface area, together with abundant and uniformly-distributed chiral sites. In the presence of [Ti(OiPr)4], TADDOL-CPP acts as a highly efficient and recyclable catalyst in the asymmetric addition of diethylzinc (Et2Zn) to aromatic aldehydes. Based on the direct observation of the key intermediates, the reaction mechanism has been revealed by solid-state (13)C magic-angle spinning (MAS) NMR spectroscopy. In combination with the catalytic testing results, characterization on the working catalyst provides further information for understanding the structure-activity relationship. We suggest that the catalytic activity of TADDOL-CPP is largely affected by the structural rigidity, cooperative catalysis, local chiral environment, and hierarchical porous framework. We expect that the information obtained herein will benefit to the designed synthesis of robust POP catalysts toward practical applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Application of non-thermal plasma reactor and Fenton reaction for degradation of ibuprofen

    Energy Technology Data Exchange (ETDEWEB)

    Marković, Marijana [Center of Chemistry, Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Studentski trg 12-16, 11000 Belgrade (Serbia); Jović, Milica; Stanković, Dalibor [Innovation Center, Faculty of Chemistry, University of Belgrade, P.O. Box 51, 11058 Belgrade 118 (Serbia); Kovačević, Vesna [Faculty of Physics, University of Belgrade, P.O. Box 44, 11000 Belgrade (Serbia); Roglić, Goran [Faculty of Chemistry, University of Belgrade, P.O. Box 51, 11058 Belgrade 118 (Serbia); Gojgić-Cvijović, Gordana [Center of Chemistry, Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Studentski trg 12-16, 11000 Belgrade (Serbia); Manojlović, Dragan, E-mail: manojlo@chem.bg.ac.rs [Faculty of Chemistry, University of Belgrade, P.O. Box 51, 11058 Belgrade 118 (Serbia)

    2015-02-01

    Pharmaceutical compounds have been detected frequently in surface and ground water. Advanced Oxidation Processes (AOPs) were reported as very efficient for removal of various organic compounds. Nevertheless, due to incomplete degradation, toxic intermediates can induce more severe effects than the parent compound. Therefore, toxicity studies are necessary for the evaluation of possible uses of AOPs. In this study the effectiveness and capacity for environmental application of three different AOPs were estimated. They were applied and evaluated for removal of ibuprofen from water solutions. Therefore, two treatments were performed in a non-thermal plasma reactor with dielectric barrier discharge with and without a homogenous catalyst (Fe{sup 2+}). The third treatment was the Fenton reaction. The degradation rate of ibuprofen was measured by HPLC-DAD and the main degradation products were identified using LC–MS TOF. Twelve degradation products were identified, and there were differences according to the various treatments applied. Toxicity effects were determined with two bioassays: Vibrio fischeri and Artemia salina. The efficiency of AOPs was demonstrated for all treatments, where after 15 min degradation percentage was over 80% accompanied by opening of the aromatic ring. In the treatment with homogenous catalyst degradation reached 99%. V. fischeri toxicity test has shown greater sensitivity to ibuprofen solution after the Fenton treatment in comparison to A. salina. - Highlights: • Twelve ibuprofen degradation products were identified in total. • The degradation percentage differed between treatments (DBD/Fe{sup 2+} was 99%). • In DBD/Fe{sup 2+} only aliphatic degradation products were identified. • V. fischeri was sensitive to ibuprofen solution after the Fenton treatment. • A. salina showed no toxic effect when exposed to all post treatment solutions.

  12. B{sub 2}O{sub 3}/Al{sub 2}O{sub 3} as a new, highly efficient and reusable heterogeneous catalyst for the selective synthesis of {beta}-enamino ketones and esters under solvent-free conditions

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jiu-Xi; Gao, Wen-Xia; Jin, Hui-Le; Ding, Jin-Chang; Wu, Hua-Yue, E-mail: huayuewu@wzu.edu.c [Wenzhou University, Wenzhou (China). Coll. of Chemistry and Materials Engineering; Zhang, Chang-Fu [Wenzhou Vocational and Technical College, Wenzhou (China)

    2010-07-01

    Boron oxide adsorbed on alumina (B{sub 2}O{sub 3}/Al{sub 2}O{sub 3}) has been found to be a new and highly efficient heterogeneous catalyst for the synthesis of {beta}-enamino ketones and esters by the enamination of various primary and secondary amines with {beta}-dicarbonyl compounds under solvent-free conditions. The important features of this methodology are broad substrate scope, high yield, no requirement of metal catalysts, high regio- and chemoselectivity and environmental friendliness. In addition, the catalyst could be recovered easily after the reactions and reused without evident loss of reactivity. (author)

  13. Electrochemical destruction of chlorophenoxy herbicides by anodic oxidation and electro-Fenton using a boron-doped diamond electrode

    Energy Technology Data Exchange (ETDEWEB)

    Brillas, Enric; Boye, Birame; Sires, Ignasi; Garrido, Jose Antonio; Rodriguez, Rosa Maria; Arias, Conchita; Cabot, Pere-Lluis; Comninellis, Christos

    2004-10-01

    The degradation of herbicides 4-chlorophenoxyacetic acid (4-CPA), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in aqueous medium of pH 3.0 has been comparatively studied by anodic oxidation and electro-Fenton using a boron-doped diamond (BDD) anode. All solutions are totally mineralized by electro-Fenton, even at low current, being the process more efficient with 1 mM Fe{sup 2+} as catalyst. This is due to the production of large amounts of oxidant hydroxyl radical (OH{center_dot}) on the BDD surface by water oxidation and from Fenton's reaction between added Fe{sup 2+} and H{sub 2}O{sub 2} electrogenerated at the O{sub 2}-diffusion cathode. The herbicide solutions are also completely depolluted by anodic oxidation. Although a quicker degradation is found at the first stages of electro-Fenton, similar times are required for achieving overall mineralization in both methods. The decay kinetics of all herbicides always follows a pseudo first-order reaction. Reversed-phase chromatography allows detecting 4-chlorophenol, 4-chloro-o-cresol, 2,4-dichlorophenol and 2,4,5-trichlorophenol as primary aromatic intermediates of 4-CPA, MCPA, 2,4-D and 2,4,5-T, respectively. Dechlorination of these products gives Cl{sup -}, which is slowly oxidized on BDD. Ion-exclusion chromatography reveals the presence of persistent oxalic acid in electro-Fenton by formation of Fe{sup 3+}-oxalato complexes, which are slowly destroyed by OH{center_dot} adsorbed on BDD. In anodic oxidation, oxalic acid is mineralized practically at the same rate as generated.

  14. Fenton-like oxidation of azo dye using mesoporous Fe/TiO2 prepared by microwave-assisted hydrothermal process

    Directory of Open Access Journals (Sweden)

    Nešić Jelena

    2014-01-01

    Full Text Available Fe-doped TiO2 photocatalysts with different content of Fe (0.5, 1.6, 3.4 and 6.4% were synthesized by the microwave-hydrothermal method and characterized by XRD, N2 physisorption at 77 K and DRS. The characterization showed that Fe ions are highly dispersed in the TiO2 lattice. It was found that all the synthesized catalysts had the mesoporous structure and Fe doping increased BET surface areas. The UV-Vis study showed that the absorption spectra shifted to a longer wavelength (red shift with an increase in the dopant concentration. The photocatalytic activity of the samples was evaluated by the decolorization of textile dye Reactive Blue 52 (RB in aqueous solutions under sun-like radiation in the presence of H2O2 (heterogeneous photo-Fenton process. The photocatalyst with 3.4% Fe was found to be the most efficient with H2O2. The effect of the initial pH of the dye solution was assessed and dissolution of iron ions was studied, as a function of pH value. It was concluded that decolorization is more favorable in acidic pH and when pH >4, the releasing of Fe ions in solution was negligible. Photocatalytic degradation of 4-chlorophenol (4-CP was investigated under the optimal conditions and proved that our catalyst was capable to degrade colorless pollutants. [Projekat Ministarstva nauke Republike Srbije, br. 172030 i br. 172035

  15. Citric Acid-Modified Fenton's Reaction for the Oxidation of Chlorinated Ethylenes in Soil Solution Systems

    Energy Technology Data Exchange (ETDEWEB)

    Seol, Yongkoo; Javandel, Iraj

    2008-03-15

    Fenton's reagent, a solution of hydrogen peroxide and ferrous iron catalyst, is used for an in-situ chemical oxidation of organic contaminants. Sulfuric acid is commonly used to create an acidic condition needed for catalytic oxidation. Fenton's reaction often involves pressure buildup and precipitation of reaction products, which can cause safety hazards and diminish efficiency. We selected citric acid, a food-grade substance, as an acidifying agent to evaluate its efficiencies for organic contaminant removal in Fenton's reaction, and examined the impacts of using citric acid on the unwanted reaction products. A series of batch and column experiments were performed with varying H{sub 2}O{sub 2} concentrations to decompose selected chlorinated ethylenes. Either dissolved iron from soil or iron sulfate salt was added to provide the iron catalyst in the batch tests. Batch experiments revealed that both citric and sulfuric acid systems achieved over 90% contaminant removal rates, and the presence of iron catalyst was essential for effective decontamination. Batch tests with citric acid showed no signs of pressure accumulation and solid precipitations, however the results suggested that an excessive usage of H{sub 2}O{sub 2} relative to iron catalysts (Fe{sup 2+}/H{sub 2}O{sub 2} < 1/330) would result in lowering the efficiency of contaminant removal by iron chelations in the citric acid system. Column tests confirmed that citric acid could provide suitable acidic conditions to achieve higher than 55% contaminant removal rates.

  16. Transesterification of rapeseed oil for biodiesel production in trickle-bed reactors packed with heterogeneous Ca/Al composite oxide-based alkaline catalyst.

    Science.gov (United States)

    Meng, Yong-Lu; Tian, Song-Jiang; Li, Shu-Fen; Wang, Bo-Yang; Zhang, Min-Hua

    2013-05-01

    A conventional trickle bed reactor and its modified type both packed with Ca/Al composite oxide-based alkaline catalysts were studied for biodiesel production by transesterification of rapeseed oil and methanol. The effects of the methanol usage and oil flow rate on the FAME yield were investigated under the normal pressure and methanol boiling state. The oil flow rate had a significant effect on the FAME yield for the both reactors. The modified trickle bed reactor kept over 94.5% FAME yield under 0.6 mL/min oil flow rate and 91 mL catalyst bed volume, showing a much higher conversion and operational stability than the conventional type. With the modified trickle bed reactor, both transesterification and methanol separation could be performed simultaneously, and glycerin and methyl esters were separated additionally by gravity separation. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. Core-shell Fe3O4@MIL-101(Fe) composites as heterogeneous catalysts of persulfate activation for the removal of Acid Orange 7.

    Science.gov (United States)

    Yue, Xinxin; Guo, Weilin; Li, Xianghui; Zhou, Haihong; Wang, Ruiqin

    2016-08-01

    In this study, a novel core-shell Fe3O4@MIL-101 (MIL stands for Materials of Institute Lavoisier) composite was successfully synthesized by hydrothermal method and was fully characterized by X-ray diffraction, transmission electron microscopy, Fourier-transform infrared spectra, and X-ray photoelectron spectroscopy. The composite was introduced as a catalyst to generate powerful radicals from persulfate for the removal of Acid Orange 7 in an aqueous solution. Effects of the central metal ions of MIL-101, amino group content of MIL-101, and pH were evaluated in batch experiments. It was found that both hydroxyl and sulfate radicals were generated; importantly, sulfate radicals were speculated to serve as the dominant active species in the catalytic oxidation of Acid Orange 7. In addition, a possible mechanism was proposed. This study provides new physical insights for the rational design of advanced metal-organic frameworks (MOF)-based catalysts for improved environmental remediation.

  18. Graphite-Supported Perchloric Acid (HClO4-C: An Efficient and Recyclable Heterogeneous Catalyst for the One-Pot Synthesis of Amidoalkyl Naphthols

    Directory of Open Access Journals (Sweden)

    Zhen-Kai Lei

    2013-01-01

    Full Text Available An efficient and direct protocol for the preparation of amidoalkylnaphthols employing a multi-component, one-pot condensation reaction of 2-naphthol, aromatic aldehydes and acetamide or benzamide in the presence of graphite supported perchloric acid under solvent-free conditions is described. The thermal solvent-free procedure offers advantages such as simple work-up, shorter reaction times and higher product yields, and the catalyst exhibited remarkable reactivity and can be recycled.

  19. Graphite-supported perchloric acid (HClO4-C): an efficient and recyclable heterogeneous catalyst for the one-pot synthesis of amidoalkyl naphthols.

    Science.gov (United States)

    Lei, Zhen-Kai; Xiao, Li; Lu, Xiao-Quan; Huang, He; Liu, Chen-Jiang

    2013-01-28

    An efficient and direct protocol for the preparation of amidoalkylnaphthols employing a multi-component, one-pot condensation reaction of 2-naphthol, aromatic aldehydes and acetamide or benzamide in the presence of graphite supported perchloric acid under solvent-free conditions is described. The thermal solvent-free procedure offers advantages such as simple work-up, shorter reaction times and higher product yields, and the catalyst exhibited remarkable reactivity and can be recycled.

  20. Sulfurized hematite for photo-Fenton catalysis

    Directory of Open Access Journals (Sweden)

    Yaping Zhang

    2017-08-01

    Full Text Available A hematite/amorphous sulfur composite was prepared via simple heating hematite and α-sulfur in Teflon-lined autoclave at low temperature. The composite was characterized by X-ray diffraction (XRD, Raman spectrum, Thermal Gravity Analysis (TGA, Transmission Electron Microscopy (TEM and X-ray photoelectron spectroscopy (XPS. The results revealed that an allotrope sulfur at 5–37% weight percent was found in the composite. After sulfuration, Sn2- or S22- was doped in the lattice of hematite, large amounts of OH and SO4 were adsorbed on the surface of hematite. Hematite/amorphous sulfur composite had superior photo-Fenton activities than pure hematite. This work also demonstrated that amorphous sulfur also had the activity of photo-Fenton catalysis. OH- and SO4 radicals facilitated dye adsorption and acted as a bridge to link H2O2. Moreover, SO4 radicals on hematite served as electron trapping center that can receive photo-induced electron from conduction band of hematite and transfer it to the adsorbed H2O2, increasing the rate of photo-Fenton reaction eventually.

  1. DEGRADATION OF MTBE USING FENTON REAGENT

    Directory of Open Access Journals (Sweden)

    A. Khavanin, S. M. Mousavian, S. B. Mortazavi, A. Rezaee and H. Asiliyan

    2005-07-01

    Full Text Available Methyl tertiary-butyl ether (MTBE has been commonly used as a fuel additive because of its many favorable properties that allow it to improve fuel combustion. Unfortunately, increased production and use have led to its introduction into the water supplies. Accordingly, research studies have been initiated to investigate the treatment of contaminated water. Degradation of MTBE in aqueous solution by Fenton reagent (Fe2+ and H2O2 was investigated. This study used Fenton reagent to oxidize MTBE with an attempt to explore the behavior of MTBE decomposition and measure how factors such as pH, [H2O2] and [Fe2+] may influence the degradation of MTBE, and finally the optimum conditions were obtained. Under optimum conditions of 50 mL H2O2, 0.65 g/L Fe2+, pH=3-4 and room temperature, the initial 1000 mg/L MTBE solution was reduced by 99% within 120 min. The results showed that application of Fenton reagent was an effective method for degradation of MTBE.

  2. Review of iron-free Fenton-like systems for activating H{sub 2}O{sub 2} in advanced oxidation processes

    Energy Technology Data Exchange (ETDEWEB)

    Bokare, Alok D.; Choi, Wonyong, E-mail: wchoi@postech.edu

    2014-06-30

    Graphical abstract: - Highlights: • Elements with multiple redox states efficiently decompose H{sub 2}O{sub 2} at neutral pH. • Activation of H{sub 2}O{sub 2} is entirely governed by solution pH and catalyst composition. • Metal leaching and toxicity is an important factor for practical applications. • Iron-free Fenton systems work only in specialized reaction conditions. - Abstract: Iron-catalyzed hydrogen peroxide decomposition for in situ generation of hydroxyl radicals (HO{sup •} ) has been extensively developed as advanced oxidation processes (AOPs) for environmental applications. A variety of catalytic iron species constituting metal salts (in Fe{sup 2+} or Fe{sup 3+} form), metal oxides (e.g., Fe{sub 2}O{sub 3}, Fe{sub 3}O{sub 4}), and zero-valent metal (Fe{sup 0}) have been exploited for chemical (classical Fenton), photochemical (photo-Fenton) and electrochemical (electro-Fenton) degradation pathways. However, the requirement of strict acidic conditions to prevent iron precipitation still remains the bottleneck for iron-based AOPs. In this article, we present a thorough review of alternative non-iron Fenton catalysts and their reactivity towards hydrogen peroxide activation. Elements with multiple redox states (like chromium, cerium, copper, cobalt, manganese and ruthenium) all directly decompose H{sub 2}O{sub 2} into HO{sup •} through conventional Fenton-like pathways. The in situ formation of H{sub 2}O{sub 2} and decomposition into HO{sup •} can be also achieved using electron transfer mechanism in zero-valent aluminum/O{sub 2} system. Although these Fenton systems (except aluminum) work efficiently even at neutral pH, the H{sub 2}O{sub 2} activation mechanism is very specific to the nature of the catalyst and critically depends on its composition. This review describes in detail the complex mechanisms and emphasizes on practical limitations influencing their environmental applications.

  3. Differentiating homogeneous and heterogeneous water oxidation catalysis: confirmation that [Co4(H2O)2(α-PW9O34)2]10- is a molecular water oxidation catalyst.

    Science.gov (United States)

    Vickers, James W; Lv, Hongjin; Sumliner, Jordan M; Zhu, Guibo; Luo, Zhen; Musaev, Djamaladdin G; Geletii, Yurii V; Hill, Craig L

    2013-09-25

    Distinguishing between homogeneous and heterogeneous catalysis is not straightforward. In the case of the water oxidation catalyst (WOC) [Co4(H2O)2(PW9O34)2](10-) (Co4POM), initial reports of an efficient, molecular catalyst have been challenged by studies suggesting that formation of cobalt oxide (CoOx) or other byproducts are responsible for the catalytic activity. Thus, we describe a series of experiments for thorough examination of active species under catalytic conditions and apply them to Co4POM. These provide strong evidence that under the conditions initially reported for water oxidation using Co4POM (Yin et al. Science, 2010, 328, 342), this POM anion functions as a molecular catalyst, not a precursor for CoOx. Specifically, we quantify the amount of Co(2+)(aq) released from Co4POM by two methods (cathodic adsorptive stripping voltammetry and inductively coupled plasma mass spectrometry) and show that this amount of cobalt, whatever speciation state it may exist in, cannot account for the observed water oxidation. We document that catalytic O2 evolution by Co4POM, Co(2+)(aq), and CoOx have different dependences on buffers, pH, and WOC concentration. Extraction of Co4POM, but not Co(2+)(aq) or CoOx into toluene from water, and other experiments further confirm that Co4POM is the dominant WOC. Recent studies showing that Co4POM decomposes to a CoOx WOC under electrochemical bias (Stracke and Finke, J. Am. Chem. Soc., 2011, 133, 14872), or displays an increased ability to reduce [Ru(bpy)3](3+) upon aging (Scandola, et al., Chem. Commun., 2012, 48, 8808) help complete the picture of Co4POM behavior under various conditions but do not affect our central conclusions.

  4. The study of CaO and MgO heterogenic nano-catalyst coupling on transesterification reaction efficacy in the production of biodiesel from recycled cooking oil.

    Science.gov (United States)

    Tahvildari, Kambiz; Anaraki, Yasaman Naghavi; Fazaeli, Reza; Mirpanji, Sogol; Delrish, Elham

    2015-01-01

    Fossil fuels' pollution and their non-renewability have motivated the search for alternative fuels. Some common example of seed oils are sunflower oil, date seed oil, soy bean oil. For instance, soy methyl and soy-based biodiesel are the main biodiesel. Biodiesel is a clean diesel fuel that can be produced through transesterification reaction. Recycled cooking oil, on the other hand, is one of the inexpensive, easily available sources for producing biodiesel. This article is aimed at production of biodiesel via trans-esterification method, Nano CaO synthesis using sol-gel method, and Nano MgO synthesis using sol-gel self-combustion. Two catalysts' combination affecting the reaction's efficacy was also discussed. Optimum conditions for the reaction in the presence of Nano CaO are 1.5 % weight fracture, 1:7 alcohol to oil proportion and 6 h in which biodiesel and glycerin (the byproduct) are produced. Moreover, the optimum conditions for this reaction in the presence of Nano CaO and Nano MgO mixture are 3 % weight fracture (0.7 g of Nano CaO and 0.5 g of Nano MgO), 1:7 alcohols to oil proportion and 6 h. Nano MgO is not capable of catalyzing the transesterification by itself, because it has a much weaker basic affinity but when used with Nano CaO due to its surface structure, the basic properties increase and it becomes a proper base for the catalyst so that CaO contact surface increases and transesterification reaction yield significantly increases as well. This study investigates the repeatability of transesterification reaction in the presence of these Nano catalysts as well.

  5. Nanocrystalline magnesium oxide: an efficient promoter and heterogeneous nano catalyst for the one-pot synthesis of pyrazolotriazoles in green medium

    Science.gov (United States)

    Naeimi, Hossein; Rashid, Zahra; Zarnani, Amir-Hassan; Ghahremanzadeh, Ramin

    2014-05-01

    A simple, efficient, and relatively clean method for the synthesis of pyrazolo[1,2- a][1,2,4]triazole derivatives via a one-pot three-component reaction of aromatic aldehydes, 4-phenyl-1,2,4-triazolidine-3,5-dione, and malononitrile or alkyl cyanoacetates in the presence of a catalytic amount of nanocrystalline (NC) magnesium oxide has been developed. This method has several advantages such as, high to excellent product yields, reusability of catalyst, and simple work-up procedure in the nontoxic medium.

  6. A Copper-Based Metal-Organic Framework as an Efficient and Reusable Heterogeneous Catalyst for Ullmann and Goldberg Type C–N Coupling Reactions

    Directory of Open Access Journals (Sweden)

    Wei Long

    2015-11-01

    Full Text Available A highly porous metal-organic framework (Cu-TDPAT, constructed from a paddle-wheel type dinuclear copper cluster and 2,4,6-tris(3,5-dicarboxylphenylamino-1,3,5-triazine (H6TDPAT, has been tested in Ullmann and Goldberg type C–N coupling reactions of a wide range of primary and secondary amines with halobenzenes, affording the corresponding N-arylation compounds in moderate to excellent yields. The Cu-TDPAT catalyst could be easily separated from the reaction mixtures by simple filtration, and could be reused at least five times without any significant degradation in catalytic activity.

  7. Homogeneous, Heterogeneous, and Enzymatic Catalysis.

    Science.gov (United States)

    Oyama, S. Ted; Somorjai, Gabor A.

    1988-01-01

    Discusses three areas of catalysis: homegeneous, heterogeneous, and enzymatic. Explains fundamentals and economic impact of catalysis. Lists and discusses common industrial catalysts. Provides a list of 107 references. (MVL)

  8. Polyionic polymers – heterogeneous media for metal nanoparticles as catalyst in Suzuki–Miyaura and Heck–Mizoroki reactions under flow conditions

    Directory of Open Access Journals (Sweden)

    Klaas Mennecke

    2009-05-01

    Full Text Available The preparation of monolithic polyionic supports which serve as efficient heterogeneous supports for palladium(0 nanoparticles is described. These functionalized polymers were incorporated inside a flow reactor and employed in Suzuki–Miyaura and Heck cross couplings under continuous flow conditions.

  9. Stabilization of hydrogen peroxide using tartaric acids in Fenton and fenton-like oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Hyung Suk; Kim, Jeong-Jin; Kim, Young-Hun [Andong National University, Andong (Korea, Republic of)

    2016-03-15

    The stabilization of hydrogen peroxide is a key factor in the efficiency of a Fenton reaction. The stability of hydrogen peroxide was evaluated in a Fenton reaction and Fenton-like reactions in the presence of tartaric acid as a stabilizer. The interactions between ferrous or ferric iron and tartaric acid were observed through spectroscopic monitoring at variable pH around pKa{sub 1} and pKa{sub 2} of the stabilizer. Ferric iron had a strong interaction with the stabilizer, and the strong interaction was dominant above pKa{sub 2}. At a low pH, below pKa{sub 1}, the stabilizing effect was at its maximum and the prolonged life-time of hydrogen peroxide gave a higher efficiency to the oxidative degradation of nitrobenzene. In Fenton-like reactions with hematite, the acidic conditions caused dissolution of iron from an iron oxide, and an increase in iron species was the result. Tartaric acid showed a stabilizing effect on hydrogen peroxide in the Fentonlike system. The stabilization by tartaric acid might be due to an inhibition of catalytic activity of dissolved iron, and the stabilization strongly depends on the ionization state of the stabilizer.

  10. Oil refinery wastewater treatment using physicochemical, Fenton and Photo-Fenton oxidation processes.

    Science.gov (United States)

    Tony, Maha A; Purcell, Patrick J; Zhao, Yaqian

    2012-01-01

    The objective of this study was to investigate the application of advanced oxidation processes (AOPs) to the treatment of wastewaters contaminated with hydrocarbon oil. Three different oil-contaminated wastewaters were examined and compared: (i) a 'real' hydrocarbon wastewater collected from an oil refinery (Conoco-Phillips Whitegate refinery, County Cork, Ireland); (ii) a 'real' hydrocarbon wastewater collected from a car-wash facility located at a petroleum filling station; and (iii) a 'synthetic' hydrocarbon wastewater generated by emulsifying diesel oil and water. The AOPs investigated were Fe(2+)/H(2)O(2) (Fenton's reagent), Fe(2+)/H(2)O(2)/UV (Photo-Fenton's reagent) which may be used as an alternative to, or in conjunction with, conventional treatment techniques. Laboratory-scale batch and continuous-flow experiments were undertaken. The photo-Fenton parametric concentrations to maximize COD removal were optimized: pH = 3, H(2)O(2) = 400 mg/L, and Fe(2+) = 40 mg/L. In the case of the oil-refinery wastewater, photo-Fenton treatment achieved approximately 50% COD removal and, when preceded by physicochemical treatment, the percentage removal increased to approximately 75%.

  11. Fenton and solar photo-Fenton processes for the removal of ...

    African Journals Online (AJOL)

    Fenton (H2O2/Fe2+/solar light) processes was investigated. A laboratory-scale reactor was designed to evaluate and select the optimal oxidation condition. The degradation rate is strongly dependent on pH, temperature, H2O2 dosing rate, ...

  12. Fenton and solar photo-Fenton processes for the removal of ...

    African Journals Online (AJOL)

    2011-10-10

    Fenton (H2O2/Fe2+/solar light) processes was investigated. A laboratory-scale reactor was designed to evaluate and select the optimal oxidation condition. The degrada- tion rate is strongly dependent on pH, temperature, ...

  13. Mineralization of sulfamethizole in photo-Fenton and photo-Fenton-like systems.

    Science.gov (United States)

    Wu, C H; Wu, J T; Lin, Y H

    2016-01-01

    In this investigation, UV/H2O2, UV/H2O2/Fe(2+) (photo-Fenton) and UV/H2O2/Fe(3+) (photo-Fenton-like) systems were used to mineralize sulfamethizole (SFZ). The optimal doses of H2O2 (1-20 mM) in UV/H2O2 and iron (0.1-1 mM) in photo-Fenton and photo-Fenton-like systems were determined. Direct photolysis by UV irradiation and direct oxidation by added H2O2, Fe(2+) and Fe(3+) did not mineralize SFZ. The optimal dose of H2O2 was 10 mM in UV/H2O2 and that of iron (Fe(2+) or Fe(3+)) was 0.2 mM in both UV/H2O2/Fe(2+) and UV/H2O2/Fe(3+) systems. Under the best experimental conditions and after 60 min of reaction, the SFZ mineralization percentages in UV/H2O2, UV/H2O2/Fe(2+) and UV/H2O2/Fe(3+) systems were 16, 90 and 88%, respectively. The UV/H2O2/Fe(2+) and UV/H2O2/Fe(3+) systems effectively mineralized SFZ.

  14. Removing persistant pollutants from industrial effluents. Wet chemical oxidation initiated by heterogeneous catalysis applicable in principle; Persistente Schadstoffe aus Industrieabwaessern beseitigen. Heterogenkatalytisch initiierte nasschemische Oxidation prinzipiell geeignet

    Energy Technology Data Exchange (ETDEWEB)

    Maeurer, H.; Bach, G.; Schneider, J. [Inst. fuer Neuwertwirtschaft GmbH, Dresden (Germany)

    2003-02-01

    Persistent pollutants in industrial effluents can not be fully removed by conventional processes; they must be treated prior to discharge into the sewage system. Heterogeneously catalyzed wet oxidation may be useful as it avoids the disadvantages of the commonly employed Fenton process and has a much higher oxidation effectivity. The influencing parameters of the experimental principles - based on the reaction of hydrogen peroxide into highly active hydroxyl radicals on immobile Fe(II) centres at the surface of iron catalysts on a matrix - were investigated and optimized, and the method was tested in practical conditions with effluents of a low-temperature carbonization plant. [German] Persistente Schadstoffe in Abwaessern der Industrie koennen mit eingefuehrten konventionellen Verfahren haeufig nicht bis zu den geforderten Grenzwerten abgereichert werden; sie beduerfen deshalb vor der Einleitung in die Klaeranlage einer Zusatzbehandlung. Die heterogenkatalysierte Nassoxidation kann hier Abhilfe schaffen, dabei die Nachteile der derzeit praktizierten homogenkatalytisch initiierten Verfahrensvariante, dem so genannten Fenton-Prozess, ueberwinden und eine deutlich hoehere Oxidationseffektivitaet erreichen. Die Einflussparameter des erprobten Verfahrensprinzips - basierend auf der Umwandlung von Wasserstoffperoxid zu hochaktiven Hydroxylradikalen an immobilen Fe(II)-Zentren auf der Oberflaeche von getraegerten Eisenkatalysatoren - wurden untersucht und optimiert, das Verfahren am Beispiel von Abwaessern aus Schwelereien unter praxisrelevanten Bedingungen erprobt. (orig.)

  15. Electronic Structure and Reactivity of TM-Doped La1-xSrxCoO3 (TM=Ni, Fe Heterogeneous Catalysts

    Directory of Open Access Journals (Sweden)

    S. A. Jones

    2001-11-01

    Full Text Available The catalytic properties of LaCoO3 in aqueous oxidation are explored as a function of doping. Both Sr substitution for La and Fe/Ni substitution for Co are studied. The reaction of interest is the aqueous epoxidation of crotyl alcohol with hydrogen peroxide. The reaction products are measured using GC, and the decomposition of hydrogen peroxide is studied using the volume of oxygen evolved during reaction. Strong variations in the activity to epoxide formation are observed, with Fe-doped samples being rather inactive in the reaction. SR VUV photoemission is used to explore the surface reactivity of the ceramic catalysts in aqueous solution, using H2O as a probe molecule. These measurements are complemented by XANES measurements designed to probe the local defect structure and XPS measurements of surface composition. We relate the observed catalytic activity to the defect structure of the doped materials. In Ni-doped materials, oxygen vacancies appear to be the predominant defect, whereas in Fe-doped samples, electron holes are stabilized on Fe, leading to very different catalytic behaviour. Surface studies in combination with AA measurements reveal some dissolution of the catalyst into solution during the reaction. The surface reactivity to water is influenced by the TM d electron count, with water binding more strongly to Fe-doped materials than to those containing Ni. The influence of these factors on the rate of the unwanted hydrogen peroxide decomposition reaction and hence on activity in epoxidation is discussed.

  16. Comparison of Cu-ZSM-5 zeolites and Cu-MOF-505 metal-organic frameworks as heterogeneous catalysts for the Mukaiyama aldol reaction: a DFT mechanistic study.

    Science.gov (United States)

    Yadnum, Sudarat; Choomwattana, Saowapak; Khongpracha, Pipat; Sirijaraensre, Jakkapan; Limtrakul, Jumras

    2013-04-02

    The density functional theory (DFT) model ONIOM(M06L/6-311++G(2df,2p):UFF was employed to reveal the catalytic activity of Cu(II) in the paddle-wheel unit of the metal-organic framework (MOF)-505 material in the Mukaiyama aldol reaction compared with the activity of Cu-ZSM-5 zeolites. The aldol reaction between a silyl enol ether and formaldehyde catalyzed by the Lewis acidic site of both materials takes place through a concerted pathway, in which the formation of the CC bond and the transfer of the silyl group occurs in a single step. MOF-505 and Cu-ZSM-5 are predicted to be efficient catalysts for this reaction as they strongly activate the formaldehyde carbonyl carbon electrophile, which leads to a considerably lower reaction barrier compared with the gas-phase system. Both MOF-505 and Cu-ZSM-5 catalysts stabilize the reacting species along the reaction coordinate, thereby lowering the activation energy, compared to the gas-phase system. The activation barriers for the MOF-505, Cu-ZSM-5, and gas-phase system are 48, 21, and 61 kJ mol(-1) , respectively. Our results show the importance of the enveloping framework by stabilizing the reacting species and promoting the reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Greener Route for Synthesis of aryl and alkyl-14H-dibenzo [a.j] xanthenes using Graphene Oxide-Copper Ferrite Nanocomposite as a Recyclable Heterogeneous Catalyst

    Science.gov (United States)

    Kumar, Aniket; Rout, Lipeeka; Achary, Lakkoji Satish Kumar; Dhaka, Rajendra. S.; Dash, Priyabrat

    2017-02-01

    A facile, efficient and environmentally-friendly protocol for the synthesis of xanthenes by graphene oxide based nanocomposite (GO-CuFe2O4) has been developed by one-pot condensation route. The nanocomposite was designed by decorating copper ferrite nanoparticles on graphene oxide (GO) surface via a solution combustion route without the use of template. The as-synthesized GO-CuFe2O4 composite was comprehensively characterized by XRD, FTIR, Raman, SEM, EDX, HRTEM with EDS mapping, XPS, N2 adsorption-desorption and ICP-OES techniques. This nanocomposite was then used in an operationally simple, cost effective, efficient and environmentally benign synthesis of 14H-dibenzo xanthene under solvent free condition. The present approach offers several advantages such as short reaction times, high yields, easy purification, a cleaner reaction, ease of recovery and reusability of the catalyst by a magnetic field. Based upon various controlled reaction results, a possible mechanism for xanthene synthesis over GO-CuFe2O4 catalyst was proposed. The superior catalytic activity of the GO-CuFe2O4 nanocomposite can be attributed to the synergistic interaction between GO and CuFe2O4 nanoparticles, high surface area and presence of small sized CuFe2O4 NPs. This versatile GO-CuFe2O4 nanocomposite synthesized via combustion method holds great promise for applications in wide range of industrially important catalytic reactions.

  18. Photocatalytic degradation and photo-Fenton oxidation of Congo red dye pollutants in water using natural chromite—response surface optimization

    Science.gov (United States)

    Shaban, Mohamed; Abukhadra, Mostafa R.; Ibrahim, Suzan S.; Shahien, Mohamed. G.

    2017-12-01

    Refined natural Fe-chromite was characterized by XRD, FT-IR, reflected polarized microscope, XRF and UV spectrophotometer. Photocatalytic degradation and photo-Fenton oxidation of Congo red dye by Fe-chromite was investigated using 1 mL H2O2. The degradation of dye was studied as a function of illumination time, chromite mass, initial dye concentration, and pH. Fe-chromite acts as binary oxide system from chromium oxide and ferrous oxide. Thus, it exhibits photocatalytic properties under UV illumination and photo-Fenton oxidation after addition of H2O2. The degradation in the presence of H2O2 reached the equilibrium stage after 8 h (59.4%) but in the absence of H2O2 continued to 12 h (54.6%). Photocatalytic degradation results fitted well with zero, first order and second order kinetic model but it represented by second order rather than by the other models. While the photo-Fenton oxidation show medium fitting with the second order kinetic model only. The values of kinetic rate constants for the photo-Fenton oxidation were greater than those for the photocatalytic degradation. Thus, degradation of Congo red dye using chromite as catalyst is more efficient by photo-Fenton oxidation. Based on the response surface analysis, the predicted optimal conditions for maximum removal of Congo red dye by photocatalytic degradation (100%) were 12 mg/l, 0.14 g, 3, and 11 h for dye concentration, chromite mass, pH, and illumination time, respectively. Moreover, the optimum condition for photo-Fenton oxidation of dye (100%) is 13.5 mg/l, 0.10 g, 4, and 10 h, respectively.

  19. Photocatalytic degradation and photo-Fenton oxidation of Congo red dye pollutants in water using natural chromite—response surface optimization

    Science.gov (United States)

    Shaban, Mohamed; Abukhadra, Mostafa R.; Ibrahim, Suzan S.; Shahien, Mohamed. G.

    2017-11-01

    Refined natural Fe-chromite was characterized by XRD, FT-IR, reflected polarized microscope, XRF and UV spectrophotometer. Photocatalytic degradation and photo-Fenton oxidation of Congo red dye by Fe-chromite was investigated using 1 mL H2O2. The degradation of dye was studied as a function of illumination time, chromite mass, initial dye concentration, and pH. Fe-chromite acts as binary oxide system from chromium oxide and ferrous oxide. Thus, it exhibits photocatalytic properties under UV illumination and photo-Fenton oxidation after addition of H2O2. The degradation in the presence of H2O2 reached the equilibrium stage after 8 h (59.4%) but in the absence of H2O2 continued to 12 h (54.6%). Photocatalytic degradation results fitted well with zero, first order and second order kinetic model but it represented by second order rather than by the other models. While the photo-Fenton oxidation show medium fitting with the second order kinetic model only. The values of kinetic rate constants for the photo-Fenton oxidation were greater than those for the photocatalytic degradation. Thus, degradation of Congo red dye using chromite as catalyst is more efficient by photo-Fenton oxidation. Based on the response surface analysis, the predicted optimal conditions for maximum removal of Congo red dye by photocatalytic degradation (100%) were 12 mg/l, 0.14 g, 3, and 11 h for dye concentration, chromite mass, pH, and illumination time, respectively. Moreover, the optimum condition for photo-Fenton oxidation of dye (100%) is 13.5 mg/l, 0.10 g, 4, and 10 h, respectively.

  20. Zn-Fe-CNTs catalytic in situ generation of H2O2 for Fenton-like degradation of sulfamethoxazole.

    Science.gov (United States)

    Liu, Yong; Fan, Qin; Wang, Jianlong

    2018-01-15

    A novel Fenton-like catalyst (Zn-Fe-CNTs) capable of converting O2 to H2O2 and further to OH was prepared through infiltration fusion method followed by chemical replacement in argon atmosphere. The catalyst was characterized by SEM, EDS, TEM, XRD and XPS. The reaction between Zn-Fe-CNTs and O2 in aqueous solution could generate H2O2 in situ, which was further transferred to OH. The Fenton-like degradation of sulfamethoxazole (SMX) using Zn-Fe-CNTs as catalyst was evaluated. The results indicated that Zn-Fe-CNTs had a coral porous structure with a BET area of 51.67m(2)/g, exhibiting excellent adsorption capacity for SMX, which enhanced its degradation. The particles of Zn(0) and Fe(0)/Fe2O3 were observed on the surface of Zn-Fe-CNTs. The mixture of Zn(0) and CNTs could reduce O2 into H2O2 by micro-electrolysis and Fe(0)/Fe2O3 could catalyze in-situ generation of H2O2 to produce OH through Fenton-like process. When initial pH=1.5, T=25°C, O2 flow rate=400mL/min, Zn-Fe-CNTs=0.6g/L, SMX=25mg/L and reaction time=10min, the removal efficiency of SMX and TOC was 100% and 51.3%, respectively. The intermediates were detected and the possible pathway of SMX degradation and the mechanism of Zn-Fe-CNTs/O2 process were tentatively proposed. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Application of intensified Fenton oxidation to the treatment of sawmill wastewater.

    Science.gov (United States)

    Munoz, Macarena; Pliego, Gema; de Pedro, Zahara M; Casas, Jose A; Rodriguez, Juan J

    2014-08-01

    The application of the Fenton process for the treatment of sawmill wastewater has been investigated. The sawmill wastewater was characterized by a moderate COD load (≈3gL(-1)), high ecotoxicity (≈ 40 toxicity units) and almost negligible BOD/COD ratio (5×10(-3)) due to the presence of different fungicides such as propiconazole and 3-iodo-2-propynyl butyl carbamate, being the wastewater classified as non-biodegradable. The effect of the key Fenton variables (temperature (50-120°C), catalyst concentration (25-100 mg L(-1) Fe(3+)), H2O2 dose (1 and 2 times the stoichiometric dose) and the mode of H2O2 addition) on COD reduction and mineralization was investigated in order to fulfill the allowable local limits for industrial wastewater discharge and achieve an efficient consumption of H2O2 in short reaction times (1h). Increasing the temperature clearly improved the oxidation rate and mineralization degree, achieving 60% COD reduction and 50% mineralization at 120°C after 1h with the stoichiometric H2O2 dose and 25 mg L(-1) Fe(3+). The distribution of H2O2 in multiple additions throughout the reaction time was clearly beneficial avoiding competitive scavenging reactions and thus, achieving higher efficiencies of H2O2 consumption (XCOD ≈ 80%). The main by-products were non-toxic short-chain organic acids (acetic, oxalic and formic). Thus, the application of the Fenton process allowed reaching the local limits for industrial wastewater discharge into local sewer system at a relatively low cost. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. On the applicability of Arrhenius plot methods to determine surface energetic heterogeneity of adsorbents and catalysts surfaces from experimental TPD spectra.

    Science.gov (United States)

    Rudzinski, W; Borowiecki, T; Panczyk, T; Dominko, A

    2000-01-01

    Recovering adsorption energy distribution from experimental data belongs to most difficult problems of adsorption science. In the case when thermodesorption data are used as a source of information, that difficult problem is overcome by the common use of the Arrhenius plot methods. So, we decided to carry out an extensive model investigation to show, how reliable information concerning the surface energetic heterogeneity is obtained by using the Arrhenius plot methods. Like in our previous publications we have used the Statistical Rate Theory of Interfacial Transport to describe the adsorption/desorption kinetics. Our model investigations showed, that the Arrhenius plot methods, cannot provide reliable information about the surface energetic heterogeneity. Moreover, for strongly heterogeneous surfaces a linear relationship exists between the logarithm of the pre-exponential constant and the adsorption energy, for certain adsorption coverages. That kind of compensation effect has, so far, been ascribed to interactions between the adsorbed molecules. The failure of the popular Arrhenius plot method puts, as an urgent agenda, the development of reliable methods for recovering adsorption energy distribution from the thermodesorption data.

  3. Hydrogen Production from Water by Photolysis, Sonolysis and Sonophotolysis with Solid Solutions of Rare Earth, Gallium and Indium Oxides as Heterogeneous Catalysts

    Directory of Open Access Journals (Sweden)

    Marta Penconi

    2015-07-01

    Full Text Available In this work, we present the hydrogen production by photolysis, sonolysis and sonophotolysis of water in the presence of newly synthesized solid solutions of rare earth, gallium and indium oxides playing as catalysts. From the experiments of photolysis, we found that the best photocatalyst is the solid solution Y0.8Ga0.2InO3 doped by sulphur atoms. In experiments of sonolysis, we optimized the rate of hydrogen production by changing the amount of water, adding ethanol and tuning the power of our piezoelectric transducer. Finally, we performed sonolysis and sonophotolysis experiments in the presence of S:Y0.8Ga0.2InO3 finding a promising synergistic effect of UV-visible electromagnetic waves and 38 kHz ultrasound waves in producing H2.

  4. Visualization of the heterogeneity of cerium oxidation states in single Pt/Ce₂Zr₂O(x) catalyst particles by nano-XAFS.

    Science.gov (United States)

    Ishiguro, Nozomu; Uruga, Tomoya; Sekizawa, Oki; Tsuji, Takuya; Suzuki, Motohiro; Kawamura, Naomi; Mizumaki, Masaichiro; Nitta, Kiyofumi; Yokoyama, Toshihiko; Tada, Mizuki

    2014-06-06

    The cerium oxidation states in single catalyst particles of Pt/Ce2Zr2O(x) (x=7 to 8) were investigated by spatially resolved nano X-ray absorption fine structure (nano-XAFS) using an X-ray nanobeam. Differences in the distribution of the Ce oxidation states between Pt/Ce2Zr2O(x) single particles of different oxygen compositions x were visualized in the obtained two-dimensional X-ray fluorescent (XRF) mapping images and the Ce L(III)-edge nano X-ray absorption near-edge structure (nano-XANES) spectra. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Sulfonated starch nanoparticles: An effective, heterogeneous and bio-based catalyst for synthesis of 14-aryl-14-H-dibenzo[a,j]xanthenes

    Science.gov (United States)

    Safari, Javad; Aftabi, Pegah; Ahmadzadeh, Majid; Sadeghi, Masoud; Zarnegar, Zohre

    2017-08-01

    In recent years, biodegradable polymer based nanoparticles have attracted wide attention for the synthesis of high-performance and green catalytic species. Polymeric nanoparticles used for catalytic processes must be biocompatible and biodegradable. The objective of this study is to fabricate starch nanoparticles from native starch and preparation of sulfonated starch nanoparticles (HO3S-SNPs) as acidic nanocatalyst in the synthesis of 14-aryl-14-H-dibenzo[a,j]xanthenes under solvent free conditions. This procedure has a lot of advantages such as very easy reaction conditions, low-cost production and natural catalyst and absence of any tedious workup or purification. The corresponding products have been obtained in excellent yields, high purity and short reaction times.

  6. Sequence-Fenton Reaction for Decreasing Phenol Formation during Benzene Chemical Conversion in Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    SB Mortazavi, A Sabzali, A Rezaee

    2005-04-01

    Full Text Available Advanced oxidation processes such as Fenton reagent generates highly reactive hydroxyl free radicals to oxidize various compounds in the water and wastewater. The efficiency of different Fenton-related oxidative processes such as Fenton, solar-Fenton, UV-Fenton and Fenton reactions in different batch reactors was examined using benzene as pollutant in aqueous solutions. A batch study was conducted to optimize parameters like pH, hydrogen peroxide concentration, temperature, reaction time and ferrous ion concentration governing the Fenton process. The concentrations of produced phenol were measured at the end of the reactions. The role of sequence reaction was tested for decreasing phenol formation during benzene conversion. At optimum conditions, different Fenton-related processes were compared for the degradation of benzene. Increased degradation efficiency was observed in photo-Fenton processes as compared to conventional Fenton process. The formation of phenol in Fenton reaction depended on reaction time, sequence in reaction, purity of hydrogen peroxide and other compounds such as alcohols that contributed into the reaction. In the Fenton process, carboxylic acids like acetic acid and oxalic acid were formed as the end products during the complete degradation of benzene. With the increase in mono-valence, two-valence ions and hardness, Fenton's efficiency decreased, respectively. Sequence Fenton reaction produced less phenol and its end products had smaller COD as compared to conventional Fenton process.

  7. Density functional study on the heterogeneous oxidation of NO over α-Fe2O3 catalyst by H2O2: Effect of oxygen vacancy

    Science.gov (United States)

    Song, Zijian; Wang, Ben; Yu, Jie; Ma, Chuan; Zhou, Changsong; Chen, Tao; Yan, Qianqian; Wang, Ke; Sun, Lushi

    2017-08-01

    Catalytic oxidation with H2O2 is a promising method for NOx emission control in coal-fired power plants. Hematite-based catalysts are attracting increased attention because of their surface redox reactivity. To elucidate the NO oxidation mechanism on α-Fe2O3 surfaces, density functional theory (DFT) calculations were conducted by investigating the adsorption characteristics of nitric oxide (NO) and hydrogen peroxide (H2O2) on perfect and oxygen defect α-Fe2O3 (0 0 1) surfaces. Results show that NO was molecularly adsorbed on two kinds of surfaces. H2O2 adsorption on perfect surface was also in a molecular form; however, H2O2 dissociation occurred on oxygen defect α-Fe2O3 (0 0 1) surface. The adsorption intensities of the two gas molecules in perfect α-Fe2O3 (0 0 1) surface followed the order NO > H2O2, and the opposite was true for the oxygen defect α-Fe2O3 (0 0 1). Oxygen vacancy remarkably enhanced the adsorption intensities of NO and H2O2 and promoted H2O2 decomposition on catalyst surface. As an oxidative product of NO, HNO2 was synthesized when NO and H2O2 co-adsorbed on the oxygen defect α-Fe2O3 (0 0 1) surface. Analyses of Mulliken population, electron density difference, and partial density of states showed that H2O2 decomposition followed the Haber-Weiss mechanism. The trends of equilibrium constants suggested that NO adsorption on α-Fe2O3 (0 0 1) surface was more favorable at low than at high temperatures, whereas H2O2 adsorption was favorable between 375 and 450 K. These calculations results well agreed with the experimental ones and further elucidates the reaction mechanisms.

  8. European workshop on spent catalysts. Book of abstracts

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2006-07-01

    In 1999 and 2002 two well attended workshops on recycling, regeneration, reuse and disposal of spent catalysts took place in Frankfurt. This series has been continued in Berlin. The workshop was organized in collaboration with DGMK, the German Society for Petroleum and Coal Science and Technology. Contributions were in the following areas of catalyst deactivation: recycling of spent catalysts in chemical and petrochemical industry, recycling of precious metal catalysts and heterogenous base metal catalysts, legal aspects of transboundary movements, catalyst regeneration, quality control, slurry catalysts, commercial reactivation of hydrotreating catalysts. (uke)

  9. Novel metalloporphyrin catalysts for the oxidation of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Showalter, M.C.; Nenoff, T.M.; Shelnutt, J.A.

    1996-11-01

    Work was done for developing biomimetic oxidation catalysts. Two classes of metalloporphyrin catalysts were studied. The first class of catalysts studied were a novel series of highly substituted metalloporphyrins, the fluorinated iron dodecaphenylporphyrins. These homogeneous metalloporphyrin catalysts were screened for activity as catalysts in the oxidation of hydrocarbons by dioxygen. Results are discussed with respect to catalyst structural features. The second type of catalysts studied were heterogeneous catalysts consisting of metalloporphyrins applied to inorganic supports. Preliminary catalytic testing results with these materials are presented.

  10. Treatment of SRS Tank 48H Simulants Using Fenton's Reagent

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, PA

    2003-11-18

    High-level-waste Tank 48H at the Savannah River Site (SRS) contains about 50,000 lb of tetraphenylborate (TPB), which must be destroyed to return the tank to active service. Laboratory-scale tests were conducted to evaluate the use of Fenton's Reagent (hydrogen peroxide and a metal catalyst) to treat simulants of the Tank 48H waste. Samples of the treated slurry and the off-gas were analyzed to determine the reaction products. Process parameters developed earlier by AEA Technology were used for these tests; namely (for 500 mL of waste simulant), reduce pH to 7.5 with nitric acid, heat to boiling, add hydrogen peroxide at 1 mL/min for 1 h, reduce pH to 3.5, and add the remaining peroxide at 2 mL/min. These parameters were developed to minimize the formation of tarry materials during the early part of the reaction and to minimize the concentration of total organic carbon in the final treated slurry. The treated samples contained low concentrations of total organic carbon (TOC) and no detectable TPB. Tests using a mixture of iron and copper salts as the Fenton's catalyst had a lower TOC concentration in the final treated slurry than did tests that used a copper-only catalyst. TPB is known to hydrolyze to benzene, particularly at high temperature and low pH, and copper is known to increase the rate of hydrolysis. Significant amounts of benzene were present in the off-gas from the tests, especially during the early portion of the treatment, indicating that the hydrolysis reaction was occurring in parallel with the oxidation of the TPB by Fenton's reagent. For the reaction conditions used in these tests, approximately equal fractions of the TPB were converted to benzene and carbon dioxide. Minimizing the formation of benzene is important to SRS personnel; however, this consideration was not addressed in the AEA-recommended parameters, since they did not analyze for benzene in the off-gas. Smaller amounts of carbon monoxide and other organics were also

  11. Mo-II Cluster Complex-Based Coordination Polymer as an Efficient Heterogeneous Catalyst in the Suzuki–Miyaura Coupling Reaction

    Czech Academy of Sciences Publication Activity Database

    Bůžek, Daniel; Hynek, Jan; Kučeráková, Monika; Kirakci, Kaplan; Demel, Jan; Lang, Kamil

    2016-01-01

    Roč. 2016, č. 28 (2016), s. 4668-4673 ISSN 1434-1948 R&D Projects: GA ČR GA13-05114S; GA ČR GA15-12653S EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:61388980 ; RVO:68378271 Keywords : C–C coupling * Heterogeneous catalysis * Molybdenum * Palladium * Polymers Subject RIV: CA - Inorganic Chemistry; CF - Physical ; Theoretical Chemistry (FZU-D) Impact factor: 2.444, year: 2016

  12. Preparation of Fe3O4/TiO2/C Nanocomposites and Their Application in Fenton-Like Catalysis for Dye Decoloration

    Directory of Open Access Journals (Sweden)

    Xiaoyang Liu

    2016-09-01

    Full Text Available Fe2+-H2O2 Fenton system is widely applied in water treatment nowadays, but the acidification and sludge generation are crucial problems to be solved. Herein, we report that Fe3O4/TiO2/C nanocomposites (FTCNCs were able to catalyze the decomposition of H2O2 at neutral pH and can be applied in dye decoloration. FTCNCs were prepared by precipitating TiO2 on Fe3O4 cores via the hydrolysis of tetrabutyl titanate followed by the hydrothermal dehydrogenization of glucose to deposit carbon on Fe3O4/TiO2. The decoloration of methylene blue (MB in the FTCNC-H2O2 Fenton-like system was monitored to reflect the catalytic activity of FTCNC. The radical generation capability was analyzed by electron spin resonance. Our results indicated that FTCNC-H2O2 Fenton-like system was efficient in decolorizing MB, and the radicals led to the near complete oxidation of MB. The FTCNC-H2O2 Fenton-like system could be used in a wide pH range of 4–9. A greater catalyst amount, a higher H2O2 concentration, and a higher temperature accelerated the decoloration kinetics. FTCNCs showed good activity after the regeneration of 8 cycles. The implication to the practical applications of FTCNCs in water treatment is discussed.

  13. Bibliography of Work on the Heterogeneous Photocatalytic Removal of Hazardous Compounds from Water

    Energy Technology Data Exchange (ETDEWEB)

    Blake, D. M.

    1999-07-29

    The subject of this report is chemistry and engineering for the application of heterogeneous photocatalysts. The state of the art in catalysts are forms of titanium dioxide or modifications thereof, but work on other heterogeneous catalysts is included.

  14. A DFT study on the effect of hydrogen in ethylene and propylene polymerization using a Ti-based heterogeneous Ziegler–Natta catalyst

    KAUST Repository

    Bahri-Laleh, Naeimeh

    2012-11-01

    Hydrogenolysis of a series of model Ziegler-Natta (Z-N) catalysts to form Ti-H bond was studied within DFT. We focused our efforts on Ti species attached to the (110) lateral cut of MgCl 2 which exist as different centres including Ti-C 2H 5, Ti-CH 2CH(CH 3) 2, and Ti-CH(CH 3)CH 2CH 3 in ethylene and propylene polymerization. In the next step, reactivity of Ti-H bond towards ethylene and propylene (1,2- and 2,1-) insertion was investigated. Results showed that insertion of ethylene and propylene into Ti-H bond has less barrier, in comparison with their insertion in Ti-C bond, however, ethylene and propylene 2,1- insertion lead to Ti-C 2H 5 and Ti-CH(CH 3) 2 centres respectively, which were stable due to strong β-agostic interactions. Finally, by considering different possible reactions of active centre, activity depression in ethylene polymerization and activity increase in propylene polymerization were explained in detail. © 2012 Elsevier B.V.

  15. Dynamics of Catalyst Nanoparticles

    DEFF Research Database (Denmark)

    Hansen, Thomas Willum; Cavalca, Filippo; Wagner, Jakob Birkedal

    under gas exposure, dynamic phenomena such as sintering and growth can be observed with sub-Ångstrøm resolution. Metal nanoparticles contain the active sites in heterogeneous catalysts, which are important for many industrial applications including the production of clean fuels, chemicals...... and pharmaceuticals, and the cleanup of exhaust from automobiles and stationary power plants. Sintering, or thermal deactivation, is an important mechanism for the loss of catalyst activity. In order to initiate a systematic study of the dynamics and sintering of nanoparticles, various catalytic systems have been...... that particle sintering is not solely governed by the mechanisms previously proposed. These results are divided into the different phases of the catalyst lifetime....

  16. Optimization of a heterogeneous catalytic hydrodynamic cavitation reactor performance in decolorization of Rhodamine B: application of scrap iron sheets.

    Science.gov (United States)

    Basiri Parsa, Jalal; Ebrahimzadeh Zonouzian, Seyyed Alireza

    2013-11-01

    A low pressure pilot scale hydrodynamic cavitation (HC) reactor with 30 L volume, using fixed scrap iron sheets, as the heterogeneous catalyst, with no external source of H2O2 was devised to investigate the effects of operating parameters of the HC reactor performance. In situ generation of Fenton reagents suggested an induced advanced Fenton process (IAFP) to explain the enhancing effect of the used catalyst in the HC process. The reactor optimization was done based upon the extent of decolorization (ED) of aqueous solution of Rhodamine B (RhB). To have a perfect study on the pertinent parameters of the heterogeneous catalyzed HC reactor, the following cases as, the effects of scrap iron sheets, inlet pressure (2.4-5.8 bar), the distance between orifice plates and catalyst sheets (submerged and inline located orifice plates), back-pressure (2-6 bar), orifice plates type (4 various orifice plates), pH (2-10) and initial RhB concentration (2-14 mg L(-1)) have been investigated. The results showed that the highest cavitational yield can be obtained at pH 3 and initial dye concentration of 10 mg L(-1). Also, an increase in the inlet pressure would lead to an increase in the ED. In addition, it was found that using the deeper holes (thicker orifice plates) would lead to lower ED, and holes with larger diameter would lead to the higher ED in the same cross-sectional area, but in the same holes' diameters, higher cross-sectional area leads to the lower ED. The submerged operation mode showed a greater cavitational effects rather than the inline mode. Also, for the inline mode, the optimum value of 3 bar was obtained for the back-pressure condition in the system. Moreover, according to the analysis of changes in the UV-Vis spectra of RhB, both degradation of RhB chromophore structure and N-deethylation were occurred during the catalyzed HC process. Copyright © 2013 Elsevier B.V. All rights reserved.

  17. Degradação de corantes têxteis e remediação de resíduos de tingimento por processos Fenton, foto-Fenton e eletro-Fenton

    Directory of Open Access Journals (Sweden)

    Terezinha Salvador

    2012-01-01

    Full Text Available In this work the degradation of textile dyes were evaluated, using Fenton, photo-Fenton and electro-Fenton processes. Under optimized conditions Fenton and photo-Fenton processes showed high decolorization capacity of the model dyes. The electro-Fenton process was carried out in an undivided electrochemical reactor (1000 mL equipped with a carbon-felt cathode (253 cm² and a platinum gauze anode (6 cm². Under optimal conditions (J: 1.6 mA cm-2, Na2SO4: 0.075 mol L-1, pH: 3 H2O2 concentration of about 60 mg L-1 was observed. The addition of Fe2+ (15 mg L-1 induces Fenton reactions that permit almost total decolorization of textile dyes.

  18. One-step synthesis of a highly homogeneous SBA-NHC hybrid material: en route to single-site NHC-metal heterogeneous catalysts with high loadings.

    Science.gov (United States)

    Rocquin, Mansuy; Henrion, Mickaël; Willinger, Marc-Georg; Bertani, Philippe; Chetcuti, Michael J; Louis, Benoît; Ritleng, Vincent

    2014-03-07

    The one-step synthesis of a mesoporous silica of SBA type, functionalized with a 1-(2,6-diisopropylphenyl)-3-propyl-imidazolium (iPr2Ar-NHC-propyl) cation located in the pore channels, is described. This material was obtained by the direct hydrolysis and co-condensation of tetraethylorthosilicate (TEOS) and 1-(2,6-diisopropylphenyl)-3-[3-(triethoxysilyl)propyl]-imidazolium iodide in the presence of Pluronic P123 as a non-ionic structure-directing agent and aqueous HCl (37%) as an acid catalyst. Small-angle X-ray diffraction measureme