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Sample records for heteropoly acid catalyst

  1. Biomass Conversion over Heteropoly Acid Catalysts

    KAUST Repository

    Zhang, Jizhe

    2015-04-01

    Biomass is a natural resource that is both abundant and sustainable. Its efficient utilization has long been the focus of research and development efforts with the aim to substitute it for fossil-based feedstock. In addition to the production of biofuels (e.g., ethanol) from biomass, which has been to some degree successful, its conversion to high value-added chemicals is equally important. Among various biomass conversion pathways, catalytic conversion is usually preferred, as it provides a cost-effective and eco-benign route to the desired products with high selectivities. The research of this thesis is focused on the conversion of biomass to various chemicals of commercial interest by selective catalytic oxidation. Molecular oxygen is chosen as the oxidant considering its low cost and environment friendly features in comparison with commonly used hydrogen peroxide. However, the activation of molecular oxygen usually requires high reaction temperatures, leading to over oxidation and thus lower selectivities. Therefore, it is highly desirable to develop effective catalysts for such conversion systems. We use kegging-type heteropoly acids (HPAs) as a platform for catalysts design because of their high catalytic activities and ease of medication. Using HPA catalysts allows the conversion taking place at relatively low temperature, which is beneficial to saving production cost as well as to improving the reaction selectivity. The strong acidity of HPA promotes the hydrolysis of biomass of giant molecules (e.g. cellulose), which is the first as well as the most difficult step in the conversion process. Under certain circumstances, a HPA combines the merits of homogeneous and heterogeneous catalysts, acting as an efficient homogeneous catalyst during the reaction while being easily separated as a heterogeneous catalyst after the reaction. We have successfully applied HPAs in several biomass conversion systems. Specially, we prepared a HPA-based bi-functional catalyst

  2. Synthesis and properties of catalysts prepared from silicomolybdovanadium heteropoly acid

    International Nuclear Information System (INIS)

    Chumachenko, N.N.; Tarasova, D.V.; Nikoro, T.A.; Yaroslavtseva, I.V.

    1984-01-01

    Catalytic properties of samples prepared of silicomolybdovanadium heteropoly acid (HPA) have been investigated. The massive catalyst is shown to be comparatively low effective in the reaction of acrolein oxidation to acrylic acid. Impregnation of coarse-dispersed silica gel by the HPA solution results in the formation of active and selective catalyst, whereas low-active catalyst of deep oxidation is formed on the base of high-dispersed silica gel. The obtained data are explained by the formation and stabilization of different forms of vanadium- and molybdenum-containing compounds on the carrier surface

  3. Heteropoly acid promoted catalyst for SCR of NOx with ammonia

    DEFF Research Database (Denmark)

    2012-01-01

    The present invention concerns the selective removal of nitrogen oxides (NOx) from gases. In particular, the invention concerns a process, a highly alkali metal resistant heteropoly acid promoted catalyst and the use of said catalyst for removal of NOx from exhaust or flue gases, said gases...... comprising alkali or earth alkali metals. Such gases comprise for example flue gases arising from the burning of biomass, combined biomass and fossil fuel, and from waste incineration units. The process comprises the selective catalytic reduction (SCR) of NOx, such as nitrogen dioxide (NO2) and nitrogen...

  4. Heteropoly acid promoted Cu and Fe catalysts for the selective catalytic reduction of NO with ammonia

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Mossin, Susanne L.; Riisager, Anders

    2011-01-01

    Cu/TiO2, Fe/TiO2 and heteropoly acid promoted Cu/TiO2, Fe/TiO2 catalysts were prepared and characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR and EPR. The catalysts exhibited only crystalline TiO2 phases with the active metals and promoters in highly dispersed state. The acidic properties...... activity and acidity was lower for promoted catalysts than for unpromoted catalysts. In the heteropoly acid promoted catalysts the SCR active Cu and Fe metals were protected from potassium poisons by bonding of the potassium to the Brønsted acid centres. Thus heteropoly acid promoted catalysts might...... be suitable for biomass fired power plant SCR applications....

  5. Heteropoly acid promoted V2O5/TiO2 catalysts for NO abatement with ammonia in alkali containing flue gases

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Jensen, Anker Degn; Riisager, Anders

    2011-01-01

    V2O5/TiO2 and heteropoly acid promoted V2O5/TiO2 catalysts were prepared and characterized by N2 physisorption, XRPD and NH3-TPD. The influence of the calcination temperature from 400 to 700 1C on crystallinity and acidic properties was studied and compared with the activity for the selective...... catalytic reduction (SCR) of NO with ammonia. The SCR activity of heteropoly acid promoted catalysts was found to be much higher than for unpromoted catalysts. The stability of heteropoly acid promoted catalysts is dependent on calcination temperature and there is a gradual decrease in SCR activity...... and acidity with increase in calcination temperatures. Furthermore, the heteropoly acid promoted V2O5/TiO2 catalysts showed excellent alkali deactivation resistance and might therefore be alternative deNOx catalysts in biomass fired power plants....

  6. Cu-exchanged heteropoly acids as efficient and reusable catalysts ...

    Indian Academy of Sciences (India)

    Administrator

    neous catalysts has received considerable interest in different areas of organic ... easily recovered from the reaction mixture by simple filtration and can be re-used after ..... Acknowledgements. We gratefully acknowledge the financial support.

  7. Catalyst of a metal heteropoly acid salt that is insoluble in a polar solvent on a non-metallic porous support and method of making

    Science.gov (United States)

    Wang, Yong [Richland, WA; Peden, Charles H. F. [West Richland, WA; Choi, Saemin [Richland, WA

    2002-10-29

    The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

  8. 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.

  9. Study on solar chemical heat pump system. Basic experiment on dehydrogenation of 2-propanol using heteropoly-acid photo catalyst; Solar chemical heat pump no kenkyu. Heteropoly sankei hikari shokubai wo mochiita 2-propanol no dassuiso hanno

    Energy Technology Data Exchange (ETDEWEB)

    Doi, T [Electrochemical Laboratory, Tsukuba (Japan); T-Raissi, A; Muradov, N [Florida Solar Energy Center, FL (United States)

    1996-10-27

    With the purpose of converting solar heat energy to an industrial heat energy, an examination was carried out empirically on the case of using a heteropoly-acid photo catalyst for the decomposition reaction process of 2-propanol. The experiment was performed in Florida Solar Energy Center, in the U.S.A.. The device for the experiment was constituted of a reaction part, distribution manifold for feeding from the lower part of the reaction part a 2-propanol solution for which a photo catalyst was suspended, storage tank served also as a gas-liquid separating container, and circulating pump. Silica-tangstic acid was used as the photo catalyst. In an outdoor experiment using solar radiation, the quantity of inclined global solar radiation was 530-950W/m{sup 2} in clear days and 100-600W/m{sup 2} in cloudy days, with temperatures between 17 and 26{degree}C throughout the experiment period. In addition, an indoor experiment was also conducted using an artificial light source (UV light). As a result of the experiment, the energy conversion efficiency was at most about 1% of incident UV light, a low figure compared to a heat utilization ratio of approximately 15% with a thermal catalyst. 6 refs., 8 figs.

  10. Heteropoly acid catalyzed hydrolysis of glycogen to glucose

    International Nuclear Information System (INIS)

    Klein, Miri; Pulidindi, Indra Neel; Perkas, Nina; Gedanken, Aharon

    2015-01-01

    Complete conversion of glycogen to glucose is achieved by using H 3 PW 12 O 40 ·nH 2 O (HPW) and H 4 SiW 12 O 40 ·nH 2 O (HSiW) as catalysts for the hydrolysis under optimized hydrothermal conditions (mass fraction of catalyst 2.4%, 373 K and 2 h reaction time). The reusability of the catalyst (HPW) was demonstrated. In addition to carrying out the glycogen hydrolysis in an autoclave, other novel methods such as microwave irradiation and sonication have also been investigated. At higher mass fraction of the heteropoly acids (10.5%), glycogen could be completely converted to glucose under microwave irradiation. Sonication of an aqueous solution of glycogen in the presence of HPW and HSiW also yielded glucose. Thus, heteropoly acids are efficient, environmentally friendly and reusable catalysts for the conversion of glycogen to glucose. - Highlights: • Hydrothermal, microwave and sonication based methods of hydrolysis. • Heteropoly acids are green catalysts for glycogen hydrolysis. • Glycogen from cyanobacteria is demonstrated as a potential feedstock for glucose

  11. KSF-supported heteropoly acids catalyzed one-pot synthesis of α ...

    African Journals Online (AJOL)

    In the presence of KSF-supported heteropoly acid as a heterogeneous, reusable and inexpensive catalyst, three-component reactions between aldehydes or ketones, amines, and trimethylsilyl cyanide preceded to afford α-aminonitriles in excellent yields, very short reaction times, and low loading of catalyst. This catalyst ...

  12. KSF-supported heteropoly acids catalyzed one-pot synthesis of α-aminonitriles

    Directory of Open Access Journals (Sweden)

    Ezzat Rafiee

    2010-08-01

    Full Text Available In the presence of KSF-supported heteropoly acid as a heterogeneous, reusable and inexpensive catalyst, three-component reactions between aldehydes or ketones, amines, and trimethylsilyl cyanide preceded to afford α-aminonitriles in excellent yields, very short reaction times, and low loading of catalyst. This catalyst was highly selective and other functional groups including carbon-carbon double bond, and heterocyclic moieties did not affect the reaction.

  13. Application of Heteropoly Acids as Heterogeneous and Recyclable Catalysts for Friedländer Synthesis of Quinolines

    Directory of Open Access Journals (Sweden)

    Majid M. Heravi

    2010-01-01

    Full Text Available New convenient conditions for the Friedländer synthesis of quinolines are described. Quinolines were readily prepared in the presence of heteropolyacids as heterogeneous and recyclable catalysts in good yields.

  14. Pseudoliquid behavior of heteropoly compound catalysts. Unusual pressure dependencies of the rate and selectivity for ethanol dehydration

    International Nuclear Information System (INIS)

    Misono, M.; Okuhara, T.; Ichiki, T.; Arai, T.; Kanda, Y.

    1987-01-01

    Heteropoly compounds arenow utilized as industrial catalysts for olefin hydration and aldehyde oxidation and as interesting cluster models of mixed oxide catalysts. Certain heteropoly acids, like H 3 PW 12 O 40 and H 3 PMo 12 O 40 , easily absorb a large amount of water, alchols, and ethers in the solid state, although their surface areas are very low. This is not adsorption in micropores; rather molecules are absorbed between the lattice polyanions, sometimes expanding the lattice. The expansion can be seen visually as well as by x-ray diffraction. The authors showed that in some cases catalytic reactions take place in this novel bulk phase. Presumably due to this behavior, very high catalytic activity and unique selectivity as well as unusual reactivity order have been observed. They called this state the pseudoliquid phase. However, in only one case was the amount of absorbed reactant measured under the working conditions. They report here unusual pressure dependencies of the rate and selectivity of ethanol dehydration over heteropoly compounds. The dependency can only be explained by the formation of a pseudoliquid phase, i.e., a phase where the amount of absorbed ethanol has changed as a function of ethanol pressure

  15. Molybdenum-containing acidic catalysts to convert cellulosic biomass to glycolic acid

    KAUST Repository

    Han, Yu; Zhang, Jizhe; Liu, Xin

    2014-01-01

    Embodiments of the present invention include methods and compositions related to catabolic conversion of cellulosic biomass to glycolic acid using molybdenum-containing acidic catalysts. The invention includes the use of heteropoly and isopoly acids

  16. Synthesis and conductivity of heptadecatungstovanadodiphosphoric heteropoly acid with Dawson structure

    Energy Technology Data Exchange (ETDEWEB)

    Tong Xia; Zhu Weiming [Department of Chemistry, Zhejiang University, Hangzhou 310027 (China); Wu Qingyin, E-mail: qywu@zju.edu.cn [Department of Chemistry, Zhejiang University, Hangzhou 310027 (China); Qian Xueyu; Liu Zhen [Department of Chemistry, Zhejiang University, Hangzhou 310027 (China); Yan Wenfu [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012 (China); Gong Jian [Key Lab of Polyoxometalate Science, the Ministry of Education, Northeast Normal University, Changchun 130024 (China)

    2011-07-21

    A new solid high-proton conductor, heptadecatungstovanadodiphosphoric heteropoly acid H{sub 7}P{sub 2}W{sub 17}VO{sub 62}.28H{sub 2}O with Dawson structure was synthesized by the stepwise acidification and the stepwise addition of element solutions. The optimal proportion of component compounds in the synthesis reaction was given. The product was characterized by chemical analysis, potentiometric titration, IR, UV, XRD, {sup 31}P NMR, TG-DTA and electrochemical impedance spectroscopy (EIS). The results indicate that H{sub 7}P{sub 2}W{sub 17}VO{sub 62}.28H{sub 2}O possesses the Dawson structure. EIS measurements show a high conductivity (3.10 x 10{sup -2} S cm{sup -1} at 26 deg. C and 75% relative humidity), with an activation energy of 32.23 kJ mol{sup -1} for proton conduction. The mechanism of proton conduction for this heteropoly acid is Vehicle mechanism.

  17. Chromatographic determination of silicon and phosphorus as molybdic heteropoly acids with preconcentration

    International Nuclear Information System (INIS)

    Tikhomirova, T.I.; Krokhin, O.V.; Dubovik, D.B.; Ivanov, A.V.; Shpigun, O.A.

    2002-01-01

    Chromatographic behaviour of silicon and phosphorus as molybdic heteropoly acids with preconcentration as ion associations of heteropoly acid with tributylammonium bromide was studied. The technique of simultaneous analysis of silicon and phosphorus was developed. During investigation into the effect of acetonitril content in the probe on the form of chromatographic peak of molybdosilicic acid the negative influence of acetonitril on the form of peak was ascertained. This effect may be eliminated by the lowering of acetonitril content up to 50 %. It was found that under these conditions the chromatographic peak practically was absent, because of the heteropoly acid of the Mo(VI) abundance transformed in the MoO 2 2+ cation form without reaction with tributylammonium cation during concentration of heteropoly acid [ru

  18. On basicity and composition of molybdogermanium heteropoly acid

    International Nuclear Information System (INIS)

    Mirzoyan, F.V.; Tarayan, V.M.; Petrosyam, A.A.

    1984-01-01

    The data on the number of single-charged cations of the basic dye (BD) associated by anion of molybdogermanium heteropoly acid equal to effective acid basicity, as well as the data on chemical analysis of formed solid-phase BD-MGA compounds were used to establish that composition and basicity of MGA depend on the nature of dye-precipitator. The use of acridine orange results in stabilization and precipitation of octasubstituted 12MGA salt, and acriflavine-tetrasubstituted 8MGA salt. Formation of the last ones is independent of medium acidity in its wide range: pH 0.45-4.80 and pH 0-3.8 respectively

  19. Sorption of heteropoly acids by polyurethane foam

    International Nuclear Information System (INIS)

    Dmitreinko, S.G.; Goncharova, L.V.; Runov, V.K.; Zakharov, V.N.; Aslanova, L.A.

    1997-01-01

    Sorption of oxidized and reduced forms of molybdosilicic, molybdophosphoric and molybdovanadophosphoric acids by polyurethane foam based on ethers and esters is studied. On the basis of sorption dependence on solution pH, polyurethane foam type and spectral characteristics of sorbates the suggestion has been made that in the polyurethane foam phase there are two main types of sorbent-sorbate interaction: electrostatic (ion-ion) and with hydrogen bond formation: and it is impossible to determine the contribution of every interaction

  20. Synthesis, Characterization and Inhibition Effects of Vanadium Substituted Dawson-type Heteropoly Acids(Mo, P)

    Institute of Scientific and Technical Information of China (English)

    YIN Yan-bing; YANG Yu-lin; FAN Rui-qing; ZHU Yang-qing; SUN Ji-ru

    2011-01-01

    Four new vanadium substituted Dawson-type heteropoly acids H7[P2Mo17VO62]·39H2O(1),H8[P2Mo16V2O62]·41H2O(2), H9[P2Mo15V3O62]·51H2O(3) and H8[P2Mo14V4O62H2]·45H2O(4) were prepared respectively. Their structures were determined by IR and ICP. The inhibition effects of vanadium substituted Dawson-type heteropoly acids(Mo, P) on free radical polymerization of methyl methacrylate(MMA) were investigated by dilatometry. The results show that the rate of the polymerization of MMA decreases and the inhibition effects of the four heteropoly acids reach the inhibitor performance of hydroquinone at a certain ratio.

  1. Biomass Conversion over Heteropoly Acid Catalysts

    KAUST Repository

    Zhang, Jizhe

    2015-01-01

    Biomass is a natural resource that is both abundant and sustainable. Its efficient utilization has long been the focus of research and development efforts with the aim to substitute it for fossil-based feedstock. In addition to the production

  2. Conversion of industrial (ligno)cellulose feeds to isosorbide with heteropoly acids and Ru on carbon

    Energy Technology Data Exchange (ETDEWEB)

    Op de Beeck, B.; Van Lishout, J.; Jacobs, P.A.; Sels, B.F. [Centre for Surface Chemistry and Catalysis, Katholieke Universiteit Leuven, Kasteelpark Arenberg 23, 3001 Heverlee (Belgium); Geboers, J. [Max-Planck-Institut fuer Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Muelheim an der Ruhr (Germany); Van de Vyver, S. [Massachusetts Institute of Technology MIT, Massachusetts Avenue 77, Cambridge, MA 02139-4307 (United States); Snelders, J.; Courtin, C.M. [Centre for Food and Microbial Technology, Katholieke Universiteit Leuven, Kasteelpark Arenberg 22, 3001 Heverlee (Belgium); Huijgen, W.J.J. [Biomass and Energy Efficiency BEE, Energy research Centre of the Netherlands ECN, Westerduinweg 3, 1755 LE Petten (Netherlands)

    2013-01-11

    The catalytic valorization of cellulose is currently subject of intense research. Isosorbide is among the most interesting products that can be formed from cellulose as it is a potential platform molecule and can be used for the synthesis of a wide range of pharmaceuticals, chemicals, and polymers. A promising direct route from cellulose to isosorbide is presented in this work. The strategy relies on a one-pot bifunctional catalytic concept, combining heteropoly acids, viz. H4SiW12O40, and redox catalysts, viz. commercial Ru on carbon, under H2 pressure. Starting from pure microcrystalline cellulose, a rapid conversion was observed, resulting in over 50% isosorbide yield. The robustness of the developed system is evidenced by the conversion of a range of impure cellulose pulps obtained by organosolv fractionation, with isosorbide yields up to 63%. Results were compared with other (ligno)cellulose feedstocks, highlighting the importance of fractionation and purification to increase reactivity and convertibility of the cellulose feedstock.

  3. Molybdenum-containing acidic catalysts to convert cellulosic biomass to glycolic acid

    KAUST Repository

    Han, Yu

    2014-09-30

    Embodiments of the present invention include methods and compositions related to catabolic conversion of cellulosic biomass to glycolic acid using molybdenum-containing acidic catalysts. The invention includes the use of heteropoly and isopoly acids and salts as the molybdenum-containing multi-functional catalysts for biomass conversion. In embodiments of the invention, the reactions employ successive hydrolysis, retro-aldol fragmentation, and selective oxidation in a noble metal-free system.

  4. Oxidative Desulfurization of Dibenzothiophene Using Dawson Type Heteropoly Compounds/Tantalum as Catalyst

    Directory of Open Access Journals (Sweden)

    Risfidian Mohadi

    2016-03-01

    Full Text Available Catalyst (NH46[b-P2W18O62]/Ta has been synthesized by simple wet impregnation at 30-40 °C under atmospheric conditions using Dawson type polyoxometalate (NH46[b-P2W18O62] and tantalum. The catalyst was characterized by FTIR spectrophotometer, XRD, SEM, and N2 adsorption desorption methods. FTIR spectrum of (NH46[b-P2W18O62]/Ta showed that Dawson type polyoxometalate (NH46[b-P2W18O62] and Ta was successfully impregnated which was indicated by vibration spectrum at wavenumber of 900-1100 cm-1 for polyoxometalate and 550 cm-1 for Ta. The surface area of the (NH46[b-P2W18O62]/Ta after impregnation was higher than (NH46[b-P2W18O62]•nH2O and its morphology was found to be uniform. The catalytic activity of (NH46[b-P2W18O62]/Ta toward desulfurization of dibenzothiophene was three times higher than the original catalyst of (NH46[b-P2W18O62]•nH2O without impregnation. The catalytic regeneration test of catalyst (NH46[b-P2W18O62]/Ta showed that the catalytic activity for first regeneration of catalyst has similar catalytic activity with the fresh catalyst without loss of catalytic activity indicated by almost similar percent conversion.

  5. Iodination of Alcohols over Keggin-type Heteropoly Compounds: A ...

    African Journals Online (AJOL)

    NICO

    compared in the iodination of benzyl alcohol with KI under mild reaction ... Keggin-type heteropoly compounds, supported catalyst, alcohols, alkyl iodides, potassium iodide. 1. .... water), the chloride salt of the corresponding metal was added.

  6. Direct conversion of cellulose to glycolic acid with a phosphomolybdic acid catalyst in a water medium

    KAUST Repository

    Zhang, Jizhe

    2012-08-03

    Direct conversion of cellulose to fine chemicals has rarely been achieved. We describe here an eco-benign route for directly converting various cellulose-based biomasses to glycolic acid in a water medium and oxygen atmosphere in which heteromolybdic acids act as multifunctional catalysts to catalyze the hydrolysis of cellulose, the fragmentation of monosaccharides, and the selective oxidation of fragmentation products. With commercial α-cellulose powder as the substrate, the yield of glycolic acid reaches 49.3%. This catalytic system is also effective with raw cellulosic biomass, such as bagasse or hay, as the starting materials, giving rise to remarkable glycolic acid yields of ∼30%. Our heteropoly acid-based catalyst can be recovered in solid form after reaction by distilling out the products and solvent for reuse, and it exhibits consistently high performance in multiple reaction runs. © 2012 American Chemical Society.

  7. Catalytic oxidation of light alkanes (C1-C4) by heteropoly compounds

    KAUST Repository

    Sun, Miao; Zhang, Jizhe; Putaj, Piotr; Caps, Valerie; Lefè bvre, Fré dé ric; Pelletier, Jeremie; Basset, Jean-Marie

    2014-01-01

    Heteropoly compounds (HPC) have revealed their potential to generate catalyst for selectively converting light alkanes to oxygenated products. There are various structures in which they are active the primary structure being that of the heteropolyanion itself, the secondary structure is the three-dimensional arrangements of polyanions, and the tertiary structure representing the manner in which the secondary structure assembles into solid particles. There are also a huge variety of elements inside the HPA. The heteropoly acids can have acidity, which varies dramatically depending on composition. This complexity of situation makes it very difficult to really have a predictive vision of their ability to activate and functionalize alkanes. However, a large amount of data reported suggests that the initial formula of the precatalyst is pivotal to direct the selectivity of the reaction toward different oxygenates. Inclusion of alternative transition metal atoms as addenda is highly influential with iron, vanadium, and antimony being particularly outstanding.

  8. Catalytic oxidation of light alkanes (C1-C4) by heteropoly compounds

    KAUST Repository

    Sun, Miao

    2014-01-22

    Heteropoly compounds (HPC) have revealed their potential to generate catalyst for selectively converting light alkanes to oxygenated products. There are various structures in which they are active the primary structure being that of the heteropolyanion itself, the secondary structure is the three-dimensional arrangements of polyanions, and the tertiary structure representing the manner in which the secondary structure assembles into solid particles. There are also a huge variety of elements inside the HPA. The heteropoly acids can have acidity, which varies dramatically depending on composition. This complexity of situation makes it very difficult to really have a predictive vision of their ability to activate and functionalize alkanes. However, a large amount of data reported suggests that the initial formula of the precatalyst is pivotal to direct the selectivity of the reaction toward different oxygenates. Inclusion of alternative transition metal atoms as addenda is highly influential with iron, vanadium, and antimony being particularly outstanding.

  9. The active component of vanadium-molybdenum catalysts for the oxidation of acrolein to acrylic acid

    International Nuclear Information System (INIS)

    Andrushkevich, T.V.; Kuznetsova, T.G.

    1986-01-01

    The catalytic properties of the vanadium-molybdenum oxide system were investigated in the oxidation of acrolein to acrylic acid. The active component of the catalyst is the compound VMo 3 O 11 , the maximum amount of which is observed at a content of 7-15 mole% V 2 O 4 . The compound VMo 3 O 11 is formed in the thermodecomposition of silicomolybdovanadium heteropoly acids or isopoly compounds, reduced with respect to vanadium, and contains V 4+ and Mo 6+ . The optimum treatment for the formation of this compound is treatment in the reaction mixture at 400 degrees C

  10. Proton conductivity and fuel cell property of composite electrolyte consisting of Cs-substituted heteropoly acids and sulfonated poly(ether-ether ketone)

    Energy Technology Data Exchange (ETDEWEB)

    Oh, S.Y.; Yoshida, T.; Kawamura, G.; Sakai, M.; Matsuda, A. [Department of Materials Science, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi, Aichi 441-8580 (Japan); Muto, H. [Department of Materials Science and Engineering, Kurume National College of Technology, 1-1-1 Komorino, Kurume, Fukuoka 830-8555 (Japan)

    2010-09-15

    Inorganic-organic composite electrolytes were fabricated from partially Cs{sup +}-substituted heteropoly acids (Cs-HPAs) and sulfonated poly(ether-ether ketone) (SPEEK) for application in fuel cells. Heteropoly acids, such as phosphotungstic acid (H{sub 3}PW{sub 12}O{sub 40}:WPA), and silicotungstic acid (H{sub 4}SiW{sub 12}O{sub 40}:WSiA), were mechanochemically treated with cesium hydrogen sulfate (CsHSO{sub 4}) to obtain the form of Cs-HPAs. SPEEK was prepared from PEEK by sulfonation using concentrated sulfuric acid. Water durability and surface structure of HPAs were modified by introducing Cs{sup +} into HPAs. Flexible and hot water stable composite electrolytes were obtained, and their electrochemical properties were markedly improved with the addition of Cs-HPAs into the SPEEK matrix. Maximum power densities of 245 and 247 mW cm{sup -2} were obtained for 50WPA.50CsHSO{sub 4} and 50WSiA.50CsHSO{sub 4} in SPEEK (1/5 by weight) composite electrolytes, respectively, from single cell tests at 80 C and 80 RH%. These results suggest that a three-dimensional proton-conductive path was formed among homogeneously distributed Cs-HPAs particles in the SPEEK matrix. The Cs-HPAs incorporated into the SPEEK matrix increased the number of protonate sites in the electrolyte. These observations imply that the mechanochemically synthesized Cs-HPAs, which consist of hydrogen bondings between Cs-HPAs and -HSO{sub 4}{sup -}, dissociated from CsHSO{sub 4}, are promising materials as inorganic fillers in inorganic-organic composite. (author)

  11. 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  |

  12. Investigation and application of multiple reactions between molybdoniobium heteropoly acid and di- or trimethylthionines

    Energy Technology Data Exchange (ETDEWEB)

    Mirzoyam, F.B.; Karapetyan, A.A.

    1986-03-01

    This paper presents the results of the study and use of reactions of molybdoniobic acid (MNA) with di- and trimethylthiones (DMT and TMT, respectively). It was found that light absorption of acetone solutions of the products of outer-sphere interaction between MNA and DMT or TMT enabled the determination of optimum acidity for MNA formation. Reaction between TMT and MNA gives two different compounds containing two and five associated dye cations, different in molar extinction coefficient and optimum reaction acidity (pH 0.05-0.25 and 0.35-0.90). Formation of the 6th and 8th molybdenum series with an identical composition of the outer sphere is shown. A highly sensitive photometric method for determining niobium has been developed.

  13. Efficient hydrodeoxygenation of biomass-derived ketones over bifunctional Pt-polyoxometalate catalyst.

    Science.gov (United States)

    Alotaibi, Mshari A; Kozhevnikova, Elena F; Kozhevnikov, Ivan V

    2012-07-21

    Acidic heteropoly salt Cs(2.5)H(0.5)PW(12)O(40) doped with Pt nanoparticles is a highly active and selective catalyst for one-step hydrogenation of methyl isobutyl and diisobutyl ketones to the corresponding alkanes in the gas phase at 100 °C with 97-99% yield via metal-acid bifunctional catalysis.

  14. Novel Approaches to Immobilized Heteropoly Acid Systems for High Temperature, Low Relative Humidity Polymer-Type Membranes - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Herring, Andrew M; Horan, James L; Aieta, Niccolo V; Sachdeva, Sonny; Kuo, Mei-Chen; Ren, Hui; Lingutla, Anitha; Emery, Michael; Haugen, Gregory M; Yandrasits, Michael A; Sharma, Neeraj; Coggio, William D; Hamrock, Steven J; Frey, Matthew H

    2012-05-20

    Original research was carried out at the CSM and the 3M Company from March 2007 through September 2011. The research was aimed at developing new to the world proton electrolyte materials for use in hydrogen fuel cells, in particular with high proton conductivity under hot and dry conditions (>100mS/cm at 120°C and 50%RH). Broadly stated, the research at 3M and between 3M and CSM that led to new materials took place in two phases: In the first phase, hydrocarbon membranes that could be formed by photopolymerization of monomer mixtures were developed for the purpose of determining the technical feasibility of achieving the program's Go/No-Go decision conductivity target of >100mS/cm at 120°C and 50%RH. In the second phase, attempts were made to extend the achieved conductivity level to fluorinated material systems with the expectation that durability and stability would be improved (over the hydrocarbon material). Highlights included: Multiple lots of an HPA-immobilized photocurable terpolymer derived from di-vinyl-silicotungstic acid (85%), n-butyl acrylate, and hexanediol diacrylate were prepared at 3M and characterized at 3M to exhibit an initial conductivity of 107mS/cm at 120°C and 47%RH (PolyPOM85v) using a Bekktech LLC sample fixture and TestEquity oven. Later independent testing by Bekktech LLC, using a different preheating protocol, on the same material, yielded a conductivity value of approximately 20mS/cm at 120°C and 50%RH. The difference in measured values is likely to have been the result of an instability of properties for the material or a difference in the measurement method. A dispersed catalyst fuel cell was fabricated and tested using a 150¼m thick HPA-based photocurable membrane (above, PolyPOM75v), exhibiting a current density of greater than 300mA/cm2 at 0.5V (H2/Air 800/1800sccm 70°C/75%RH ambient outlet pressure). Multiple lots of a co-polymer based on poly-trifluorovinylether (TFVE) derived HPA were synthesized and fabricated into

  15. Synthesis of nanoscale layers of heteropoly compounds based on molybdophosphoric acid by ion lamination on the silica surface

    International Nuclear Information System (INIS)

    Gulina, L.B.; Tolstoj, V.P.

    2004-01-01

    Nanolayers of iso- and heteropolycompound of the composition Zr 2.6 (OH) x PMo 8.0 Sn 1.9 O y · nH 2 O were synthesized by the method of ion lamination during successive treatment of quartz substrate by water solutions of reduced molybdophosphoric acid and zirconium acetate. The compounds prepared were characterized by the methods of electronic, IR and X-ray photoelectron spectroscopy. It was shown that heating of the compounds in the air at 200-400 deg C involves removal of water molecules from the layer, Mo 5+ oxidation to Mo 6+ and formation of chemical bonds Mo-O-Zr and Mo-O-Sn [ru

  16. Ultrasound-assisted biodiesel production by a novel composite of Fe(III)-based MOF and phosphotangestic acid as efficient and reusable catalyst.

    Science.gov (United States)

    Nikseresht, Ahmad; Daniyali, Asra; Ali-Mohammadi, Mahdi; Afzalinia, Ahmad; Mirzaie, Abbas

    2017-07-01

    In this work, esterification of oleic acid by various alcohols is achieved with high yields under ultrasonic irradiation. This reaction performed with a novel heterogeneous catalyst that fabricated by heteropoly acid and Fe(III)-based MOF, namely MIL-53 (Fe). Syntheses of MIL-53 and encapsulation process carry out by ultrasound irradiation at ambient temperature and atmospheric pressure. The prepared composite was characterized by various techniques such as XRD, FT-IR, SEM, BET and ICP that demonstrate excellent catalytic activities, while being highly convenient to synthesize. The obtained results revealed that ultrasound irradiation could be used for the appropriate and rapid biodiesel production. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Dehydration of alcohols using solid acid catalysts

    OpenAIRE

    Cholerton, Mary

    2014-01-01

    Solid acid catalysts were prepared through silicon substitution into aluminophosphate frameworks. Silicon incorporation was confirmed using solid state nuclear magnetic resonance spectroscopy. The nature of the acid sites generated was determined using Fourier Transform infrared spectroscopy. These materials were tested as catalysts for the dehydration of ethanol to ethylene at low operating temperatures. The materials were active for dehydration of ethanol to ethylene with significant differ...

  18. Strategies of Coping with Deactivation of NH3-SCR Catalysts Due to Biomass Firing

    DEFF Research Database (Denmark)

    Schill, Leonhard; Fehrmann, Rasmus

    2018-01-01

    silicates, often in the form of coal fly ash, is an industrially proven method of removing K aerosols from flue gases. Tail-end placement of the SCR unit was also reported to result in acceptable catalyst stability; however, flue-gas reheating after the flue gas desulfurization is, at present, unavoidable...... number of acid sites. This can be achieved by, e.g., using zeolites as support, replacing WO3 with heteropoly acids, and by preparing highly loaded, high surface area, very active V2O5/TiO2 catalyst using a special sol-gel method....

  19. Hydrodeoxygenation of Levulinic Acid over Supported Catalysts

    NARCIS (Netherlands)

    Luo, Wenhao|info:eu-repo/dai/nl/341385972

    2014-01-01

    Levulinic acid (LA), which can be produced from the sugar fractions of lignocellulosic biomass, is a promising sustainable platform molecule that can play a major role in future biorefineries. The work described was aimed at the development of heterogeneous catalysts for the selective conversion of

  20. Acid monolayer functionalized iron oxide nanoparticle catalysts

    Science.gov (United States)

    Ikenberry, Myles

    Superparamagnetic iron oxide nanoparticle functionalization is an area of intensely active research, with applications across disciplines such as biomedical science and heterogeneous catalysis. This work demonstrates the functionalization of iron oxide nanoparticles with a quasi-monolayer of 11-sulfoundecanoic acid, 10-phosphono-1-decanesulfonic acid, and 11-aminoundecanoic acid. The carboxylic and phosphonic moieties form bonds to the iron oxide particle core, while the sulfonic acid groups face outward where they are available for catalysis. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectrometry (XPS), and dynamic light scattering (DLS). The sulfonic acid functionalized particles were used to catalyze the hydrolysis of sucrose at 80° and starch at 130°, showing a higher activity per acid site than the traditional solid acid catalyst Amberlyst-15, and comparing well against results reported in the literature for sulfonic acid functionalized mesoporous silicas. In sucrose catalysis reactions, the phosphonic-sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic-sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. Between the two sulfonic ligands, the phosphonates produced a more tightly packed monolayer, which corresponded to a higher sulfonic acid loading, lower agglomeration, lower recoverability through application of an external magnetic field, and higher activity per acid site for the hydrolysis of starch. Functionalizations with 11-aminoundecanoic acid resulted in some amine groups binding to the surfaces of iron oxide nanoparticles. This amine binding is commonly ignored in iron oxide

  1. In situ synthesized heteropoly acid/polyaniline/graphene nanocomposites to simultaneously boost both double layer- and pseudo-capacitance for supercapacitors.

    Science.gov (United States)

    Cui, Zhiming; Guo, Chun Xian; Yuan, Weiyong; Li, Chang Ming

    2012-10-05

    It is challenging to simultaneously increase double layer- and pseudo-capacitance for supercapacitors. Phosphomolybdic acid/polyaniline/graphene nanocomposites (PMo(12)-PANI/GS) were prepared by using PMo(12) as a bifunctional reagent for not only well dispersing graphene for high electrochemical double layer capacitance but also in situ chemically polymerizing aniline for high pseudocapacitance, resulting in a specific capacitance of 587 F g(-1), which is ~1.5 and 6 times higher than that of PANI/GS (392 F g(-1)) and GS (103 F g(-1)), respectively. The nanocomposites also exhibit good reversibility and stability. Other kinds of heteropolyacids such as molybdovanadophosphoric acids (PMo(12-x)V(x), x = 1, 2 and 3) were also used to prepare PMo(12-x)V(x)-PANI/GS nanocomposites, also showing enhanced double layer- and pseudo-capacitance. This further proves the proposed concept to simultaneously boost both double layer- and pseudo-capacitance and demonstrates that it could be a universal approach to significantly improve the capacitance for supercapacitors.

  2. Study of Pd-Au/MWCNTs formic acid electrooxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Mikolajczuk, Anna; Borodzinski, Andrzej; Kedzierzawski, Piotr; Lesiak, Beata [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warszawa (Poland); Stobinski, Leszek [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warszawa (Poland); Faculty of Materials Science and Engineering, Warsaw University of Technology, ul. Woloska 141, 02-507 Warsaw (Poland); Koever, Laszlo; Toth, Jozsef [Institute of Nuclear Research, Hungarian Academy of Sciences (ATOMKI), P. O. Box 51, 4001 Debrecen (Hungary); Lin, Hong-Ming [Department of Materials Engineering, Tatung University, 40, Chungshan N. Rd., 3rd Sec, 104, Taipei (China)

    2010-12-15

    The Pd-Au multiwall carbon nanotubes (MWCNTs) supported catalyst exhibits higher power density in direct formic acid fuel cell (DFAFC) than similar Pd/MWCNTs catalyst. The Pd-Au/MWCNTs catalyst also exhibits higher activity and is more stable in electrooxidation reaction of formic acid during cyclic voltammetry (CV) measurements. After preparation by polyol method, the catalyst was subjected to two type of treatments: (I) annealing at 250 C in 100% of Ar, (II) reducing in 5% of H{sub 2} in Ar atmosphere at 200 C. It was observed that the catalyst after treatment I was completely inactive, whereas after treatment II exhibited high activity. In order to explain this effect the catalysts were characterized by electron spectroscopy methods. The higher initial catalytic activity of Pd-Au/MWCNTs catalyst than Pd/MWCNTs catalyst in reaction of formic acid electrooxidation was attributed to electronic effect of gold in Pd-Au solution, and larger content of small Au nanoparticles of 1 nm size. The catalytic inactivity of Pd-Au/MWCNTs catalysts annealed in argon is attributed to carbon amorphous overlayer covering of Pd oxide shell on the metallic nanoparticles. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Acid Dissolution of Depleted Uranium from Catalyst using Microwave

    Energy Technology Data Exchange (ETDEWEB)

    Sung, Jin Hyun; Jeong, Seong Gi; Park, Kwang Heon [Kyunghee University, Yongin (Korea, Republic of)

    2011-05-15

    The separation process of uranium is one of the most important fields in nuclear industry because uranium is used primary in nuclear power plants. Uranium ores are treated by either acid or alkaline reagents. Uranium can be dissolved by acid or alkaline solutions. There are two oxidation states in which the hexavalent form, the oxide of which is UO{sub 3}, and the tetravalent form, the oxide of which is UO{sub 2}. However, depleted uranium(DU) has also been used as a catalyst in specialized chemical reaction such as ammoxidation. The preferred catalyst for propylene oxidation with ammonia was a uranium oxide-antimony oxide composition. The active phase of catalyst was known as USbO{sub 5} and USb{sub 3}O{sub 10}. There is pentavalent form. Waste catalyst containing DU was generated and stored in chemical industry. In this work, we removed DU from catalyst by acid dissolution

  4. Catalytic oxidative conversion of cellulosic biomass to formic acid and acetic acid with exceptionally high yields

    KAUST Repository

    Zhang, Jizhe

    2014-09-01

    Direct conversion of raw biomass materials to fine chemicals is of great significance from both economic and ecological perspectives. In this paper, we report that a Keggin-type vanadium-substituted phosphomolybdic acid catalyst, namely H4PVMo11O40, is capable of converting various biomass-derived substrates to formic acid and acetic acid with high selectivity in a water medium and oxygen atmosphere. Under optimized reaction conditions, H4PVMo11O40 gave an exceptionally high yield of formic acid (67.8%) from cellulose, far exceeding the values achieved in previous catalytic systems. Our study demonstrates that heteropoly acids are generally effective catalysts for biomass conversion due to their strong acidities, whereas the composition of metal addenda atoms in the catalysts has crucial influence on the reaction pathway and the product selectivity. © 2013 Elsevier B.V.

  5. The acidic properties of mixed tin and antimony oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Irving, E.A.; Taylor, D.

    1978-01-01

    The acidic properties of mixed tin + antimony oxide catalysts were studied in the isomerization of 3,3-dimethyl-1-butene, cyclopropane, 1-butene, and cis-2-butene and the dehydration of isopropanol over the mixed oxides outgassed at room temperature and 698/sup 0/K. Only the zero-order portions of the reaction were used for calculations. With catalysts outgassed at room temperature, weakly acidic sites were present, and all the reactions probably occurred by a carbonium ion mechanism with Broensted acid sites as a source of protons. The rates increased with increasing antimony content to a maximum at approx. 50 at. % and then decreased with further increase in the antimony content. Outgassing of the catalysts at 698/sup 0/K increased the isomerization rate of 3,3-dimethyl-1-butene, but decreased those for cyclopropane and isopropanol due to poisoning by the propylene produced. For 1-butene and cis-2-butene and catalysts outgassed at 698/sup 0/K, only catalysts with less than 50Vertical Bar3< antimony were active. The catalysts were poisoned by treatment with bases or with sodium acetate. A proposed correlation between rates and acidity led to the conclusion that the catalyst composition corresponding to maximum acidity differs from that for maximum selective oxidation activity. Graphs and 10 references.

  6. Environmentally Benign Bifunctional Solid Acid and Base Catalysts

    NARCIS (Netherlands)

    Elmekawy, A.; Shiju, N.R.; Rothenberg, G.; Brown, D.R.

    2014-01-01

    Solid bifunctional acid-​base catalysts were prepd. in two ways on an amorphous silica support: (1) by grafting mercaptopropyl units (followed by oxidn. to propylsulfonic acid) and aminopropyl groups to the silica surface (NH2-​SiO2-​SO3H)​, and (2) by grafting only aminopropyl groups and then

  7. Formic acid oxidation at platinum-bismuth catalysts

    Directory of Open Access Journals (Sweden)

    Popović Ksenija Đ.

    2015-01-01

    Full Text Available The field of heterogeneous catalysis, specifically catalysis on bimetallic surfaces, has seen many advances over the past few decades. Bimetallic catalysts, which often show electronic and chemical properties that are distinct from those of their parent metals, offer the opportunity to obtain new catalysts with enhanced selectivity, activity, and stability. The oxidation of formic acid is of permanent interest as a model reaction for the mechanistic understanding of the electrooxidation of small organic molecules and because of its technical relevance for fuel cell applications. Platinum is one of the most commonly used catalysts for this reaction, despite the fact that it shows a few significant disadvantages: high cost and extreme susceptibility to poisoning by CO. To solve this problem, several approaches have been used, but generally, they all consist in the modification of platinum with a second element. Especially, bismuth has received significant attention as Pt modifier. According to the results presented in this survey dealing with the effects influencing the formic acid oxidation it was found that two types of Pt-Bi bimetallic catalysts (bulk and low loading deposits on GC showed superior catalytic activity in terms of the lower onset potential and oxidation current density, as well as exceptional stability compared to Pt. The findings in this report are important for the understanding of mechanism of formic acid electrooxidation on a bulk alloy and decorated surface, for the development of advanced anode catalysts for direct formic acid fuel cells, as well as for the synthesis of novel low-loading bimetallic catalysts. The use of bimetallic compounds as the anode catalysts is an effective solution to overcoming the problems of the formic acid oxidation current stability for long term applications. In the future, the tolerance of both CO poisoning and electrochemical leaching should be considered as the key factors in the development

  8. Beaded Fiber Mats of PVA Containing Unsaturated Heteropoly Salt

    Institute of Scientific and Technical Information of China (English)

    Guo Cheng YANG; Yan PAN; Jian GONG; Chang Lu SHAO; Shang Bin WEN; Chen SHAO; Lun Yu QU

    2004-01-01

    Poly(vinyl alcohol) (PVA) fiber mats containing unsaturated heteropoly salt was prepared for the first time. IR, X-ray diffraction and SEM photographs characterized the beaded fiber mats.The viscoelasticity and the conductivity of the solution were the key factors that influence the formation of the beaded fiber mats.

  9. Hydrolysis of isocyanic acid on SCR catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Elsener, M; Kleemann, M; Koebel, M [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Standard SCR catalysts possess high activity for the hydrolysis of HNCO and thus explain the suitability of urea as a selective reducing agent for NO{sub x}. At high space velocities HNCO-slip can get perceptible over the entire temperature range. This can be attributed to the fact that the temperature dependence is strong for the SCR reaction, but weak for the hydrolysis reaction. (author) 3 figs., 5 refs.

  10. Dissolution of Metal Supported Spent Auto Catalysts in Acids

    Directory of Open Access Journals (Sweden)

    Fornalczyk A.

    2016-03-01

    Full Text Available Metal supported auto catalysts, have been used in sports and racing cars initially, but nowadays their application systematically increases. In Metal Substrate (supported Converters (MSC, catalytic functions are performed by the Platinum Group Metals (PGM: Pt, Pd, Rh, similarly to the catalysts on ceramic carriers. The contents of these metals make that spent catalytic converters are valuable source of precious metals. All over the world there are many methods for the metals recovery from the ceramic carriers, however, the issue of platinum recovery from metal supported catalysts has not been studied sufficiently yet. The paper presents preliminary results of dissolution of spent automotive catalyst on a metal carrier by means of acids: H2SO4, HCl, HNO3, H3PO4. The main assumption of the research was the dissolution of base metals (Fe, Cr, Al from metallic carrier of catalyst, avoiding dissolution of PGMs. Dissolution was the most effective when concentrated hydrochloric acid, and 2M sulfuric acid (VI was used. It was observed that the dust, remaining after leaching, contained platinum in the level of 0.8% and 0.7%, respectively.

  11. Simultaneous determination of two active components of pharmaceutical preparations by sequential injection method using heteropoly complexes

    Directory of Open Access Journals (Sweden)

    Mohammed Khair E. A. Al-Shwaiyat

    2014-12-01

    Full Text Available New approach has been proposed for the simultaneous determination of two reducing agents based on the dependence of their reaction rate with 18-molybdo-2-phosphate heteropoly complex on pH. The method was automated using the manifold typical for the sequential analysis method. Ascorbic acid and rutin were determined by successive injection of two samples acidified to different pH. The linear range for rutin determination was 0.6-20 mg/L and the detection limit was 0.2 mg/L (l = 1 cm. The determination of rutin was possible in the presence of up to a 20-fold excess of ascorbic acid. The method was successfully applied to the determination of ascorbic acid and rutin in ascorutin tablets. The applicability of the proposed method for the determination of total polyphenol content in natural plant samples was shown.

  12. Polyvinylpolypyrrolidone Supported Brønsted Acidic Catalyst for Esterification

    Directory of Open Access Journals (Sweden)

    Song Wang

    2016-01-01

    Full Text Available A polyvinylpolypyrrolidone (PVPP supported Brønsted acidic catalyst ([PVPP-BS]HSO4 was prepared by coupling SO3H-functionalized polyvinylpolypyrrolidone with H2SO4 in this work. After the characterization through FT-IR, FESEM, TG, BET, and elemental analysis, it was found that 1,4-butane sultone (BS and sulfuric acid reacted with PVPP and were immobilized on PVPP surface. The prepared [PVPP-BS]HSO4 catalyst shows high catalytic activity for a series of esterification reactions and could be separated from the reacted mixture easily. Moreover, this catalyst could be recycled and reused for six times without significant loss of catalytic performance.

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

    African Journals Online (AJOL)

    As the current global environmental concerns have prompted regulations to reduce the level of aromatic compounds, particularly benzene and its derivatives in gasoline, ydroisomerisation of n-alkanes is becoming a major alternative for enhancing octane number. Series of solid acid catalysts comprising of Freidel crafts, ...

  14. Selective production of aromatics from alkylfurans over solid acid catalysts

    DEFF Research Database (Denmark)

    Wang, Dong; Dumesic, James A.; Osmundsen, Christian Mårup

    2013-01-01

    to deactivation by carbon deposition than do microporous materials. Results from Raman spectroscopy and the trend of turnover frequency with varying tungsten surface densities for a series of WOx-ZrO2 catalysts are consistent with previous investigations of other acid-catalyzed reactions; this suggests...

  15. Impacts of acid gases on mercury oxidation across SCR catalyst

    International Nuclear Information System (INIS)

    Zhuang, Ye; Laumb, Jason; Liggett, Richard; Holmes, Mike; Pavlish, John

    2007-01-01

    A series of bench-scale experiments were completed to evaluate acid gases of HCl, SO 2 , and SO 3 on mercury oxidation across a commercial selective catalytic reduction (SCR) catalyst. The SCR catalyst was placed in a simulated flue gas stream containing O 2 , CO 2 , H 2 O, NO, NO 2 , and NH 3 , and N 2 . HCl, SO 2 , and SO 3 were added to the gas stream either separately or in combination to investigate their interactions with mercury over the SCR catalyst. The compositions of the simulated flue gas represent a medium-sulfur and low- to medium-chlorine coal that could represent either bituminous or subbituminous. The experimental data indicated that 5-50 ppm HCl in flue gas enhanced mercury oxidation within the SCR catalyst, possibly because of the reactive chlorine species formed through catalytic reactions. An addition of 5 ppm HCl in the simulated flue gas resulted in mercury oxidation of 45% across the SCR compared to only 4% mercury oxidation when 1 ppm HCl is in the flue gas. As HCl concentration increased to 50 ppm, 63% of Hg oxidation was reached. SO 2 and SO 3 showed a mitigating effect on mercury chlorination to some degree, depending on the concentrations of SO 2 and SO 3 , by competing against HCl for SCR adsorption sites. High levels of acid gases of HCl (50 ppm), SO 2 (2000 ppm), and SO 3 (50 ppm) in the flue gas deteriorate mercury adsorption on the SCR catalyst. (author)

  16. Recovery of vanadium (V) from used catalysts in sulfuric acid production units by oxalic acid

    International Nuclear Information System (INIS)

    Abdulbaki, M.; Shino, O.

    2009-07-01

    Vanadium penta oxide (V 2 O 5 ), is used, in large quantities as a catalyst for the oxidation of SO 2 to SO 3 in sulfuric acid production units, during the oxidation process the level of the oxidation declines with the time because of catalyst poisoning. So the spent catalyst is usually through out in a specified special places by General Fertilizer Company which causes a pollution of the land. The present paper, studies the recovery of vanadium from the spent catalyst by using the oxalic acid. The optimal conditions of spent catalyst leaching have been studied. It has been shown that 2%(w/w) of oxalic acid is the most suitable for leaching process at 70 degree centigrade. The precipitation of vanadium using some alkaline media NH 4 OH has been also studied, it has been shown that ammonium hydroxide was the best at 50 degree centigrade. (author)

  17. Carbon catalysts for electrochemical hydrogen peroxide production in acidic media

    DEFF Research Database (Denmark)

    Čolić, Viktor; Yang, Sungeun; Révay, Zsolt

    2018-01-01

    Hydrogen peroxide is a commodity chemical, as it is an environmentally friendly oxidant. The electrochemical production of H2O2 from oxygen and water by the reduction of oxygen is of great interest, as it would allow the decentralized, on-site, production of pure H2O2. The ability to run...... the reaction in an acidic electrolyte with high performance is particularly important, as it would allow the use of polymer solid electrolytes and the production of pH-neutral hydrogen peroxide. Carbon catalysts, which are cheap, abundant, durable and can be highly selective show promise as potential catalysts...... for such systems. In this work, we examine the electrocatalytic performance and properties of seven commercially available carbon materials for H2O2 production by oxygen electroreduction. We show that the faradaic efficiencies for the reaction lie in a wide range of 18-82% for different carbon catalysts. In order...

  18. Naphthenic acid removal from HVGO by alkaline earth metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ding, L.; Rahimi, P.; Hawkins, R.; Bhatt, S.; Shi, Y. [National Centre for Upgrading Technology, Devon, AB (Canada); Natural Resources Canada, Devon, AB (Canada). CanmetENERGY

    2009-07-01

    This poster highlighted a study that investigated naphthenic acid removal from bitumen-derived heavy vacuum gas oil (HVGO) by thermal cracking and catalytic decarboxylation over alkaline earth-metal oxides and ZnO catalysts in a batch reactor and a continuous fixed-bed reactor. X-ray diffraction (XRD), thermogravimetric-differential thermal analysis (TG-DTA) temperature-programmed desorption (TPD) of carbon dioxide (CO{sub 2}-TPD), and scanning electron microscopy were used to characterize the fresh and spent catalysts. With MgO and ZnO, naphthenic acid removal proceeded via catalytic decarboxylation. No crystalline phase changes were observed after reaction. With CaO, multiple pathways such as catalytic decarboxylation, neutralization, and thermal cracking were responsible for naphthenic acid conversion. The spent catalysts contained Ca(OH){sub 2} and CaCO{sub 3}. With BaO, naphthenic acid conversion occurred through neutralization. All BaO was converted to Ba(OH){sub 2} during the reaction. tabs., figs.

  19. Nanocomposite catalyst with palladium nanoparticles encapsulated in a polymeric acid: A model for tandem environmental catalysis

    KAUST Repository

    Isimjan, Tayirjan T.; He, Quan; Liu, Yong; Zhu, Jesse; Puddephatt, Richard J.; Anderson, Darren Jason

    2013-01-01

    The synthesis and characterization of a novel hybrid nanocomposite catalyst comprised of palladium nanoparticles embedded in polystyrene sulfonic acid (PSSH) and supported on metal oxides is reported. The catalysts are intended for application

  20. POROUS ALUMINOPHOSPHATES :From Molecular Sieves to Designed Acid Catalysts

    Science.gov (United States)

    Pastore, H. O.; Coluccia, S.; Marchese, L.

    2005-08-01

    This review covers the synthesis, characterization, and physico-chemical properties of microporous and mesoporous aluminophosphates and silicoaluminophosphates molecular sieves. Particular emphasis is given to the materials that have found applications as acid catalysts. We consider the evolution of the synthesis procedures from the first discoveries to the current methodologies and give perspectives for new possible synthesis strategies. Emphasis is given to the use of specially prepared precursors/reactants designed for the use as molecular sieves. Experimental (especially MAS-NMR and FTIR spectroscopy) and theoretical approaches to the description of the Si insertion into the ALPO framework and to the acidic properties of SAPOs and MeAPSOs materials are discussed.

  1. Investigation of heterogeneous solid acid catalyst performance on low grade feedstocks for biodiesel production: A review

    International Nuclear Information System (INIS)

    Mansir, Nasar; Taufiq-Yap, Yun Hin; Rashid, Umer; Lokman, Ibrahim M.

    2017-01-01

    Highlights: • Solid acid catalysts are proficient to esterifying high free fatty acid feedstocks to biodiesel. • Heterogeneous catalysts have the advantage of easy separation and reusability. • Heterogeneous basic catalysts have limitations due to high FFA of low cost feedstocks. • Solid catalysts having acid and base sites reveal better catalyst for biodiesel production. - Abstract: The conventional fossil fuel reserves are continually declining worldwide and therefore posing greater challenges to the future of the energy sources. Biofuel alternatives were found promising to replace the diminishing fossil fuels. However, conversion of edible vegetable oils to biodiesel using homogeneous acids and base catalysts is now considered as indefensible for the future particularly due to food versus fuel competition and other environmental problems related to catalyst system and feedstock. This review has discussed the progression in research and growth related to heterogeneous catalysts used for biodiesel production for low grade feedstocks. The heterogeneous base catalysts have revealed effective way to produce biodiesel, but it has the limitation of being sensitive to high free fatty acid (FFA) or low grade feedstocks. Alternatively, solid acid catalysts are capable of converting the low grade feedstocks to biodiesel in the presence of active acid sites. The paper presents a comprehensive review towards the investigation of solid acid catalyst performance on low grade feedstock, their category, properties, advantages, limitations and possible remedy to their drawbacks for biodiesel production.

  2. Starch saccharification by carbon-based solid acid catalyst

    Science.gov (United States)

    Yamaguchi, Daizo; Hara, Michikazu

    2010-06-01

    The hydrolysis of cornstarch using a highly active solid acid catalyst, a carbon material bearing SO 3H, COOH and OH groups, was investigated at 353-393 K through an analysis of variance (ANOVA) and an artificial neural network (ANN). ANOVA revealed that reaction temperature and time are significant parameters for the catalytic hydrolysis of starch. The ANN model indicated that the reaction efficiency reaches a maximum at an optimal condition (water, 0.8-1.0 mL; starch, 0.3-0.4 g; catalyst, 0.3 g; reaction temperature, 373 K; reaction time, 3 h). The relationship between the reaction and these parameters is discussed on the basis of the reaction mechanism.

  3. Meso- and macroporous sulfonated starch solid acid catalyst for esterification of palm fatty acid

    Directory of Open Access Journals (Sweden)

    Ibrahim M. Lokman

    2016-03-01

    Full Text Available In the present work, a heterogeneous solid acid catalyst was successfully developed from starch. The catalyst was prepared by a significant two-step process; the initial step was incomplete carbonization of starch (ICS at 400 °C for 12 h and consequently followed by sulfonation process using concentrated H2SO4 to produce sulfonated-incomplete carbonized starch (ICS-SO3H. The characterization of the ICS-SO3H catalyst was done for chemical and physical properties such as X-ray diffraction (XRD, ammonia-temperature programmed desorption (NH3-TPD, surface area analysis, thermal gravimetric analysis (TGA, elemental analysis and morphology analysis by scanning electron microscope (SEM. BET results showed the structure of ICS-SO3H consists of meso- and macro-porous properties, which allowed high density of the SO3H group attached on its carbon networks. The catalytic activity of ICS-SO3H catalyst was determined by analyzing the catalyst performance to esterify palm fatty acid distillate (PFAD and sequentially produced methyl ester. The maximum free fatty acid (FFA conversion and FAME yield were as high as 94.6% and 90.4%, respectively, at 75 °C using 10:1 methanol-to-PFAD molar ratio and 2 wt.% of catalyst within 3 h. The catalyst has sufficient potential to recycle up to 6 reactions without reactivation step and any remarkable loss of catalytic activity. It revealed that the heterogeneous ICS-SO3H catalyst exhibits high stability, reusability and catalytic activity.

  4. Effects of water on the esterification of free fatty acids by acid catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Park, Ji-Yeon; Kim, Deog-Keun; Lee, Jin-Suk [Korea Institute of Energy Research, 71-2, Jang-dong, Yuseong-gu, Daejeon 305-343 (Korea); Wang, Zhong-Ming [Guangzhou Institute of Energy Conversion, No. 2 Nengyuan Rd, Wushan, Tianhe, Guangzhou 510-640 (China)

    2010-03-15

    To maximize the production of biodiesel from soybean soapstock, the effects of water on the esterification of high-FFA (free fatty acid) oils were investigated. Oleic acid and high acid acid oil (HAAO) were esterified by reaction with methanol in the presence of Amberlyst-15 as a heterogeneous catalyst or sulfuric acid as a homogeneous catalyst. The yield of fatty acid methyl ester (FAME) was studied at oil to methanol molar ratios of 1:3 and 1:6 and reaction temperatures of 60 and 80 C. The rate of esterification of oleic acid significantly decreased as the initial water content increased to 20% of the oil. The activity of Amberlyst-15 decreased more rapidly than that of sulfuric acid, due to the direct poisoning of acid sites by water. Esterification using sulfuric acid was not affected by water until there was a 5% water addition at a 1:6 molar ratio of oil to methanol. FAME content of HAAO prepared from soapstock rapidly increased for the first 30 min of esterification. Following the 30-min mark, the rate of FAME production decreased significantly due to the accumulation of water. When methanol and Amberlyst-15 were removed from the HAAO after 30 min of esterification and fresh methanol and a catalyst were added, the time required to reach 85% FAME content was reduced from 6 h to 1.8 h. (author)

  5. Fructose dehydration to 5-hydroxymethylfurfural over solid acid catalysts in a biphasic system

    NARCIS (Netherlands)

    Ordomskiy, V.; Schouten, J.C.; Schaaf, van der J.; Nijhuis, T.A.

    2012-01-01

    Different acidic heterogeneous catalysts like alumina, aluminosilicate, zirconium phosphate, niobic acid, ion-exchange resin Amberlyst-15, and zeolite MOR have been studied in fructose dehydration to 5-hydroxymethylfurfural (HMF). The acidity of these materials was characterized using

  6. On the role of acidity in amorphous silica-alumina based catalysts

    NARCIS (Netherlands)

    Poduval, D.G.

    2011-01-01

    Amorphous silica-alumina (ASA) is widely used as a solid acid catalyst or as a carrier for well-dispersed metal sulfide or metal catalysts. They are often involved in hydrocracking catalyst formulations, especially so when the aim is to produce middle distillates from heavy oil fractions. With

  7. Palladium catalyst system comprising zwitterion and/or acid-​functionalized ionic liquid

    DEFF Research Database (Denmark)

    2011-01-01

    The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH3COO)2, PdCI2, Pd(CH3...... methyl methacrylate and/or methacrylic acid. Catalyst systems according to the invention are suitable for reactions forming separable product and catalyst phases and supported ionic liquid phase SILP applications....

  8. Cyclic Acetalization of Furfural on Porous Aluminosilicate Acid Catalysts

    Directory of Open Access Journals (Sweden)

    Hartati Hartati

    2016-12-01

    Full Text Available Porous aluminosilicate materials included microporous and mesoporous ZSM-5, hierarchical aluminosilicates, and mesoporous aluminosilicate were tested for acetalization of furfural (furan-2-carbaldehyde with propylene glycol. The existing synthesis methods for aluminosilicate and ZSM-5 were modified to produce aluminosilicate material with hierarchical porous structure. Catalytic activity in acetalization of furfural by propylene glycol were conducted by refluxed of the mixture of furfural, propylene glycol and catalyst, using toluene as solvent and nitrobenzene as internal standard, at 106 °C for 4 h. The result showed that a combination of two structure directing agents, tetrapropylammonium hydroxide (TPAOH and cetyltrimethylammonium bromide (CTAB and modification of catalytic crystallization produced an active aluminosilicate framework that provides a wide access for a bulky reactants and strong acid sites to catalyze the reaction. The pore structure and the strength of the Brønsted acid sites were crucial for the high conversion of furfural to produce a cyclic acetal.

  9. Staining of fluid-catalytic cracking catalysts: Localising Brønsted acidity within a single catalyst particle

    NARCIS (Netherlands)

    Buurmans, I.L.C.; Ruiz Martinez, J.; van Leeuwen, S.L.; van der Beek, D.; Bergwerff, J.A.; Knowles, W.V.; Vogt, Eelco; Weckhuysen, B.M.

    2012-01-01

    A time-resolved in situ micro-spectroscopic approach has been used to investigate the Brønsted acidic properties of fluid-catalytic-cracking (FCC) catalysts at the single particle level by applying the acid-catalysed styrene oligomerisation probe reaction. The reactivity of individual FCC components

  10. Esterification free fatty acid in palm fatty acid distillate using sulfonated rice husk ash catalyst

    Science.gov (United States)

    Hidayat, Arif; Sutrisno, Bachrun

    2017-01-01

    Indonesia, as one of the biggest palm oil producers and exporters in the world, is producing large amounts of low-grade oil such as Palm Fatty Acid Distillate (PFAD) from palm oil industries. The use of PFAD can reduce the cost of biodiesel production significantly, which makes PFAD a highly potential alternative feedstock for biodiesel production. In this paper, the esterification of free fatty acid (FFA) on PFAD was studied using rice husk ash (RHA) as heterogeneous catalyst. The rice husk ash catalyst was synthesized by sulfonation using concentrated sulfuric acid. The RHA catalyst were characterized by using different techniques, such as porosity analysis, Fourier transform infrared (FT-IR) spectroscopy, total number of acid sites and elemental analysis. The effects of the molar ratio of methanol to PFAD (1-10%), the molar ratio of methanol to PFAD (4:1-10:1), and the reaction temperature (40-60°C) were studied for the conversion of FFA to optimize the reaction conditions. The results showed that the optimal conditions were an methanol to PFAD molar ratio of 10:1, the catalyst amount of 10 wt% of PFAD, and reaction temperature of 60°C.

  11. Chromium–tungsten–titanium mixed oxides solid catalyst for fatty acid methyl ester synthesis from palm fatty acid distillate

    International Nuclear Information System (INIS)

    Wan, Zuraida; Hameed, B.H.

    2014-01-01

    Highlights: • Chromium–tungsten–titanium mixed oxides as solid catalyst. • Catalyst used for esterification of palm fatty acid distillate to methyl esters. • The maximum methyl ester content is 83%. • Catalyst has shown good activity and can be recycled for 4 times. - Abstract: Chromium–tungsten–titanium mixed oxides solid catalysts were prepared and evaluated in the esterification of palm fatty acid distillate (PFAD) to produce fatty acid methyl ester (FAME). Esterification was conducted in a batch reactor at 110–200 °C temperature ranges. The catalysts were characterized by several techniques such as BET, TEM, FTIR, TGA, XRD, EDX and SEM. The treatment conditions during catalyst preparation, effect of reaction parameters, leaching of the active species and the recycled use of the catalyst were investigated. The catalyst with formula CrWTiO 2 was found to be the most active with maximum FAME content of 83% obtained at best reaction conditions of 170 °C for 3 h, 2:1 (methanol to oil molar ratio) and 2 wt.% catalyst dosage. The catalyst can be recycled for 4 times. The results revealed CrWTiO 2 good potentials for use in esterification of high acid value oil

  12. MESOPOROUS ACID SOLID AS A CARRIER FOR METALLOCENE CATALYST IN ETHYLENE POLYMERIZATION AND A CATALYST IN CATALYTIC DEGRADATION OF POLYETHYLENE

    Institute of Scientific and Technical Information of China (English)

    Wen-xi Cheng; Li-ya Shi; Shi-yun Li; Hui Chen; Tao Tang

    2007-01-01

    The possibility of mesoporous acid solid as a carrier for metallocene catalyst in ethylene polymerization and catalyst for polyethylene(PE)catalytic degradation was investigated.Here,HMCM-41 and AlMCM-41.and mesoporous silicoaluminophosphate molecular sieves(SAPO1 and SAPO2)were synthesized and used as acid solid.Much more gases were produced during catalytic degradation in PE/acid solid mixtures via in situ polymerization than those via physical mixing.The particle size distribution results exhibited that the particle size of SAPO1 in the PE/SAO1 mixture via in situ polymerization was about 1/14 times of that of the original SAPO1 or SAPO1.supported metallocene catalyst.This work shows a novel technology for chemical recycling of polyolefin.

  13. Palladium catalyst system comprising zwitterion and/or acid-functionalized ionic liquid

    DEFF Research Database (Denmark)

    2011-01-01

    The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH3COO)2, PdCI2, Pd(CH3......COCHCOCH3), Pd (CF3COO)2, Pd(PPh3)4 or Pd2(dibenzylideneacetone)3. Such catalyst systems can be used for e.g. alkoxycarbonylation reactions, carboxylation reactions, and/or in a co-polymerization reaction, e.g. in the production of methyl propionate and/or propanoic acid, optionally in processes forming...... methyl methacrylate and/or methacrylic acid. Catalyst systems according to the invention are suitable for reactions forming separable product and catalyst phases and supported ionic liquid phase SILP applications....

  14. Preparation and Characterization of a Solid Acid Catalyst from Macro Fungi Residue for Methyl Palmitate Production

    Directory of Open Access Journals (Sweden)

    Min Wang

    2015-07-01

    Full Text Available During the process of fungal polysaccharide extraction for health care products and food factories, a large quantity of macro-fungi residues are produced, but most of the residues are abandoned and become environmental pollutants. A solid acid catalyst, prepared by sulfonating carbonized Phellinus igniarius residue, was shown to be an efficient and environmentally benign catalyst for the esterification of palmitate acid (PA and methanol. As a comparison, two types of common biomass catalysts, wheat straws and wood chips, were prepared. In this study, characterizations, including scanning electron microscopy, thermo-gravimetric analysis, Fourier transform infrared spectrometry, Brunauer-Emmett-Teller assays and elemental analysis, and reaction conditions for the synthesis of methyl palmitate (MP using solid acid catalysts were investigated. Experiments showed that the solid acid catalyst prepared from P. igniarius residue had a higher catalytic activity than the other two catalysts, and the highest yield of MP catalyzed by P. igniarius residue solid acid catalyst was 91.5% under the following optimum conditions: molar ratio of methanol/PA of 10:1, reaction temperature of 60 °C, mass ratio of catalyst/substrate of 2%, and a reaction time of 1.5 h. Thus, the use of this catalyst offers a method for producing MP.

  15. In-situ Spectroscopic Studies and Modelling of Crystallization Processes of Sulphuric Acid Catalysts

    DEFF Research Database (Denmark)

    Oehlers, C.; Fehrmann, Rasmus; Masters, Stephen Grenville

    1996-01-01

    Deactivation of commercial and prototype sulphuric acid catalysts has been investigated in-situ by ESR spectroscopy. The influence of support pore structure,and the chemical composition of the catalyst and the gas phase was dicussed.A statistical lattice model was applied to describe the crystall......Deactivation of commercial and prototype sulphuric acid catalysts has been investigated in-situ by ESR spectroscopy. The influence of support pore structure,and the chemical composition of the catalyst and the gas phase was dicussed.A statistical lattice model was applied to describe...

  16. Oscillatory behaviour of isomers of hydroxybenzoic acid with and without catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Nath, Masood A.; Rastogi, R.P.; Peerzada, G.M. [University of Kashmir, Srinagar (India). Dept. of Chemistry]. E-mail: nath_masood@yahoo.co.in

    2009-07-01

    The present work establishes and compares the oscillatory behaviour of mono-, di- and trihydroxybenzoic acids as organic substrates in acidic bromate (1.0 mol L{sup -1} H{sub 2}SO{sub 4}) without catalyst and in the presence of Mn{sup 2+} ion as the main catalyst. The oscillations are also affected by other catalyst such as Fe{sup 2+} ion. Further, the oscillations start diminishing in mixed catalyst systems. The experimental parameters were obtained potentiometrically and the results have been interpreted on the basis of FKN mechanism. (author)

  17. Kinetics of acetic acid synthesis from ethanol over a Cu/SiO2 catalyst

    DEFF Research Database (Denmark)

    Voss, Bodil; Schjødt, Niels Christian; Grunwaldt, Jan-Dierk

    2011-01-01

    The dehydrogenation of ethanol via acetaldehyde for the synthesis of acetic acid over a Cu based catalyst in a new process is reported. Specifically, we have studied a Cu on SiO2 catalyst which has shown very high selectivity to acetic acid via acetaldehyde compared to competing condensation routes....... In light of this, an observed intrinsic activity difference between whole catalyst pellets and crushed pellets may be explained by the Cu crystal size and growth rate being functions of the catalyst particle size and time....

  18. Effect of Iminodiacetic Acid-Modified Nieuwland Catalyst on the Acetylene Dimerization Reaction

    Directory of Open Access Journals (Sweden)

    Yanhe You

    2017-12-01

    Full Text Available The iminodiacetic acid-modified Nieuwland catalyst not only improves the conversion of acetylene but also increases the selectivity of monovinylacetylene (MVA. A catalyst system containing 4.5% iminodiacetic acid exhibited excellent performance, and the yield of MVA was maintained at 32% after 24 h, producing an increase in the yield by 12% relative to the Nieuwland catalyst system. Based on a variety of characterization methods analysis of the crystal precipitated from the catalyst solution, it can be inferred that the outstanding performance and lifetime of the catalyst system was due to the presence of iminodiacetic acid, which increases the electron density of Cu+ and adjusts the acidity of the catalytic solution.

  19. Removal of free fatty acid in Palm Fatty Acid Distillate using sulfonated carbon catalyst derived from biomass wastefor biodiesel production

    Science.gov (United States)

    Hidayat, Arif; Rochmadi; Wijaya, Karna; Budiman, Arief

    2016-01-01

    In this research, the esterification of PFAD using the sulfonatedcoconut shell biochar catalyst was studied. Carbon solid catalysts were prepared by a sulfonation of carbonized coconut shells. The performances of the catalysts were evaluated in terms of the reaction temperatures, the molar ratios of methanol to PFAD, the catalyst loading and the reaction times. The reusability of the solid acid carbon catalysts was also studied in this work. The results indicated that the FFA conversion was significantly increased with increasing catalyst loading and reaction times. It can be concluded that the optimal conditions were an PFAD to methanol molar ratio of 1:12, the amount of catalyst of 10%w, and reaction temperature of 60oC.At this optimum condition, the conversion to biodieselreached 88%.

  20. Enhanced life of proton exchange membrane fuel cell catalysts using perfluorosulfonic acid stabilized carbon support

    International Nuclear Information System (INIS)

    Cheng Niancai; Mu Shichun; Chen Xiaojing; Lv Haifeng; Pan Mu; Edwards, Peter P.

    2011-01-01

    We report a new and simple solution to increase life of Pt/C catalysts using the proton-conducting polymer (perfluorosulfonic acid, PFSA) stabilized carbon support (denoted these catalysts as Pt/NFC catalysts) as compared to conventional Pt/C catalysts commonly used in PEM fuel cells. A high catalytic activity of the catalyst is observed by both CV (cyclic voltammetry) and ORR (oxygen reduction reaction) measurements. Especially, our own catalysts have a 60% better life as compared to Pt/C under electrochemically accelerated durability test conditions. The loss rate of electrochemical active area (ECA) for Pt/NFC catalysts is only 0.007 m 2 g -1 cycle -1 , compared to a value of 0.011 m 2 g -1 cycle -1 for Pt/C.

  1. Enhanced life of proton exchange membrane fuel cell catalysts using perfluorosulfonic acid stabilized carbon support

    Energy Technology Data Exchange (ETDEWEB)

    Cheng Niancai [State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, 430070 (China); Mu Shichun, E-mail: msc@whut.edu.c [State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, 430070 (China); Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, OX1 3QR (United Kingdom); Chen Xiaojing; Lv Haifeng; Pan Mu [State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, 430070 (China); Edwards, Peter P. [Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, OX1 3QR (United Kingdom)

    2011-02-01

    We report a new and simple solution to increase life of Pt/C catalysts using the proton-conducting polymer (perfluorosulfonic acid, PFSA) stabilized carbon support (denoted these catalysts as Pt/NFC catalysts) as compared to conventional Pt/C catalysts commonly used in PEM fuel cells. A high catalytic activity of the catalyst is observed by both CV (cyclic voltammetry) and ORR (oxygen reduction reaction) measurements. Especially, our own catalysts have a 60% better life as compared to Pt/C under electrochemically accelerated durability test conditions. The loss rate of electrochemical active area (ECA) for Pt/NFC catalysts is only 0.007 m{sup 2} g{sup -1} cycle{sup -1}, compared to a value of 0.011 m{sup 2} g{sup -1} cycle{sup -1} for Pt/C.

  2. Leaching behavior of lanthanum, nickel and iron from spent catalyst using inorganic acids

    Science.gov (United States)

    Astuti, W.; Prilitasari, N. M.; Iskandar, Y.; Bratakusuma, D.; Petrus, H. T. B. M.

    2018-01-01

    Highly technological applications of rare earth metals (REs) and scarcity of supply have become an incentive torecover the REs from various resources, which include high grade and low grade ores, as well as recycledwaste materials. Spent hydrocracking catalyst contain lanthanum and a variety of valuable metals such as nickel and iron. This study investigated the recovery of lanthanum, nickel and iron from spent hydrocracking catalyst by leaching using various inorganic acid (sulfuric acid, hydrochloric acid, and nitric acid). The effect of acid concentration, type of acid and leaching temperature was conducted to study the leaching behavior of each valuable metal from spent-catalyst. It has been shown that it is possible to recover more than 90% of lanthanum, however the leaching efficiency of nickel and iron in this process was very low. It can be concluded that the leaching process is selective for lanthanum recovery from hydrocracking spent-catalyst.

  3. Boehmite-An Efficient and Recyclable Acid-Base Bifunctional Catalyst for Aldol Condensation Reaction.

    Science.gov (United States)

    Reshma, P C Rajan; Vikneshvaran, Sekar; Velmathi, Sivan

    2018-06-01

    In this work boehmite was used as an acid-base bifunctional catalyst for aldol condensation reactions of aromatic aldehydes and ketones. The catalyst was prepared by simple sol-gel method using Al(NO3)3·9H2O and NH4OH as precursors. The catalyst has been characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM), UV-visible spectroscopy (DRS), BET surface area analyses. Boehmite is successfully applied as catalyst for the condensation reaction between 4-nitrobenzaldehyde and acetone as a model substrate giving α, β-unsaturated ketones without any side product. The scope of the reaction is extended for various substituted aldehydes. A probable mechanism has been suggested to explain the cooperative behavior of the acidic and basic sites. The catalyst is environmentally friendly and easily recovered from the reaction mixture. Also the catalyst is reusable up to 3 catalytic cycles.

  4. Leaching of vanadium from sulphuric acid manufacture spent catalysts

    Directory of Open Access Journals (Sweden)

    García, Diego Juan

    2001-02-01

    Full Text Available Recovery of vanadium contained in spent catalysts from the manufacture of sulphuric acid has been studied in this work, resulting in an industrial multistage process for the treatment of them avoiding direct deposition or dumping. Characterization of supplied spent catalysts samples, confirmed vanadium levels showed in the literature. The study of variables influencing leaching process: type of leaching agent, leaching agent concentration, S/L ratio, stirring speed and temperature, allows to fix the most advantageous conditions using industrial application criterion and verifying that the process is difusión controlled. The work is completed by developing an industrial leaching cycle simulation with the aim of reproducing real performance of spent catalyst, proposing operating conditions, and verifying the non-toxic character of the final residue obtained.

    En el presente trabajo se ha estudiado la recuperación del vanadio contenido en los catalizadores agotados procedentes de la fabricación del ácido sulfúrico, planteando un proceso industrial multietapa para el tratamiento de estos residuos, evitando su deposición o vertido directos. La caracterización de las muestras de catalizadores agotados disponibles confirmó los valores encontrados en la bibliografía. Se estudiaron las variables que influyen en el proceso de lixiviación (tipo de agente de lixiviación y concentración del mismo, relación S/L, velocidad de agitación y temperatura definiendo las condiciones más adecuadas desde el punto de vista industrial y verificando que el proceso está controlado por mecanismos difusionales. El trabajo se completa con la simulación de un ciclo industrial de lavado del catalizador y la verificación de la nula toxicidad de los lixiviados obtenidos por degradación del residuo final. 24 Aplicación de la resistencia de ruido al estudio de pinturas ricas en zinc Noise resistance applied to the study of zinc rich paints

  5. Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Mikolajczuk-Zychora, A., E-mail: amikolajczuk@ichf.edu.pl [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Mazurkiewicz-Pawlicka, M. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warynskiego 1, Warsaw (Poland); Stobinski, L. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warynskiego 1, Warsaw (Poland); Ciecierska, E. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Zimoch, A.; Opałło, M. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland)

    2016-12-01

    Highlights: • Palladium catalyst used on the cathode DFAFC is comparable to commercial platinum catalyst. • The treatment of carbon supports in nitric acid(V) increases the electrochemically available metal surface area and the catalytic activity in oxygen reduction reaction of catalysts. - Abstract: One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

  6. Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

    Science.gov (United States)

    Mikolajczuk-Zychora, A.; Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B.; Mazurkiewicz-Pawlicka, M.; Stobinski, L.; Ciecierska, E.; Zimoch, A.; Opałło, M.

    2016-12-01

    One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

  7. Steam Reforming of Acetic Acid over Co-Supported Catalysts: Coupling Ketonization for Greater Stability

    Energy Technology Data Exchange (ETDEWEB)

    Davidson, Stephen D. [Energy and Environmental; Spies, Kurt A. [Energy and Environmental; Mei, Donghai [Energy and Environmental; Kovarik, Libor [Energy and Environmental; Kutnyakov, Igor [Energy and Environmental; Li, Xiaohong S. [Energy and Environmental; Lebarbier Dagle, Vanessa [Energy and Environmental; Albrecht, Karl O. [Energy and Environmental; Dagle, Robert A. [Energy and Environmental

    2017-09-11

    We report on the markedly improved stability of a novel 2-bed catalytic system, as compared to a conventional 1-bed steam reforming catalyst, for the production of H2 from acetic acid. The 2-bed catalytic system comprises of i) a basic oxide ketonization catalyst for the conversion of acetic acid to acetone, and a ii) Co-based steam reforming catalyst, both catalytic beds placed in sequence within the same unit operation. Steam reforming catalysts are particularly prone to catalytic deactivation when steam reforming acetic acid, used here as a model compound for the aqueous fraction of bio-oil. Catalysts comprising MgAl2O4, ZnO, CeO2, and activated carbon (AC) both with and without Co-addition were evaluated for conversion of acetic acid and acetone, its ketonization product, in the presence of steam. It was found that over the bare oxide support only ketonization activity was observed and coke deposition was minimal. With addition of Co to the oxide support steam reforming activity was facilitated and coke deposition was significantly increased. Acetone steam reforming over the same Co-supported catalysts demonstrated more stable performance and with less coke deposition than with acetic acid feedstock. DFT analysis suggests that over Co surface CHxCOO species are more favorably formed from acetic acid versus acetone. These CHxCOO species are strongly bound to the Co catalyst surface and could explain the higher propensity for coke formation from acetic acid. Based on these findings, in order to enhance stability of the steam reforming catalyst a dual-bed (2-bed) catalyst system was implemented. Comparing the 2-bed and 1-bed (Co-supported catalyst only) systems under otherwise identical reaction conditions the 2-bed demonstrated significantly improved stability and coke deposition was decreased by a factor of 4.

  8. Impact of anode catalyst layer porosity on the performance of a direct formic acid fuel cell

    International Nuclear Information System (INIS)

    Bauskar, Akshay S.; Rice, Cynthia A.

    2012-01-01

    Highlights: ► Lithium carbonate is used as a pore-former to increase porosity of anode catalyst layer. ► Maximum power density increased by 25%. ► Onset potential for formic acid electro-oxidation reduced by 30 mV for anode catalyst layer with 17.5 wt% pore-former. ► Electrochemical impedance spectra confirm increased formic acid concentration inside the anode catalyst layer pores. - Abstract: Direct formic acid fuel cells (DFAFCs) have attracted much attention in the last few years for portable electronic devices, due to their potential of being high efficiency power sources. They have the potential to replace the state-of-the-art batteries in cell phones, PDAs, and laptop computers if their power density and durability can be improved. In the present investigation, the influence of increased anode catalyst layer porosity on DFAFC power density performance is studied. Lithium carbonate (Li 2 CO 3 ) was used as a pore-former in this study because of its facile and complete removal after catalyst layer fabrication. The anode catalyst layers presented herein contained unsupported Pt/Ru catalyst and Li 2 CO 3 (in the range of 0–50 wt%) bound with proton conducting ionomer. Higher DFAFC performance is obtained because of the increased porosity within the anode catalyst layer through enhanced reactant and product mass transport. The maximum power density of DFAFC increased by 25% when pore-former was added to the anode catalyst ink. The formic acid onset potential for the anode catalyst layer with 17.5 wt% pore-former was reduced by 30 mV. A constant phase element based equivalent-circuit model was used to investigate anode impedance spectra. Fitted values for the anode impedance spectra confirm the improvement in performance due to an increase in formic acid concentration inside the anode catalyst layer pores along with efficient transport of reactants and products.

  9. Esterification of free fatty acids in biodiesel production with sulphonated pyrolysed carbohydrate catalysts

    DEFF Research Database (Denmark)

    Madsen, Anders Theilgaard; Riisager, Anders; Fehrmann, Rasmus

    The pre-treatment of free fatty acids in oils and fats in biodiesel production is of pivotal importance, and esterification in acidic medium must be done prior to basic transesterification of glycerides. The free fatty acids may be converted over an acidic catalyst of sulphonated pyrolysed...

  10. Surface treated carbon catalysts produced from waste tires for fatty acids to biofuel conversion

    Science.gov (United States)

    Hood, Zachary D.; Adhikari, Shiba P.; Wright, Marcus W.; Lachgar, Abdessadek; Li, Yunchao; Naskar, Amit K.; Paranthaman, Mariappan Parans

    2018-02-06

    A method of making solid acid catalysts includes the step of sulfonating waste tire pieces in a first sulfonation step. The sulfonated waste tire pieces are pyrolyzed to produce carbon composite pieces having a pore size less than 10 nm. The carbon composite pieces are then ground to produce carbon composite powders having a size less than 50 .mu.m. The carbon composite particles are sulfonated in a second sulfonation step to produce sulfonated solid acid catalysts. A method of making biofuels and solid acid catalysts are also disclosed.

  11. 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...

  12. Hydrogenation of Lactic Acid to 1,2-propanediol over Ru-based catalysts

    NARCIS (Netherlands)

    Liu, K.; Huang, X.; Pidko, E.A.; Hensen, E.J.M.

    2018-01-01

    The catalytic hydrogenation of lactic acid to 1,2-propanediol with supported Ru catalysts in water was investigated. The influence of catalyst support (activated carbon, γ-Al2O3, SiO2, TiO2, and CeO2) and promoters (Pd, Au, Mo, Re, Sn) on the catalytic performance was evaluated. Catalytic tests

  13. Direct hydrothermal liquefaction of undried macroalgae Enteromorpha prolifera using acid catalysts

    International Nuclear Information System (INIS)

    Yang, Wenchao; Li, Xianguo; Liu, Shishi; Feng, Lijuan

    2014-01-01

    Highlights: • Bio-oil from liquefaction of wet E. prolifera was as feasible as dry powder. • Adding acid catalysts could improve the flow property of bio-oil. • Alkenes in the bio-oil converted to ketones in the presence of acid catalysts. • Content of 5-methyl furfural increased in the bio-oil obtained with acid catalysts. • Esters were formed in the bio-oil when adding sulfuric acid as a catalyst. - Abstract: Direct liquefaction of macroalgae Enteromorpha prolifera without predrying treatment was performed in a batch reactor. Effects of temperature, reaction time, biomass-to-water ratio and acid catalysts (sulfuric acid and acetic acid) on liquefaction products were investigated. Raw material and liquefaction products were analyzed by elemental analysis, Fourier transform infrared (FT-IR) and gas chromatography–mass spectrometry (GC–MS). Results showed that liquefaction at 290 °C for 20 min with 1:3 biomass-to-water ratio produced the highest bio-oil yield of 28.4 wt%, and high heating value (HHV) was 29.5 MJ/kg. Main components of bio-oil were fatty acids, ketones, alkenes and 5-methyl furfural, and main components of water soluble organics (WSOs) were pyridines, carboxylic acids and glycerol. In the bio-oil obtained with acid catalysts, content of ketones significantly increased while alkenes disappeared. Content of 5-methyl furfural also increased. Flow property of bio-oils was improved in the presence of acid catalysts. Moreover, esters were formed when adding sulfuric acid

  14. Silica-supported sulfonic acids as recyclable catalyst for esterification of levulinic acid with stoichiometric amounts of alcohols

    Directory of Open Access Journals (Sweden)

    Raimondo Maggi

    2016-10-01

    Full Text Available Converting biomass into value-added chemicals holds the key to sustainable long-term carbon resource management. In this context, levulinic acid, which is easily obtained from cellulose, is valuable since it can be transformed into a variety of industrially relevant fine chemicals. Here we present a simple protocol for the selective esterification of levulinic acid using solid acid catalysts. Silica supported sulfonic acid catalysts operate under mild conditions and give good conversion and selectivity with stoichiometric amounts of alcohols. The sulfonic acid groups are tethered to the support using organic tethers. These tethers may help in preventing the deactivation of the active sites in the presence of water.

  15. Palm Frond and Spikelet as Environmentally Benign Alternative Solid Acid Catalysts for Biodiesel Production

    Directory of Open Access Journals (Sweden)

    Yahaya Muhammad Sani

    2015-04-01

    Full Text Available A carbonization-sulfonation method was utilized in synthesizing sulfonated mesoporous catalysts from palm tree biomass. Brunauer-Emmet-Teller (BET, powder X-ray diffraction (XRD, energy dispersive X-ray (EDX, and field emission scanning emission microscopy (FE-SEM analyses were used to evaluate the structural and textural properties of the catalysts. Further, Fourier transform infrared (FT-IR spectroscopy and titrimetric analyses measured the strong acid value and acidity distribution of the materials. These analyses indicated that the catalysts had large mesopore volume, large surface area, uniform pore size, and high acid density. The catalytic activity exhibited by esterifying used frying oil (UFO containing high (48% free fatty acid (FFA content further indicated these properties. All catalysts exhibited high activity, with sPTS/400 converting more than 98% FFA into fatty acid methyl esters (FAMEs. The catalyst exhibited the highest acid density, 1.2974 mmol/g, determined by NaOH titration. This is outstanding considering the lower reaction parameters of 5 h, 5:1 methanol-to-oil ratio, and a moderate temperature range between 100 and 200 °C. The study further illustrates the prospect of converting wastes into highly efficient, benign, and recyclable solid acid catalysts.

  16. Synthesis and characterization of new chiral ketopinic acid-derived catalysts immobilized on polystyrene-bound imidazole

    Directory of Open Access Journals (Sweden)

    Hassan Yusuf

    2017-02-01

    Full Text Available Four new chiral ketopinic acid-derived catalysts were anchored on a polystyrene-bound imidazole via non-covalent bond. The resulting heterogeneous catalysts were successfully characterized using IR, SEM, and TGA analyses.

  17. 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.

  18. Liquid-Phase Catalytic Transfer Hydrogenation of Furfural over Homogeneous Lewis Acid-Ru/C Catalysts.

    Science.gov (United States)

    Panagiotopoulou, Paraskevi; Martin, Nickolas; Vlachos, Dionisios G

    2015-06-22

    The catalytic performance of homogeneous Lewis acid catalysts and their interaction with Ru/C catalyst are studied in the catalytic transfer hydrogenation of furfural by using 2-propanol as a solvent and hydrogen donor. We find that Lewis acid catalysts hydrogenate the furfural to furfuryl alcohol, which is then etherified with 2-propanol. The catalytic activity is correlated with an empirical scale of Lewis acid strength and exhibits a volcano behavior. Lanthanides are the most active, with DyCl3 giving complete furfural conversion and a 97 % yield of furfuryl alcohol at 180 °C after 3 h. The combination of Lewis acid and Ru/C catalysts results in synergy for the stronger Lewis acid catalysts, with a significant increase in the furfural conversion and methyl furan yield. Optimum results are obtained by using Ru/C combined with VCl3 , AlCl3 , SnCl4 , YbCl3 , and RuCl3 . Our results indicate that the combination of Lewis acid/metal catalysts is a general strategy for performing tandem reactions in the upgrade of furans. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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...

  20. Efficacy of Catalysts in the Batch Esterification of the Fatty Acids of ...

    African Journals Online (AJOL)

    The methyl, ethyl, propyl and butyl esters of the fatty acids of Thevetia peruviana seed oil were successfully prepared by the batch-esterification procedures. Various acid catalyst and various molar ratios of fatty acid to alcohol were investigated. H3PO4 was found to be ineffective to catalyze the esterification of the free fatty ...

  1. Kinetic study on the photocatalytic degradation of salicylic acid using ZnO catalyst

    International Nuclear Information System (INIS)

    Nageswara Rao, A.; Sivasankar, B.; Sadasivam, V.

    2009-01-01

    The photocatalytic degradation of salicylic acid was studied by a batch process using ZnO as the catalyst on irradiation with UV light. The effect of process parameters such as pH, catalyst loading and initial concentration of salicylic acid on the extent of degradation was investigated. The degradation of salicylic acid was found to be effective in the neutral pH range. The optimum catalyst loading was observed at 2.0 g/L. The process followed first order kinetics and the apparent rate constant decreased with increase in the initial concentration of salicylic acid. The mechanism for the degradation of salicylic acid could be explained on the basis of Langmuir-Hinshelwood mechanism. The complete mineralization of salicylic acid was observed in the presence of ZnO photocatalyst. The ZnO was found to be quite stable and undergoes photocorrosion only to a negligible extent.

  2. Production of Biodiesel by Esterification of Free Fatty Acid over Solid Catalyst from Biomass Waste

    Science.gov (United States)

    Mukti, N. I. F.; Sutrisno, B.; Hidayat, A.

    2018-05-01

    Recently, low cost feedstocks have been utilized to replace vegetable oils in order to improve the economic feasibility of biodiesel. The esterification of free fatty acid (FFA) on Palm Fatty Acid Distillate (PFAD) with methanol using solid catalyst generated from bagasse fly ash is a promising method to convert FFA into biodiesel. In this research, the esterification of FFA on PFAD using the sulfonated bagasse fly ash catalyst was studied. The performances of the catalysts were evaluated in terms of the reaction temperatures, the molar ratios of methanol to PFAD, and the catalyst loading. The effects of the mass ratio of catalyst to oil (1-10%), the molar ratio of methanol to oil (6:1-12:1), and the reaction temperature (40-60°C) were studied for the conversion of PFAD to optimize the reaction conditions. The results showed that the optimum conditions were methanol to PFAD molar ratio of 12:1, the amount of catalyst of 10%wt. of PFAD, and reaction temperature of 6°C. The reusability of the solid acid carbon catalysts was also studied in this work. The catalytic activity decreased up to 38% after third cycle. The significant decline in catalyst esterification activity was due to acid site leaching. The physico-characteristics and acid site densities were analyzed by Nitrogen gas adsorption, surface functional groups by Fourier transform infrared spectroscopy (FT-IR), elemental analysis using X-ray fluorescent (XRF), and acid-base back titration methods for determination of acid density.

  3. Promoted V2O5/TiO2 catalysts for selective catalytic reduction of NO with NH3 at low temperatures

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Schill, Leonhard; Godiksen, Anita

    2016-01-01

    characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR, Raman, FTIR and EPR spectroscopy to investigate the properties of the catalysts. XRPD, Raman and FTIR showed that promotion with 15 wt.% HPA does not cause V2O5 to be present in crystalline form, also at a loading of 5 wt.% V2O5. Hence, use of HPAs does......The influence of varying the V2O5 content (3–6 wt.%) was studied for the selective catalytic reduction (SCR) of nitrogen oxides by ammonia on heteropoly acid (HPA)- and tungsten oxide (WO3)-promoted V2O5/TiO2 catalysts. The SCR activity and alkali deactivation resistance of HPA-promoted V2O5/TiO2...... catalysts was found to be much higher than for WO3-promoted catalysts. By increasing the vanadium content from 3 to 5 wt.% the catalysts displayed a two fold increase in activity at 225 °C and retained their initial activity after alkali doping at a molar K/V ratio of 0.181. Furthermore, the catalysts were...

  4. Chance and necessity in the selection of nucleic acid catalysts

    Science.gov (United States)

    Lorsch, J. R.; Szostak, J. W.

    1996-01-01

    In Tom Stoppard's famous play [Rosencrantz and Guildenstern are Dead], the ill-fated heroes toss a coin 101 times. The first 100 times they do so the coin lands heads up. The chance of this happening is approximately 1 in 10(30), a sequence of events so rare that one might argue that it could only happen in such a delightful fiction. Similarly rare events, however, may underlie the origins of biological catalysis. What is the probability that an RNA, DNA, or protein molecule of a given random sequence will display a particular catalytic activity? The answer to this question determines whether a collection of such sequences, such as might result from prebiotic chemistry on the early earth, is extremely likely or unlikely to contain catalytically active molecules, and hence whether the origin of life itself is a virtually inevitable consequence of chemical laws or merely a bizarre fluke. The fact that a priori estimates of this probability, given by otherwise informed chemists and biologists, ranged from 10(-5) to 10(-50), inspired us to begin to address the question experimentally. As it turns out, the chance that a given random sequence RNA molecule will be able to catalyze an RNA polymerase-like phosphoryl transfer reaction is close to 1 in 10(13), rare enough, to be sure, but nevertheless in a range that is comfortably accessible by experiment. It is the purpose of this Account to describe the recent advances in combinatorial biochemistry that have made it possible for us to explore the abundance and diversity of catalysts existing in nucleic acid sequence space.

  5. Silica sulfuric acid: a versatile and reusable heterogeneous catalyst ...

    African Journals Online (AJOL)

    ... and reusable heterogeneous catalyst for the synthesis of N-acyl carbamates and ... All the reactions were done at room temperature and the N-acyl carbamates ... This method is attractive and is in a close agreement with green chemistry.

  6. Solid acid zeolite catalysts for benzene/ ethylene alkylation reactions

    OpenAIRE

    2011-01-01

    Alkylation of benzene with ethylene to ethylbenzene is widely used in the petrochemical industry. Ethylbenzene is an important raw material in the petrochemical industry. It is used as feedstock for the production of styrene, an important material for plastic and rubber production.The conventional catalyst for this alkylation process is AlCl₃, which accounted for 24% of the worldwide ethylbenzene production in 2009.As utilization of this catalyst involves problems with separation, handling, s...

  7. Synthesis of Ricinoleic Acid Estolides by the Esterification of Ricinoleic Acids Using Functional Acid Ionic Liquids as Catalysts.

    Science.gov (United States)

    Wang, Gaoshang; Sun, Shangde

    2017-07-01

    Estolides of ricinoleic acid (RA) have been used as lubricants and pigment dispersant in many industries. In this paper, functional acid ionic liquids (ILs) were firstly used as catalysts to prepare RA estolides by the esterification of RAs in solvent-free system. Different ILs were used as catalysts for the esterification. Effect of reaction variables (IL amount, reaction temperature and reaction time) on the esterification were also investigated and optimized using response surface methodology (RSM). Among all tested ILs, [BSO 3 HMIM]TS showed the best performance for the esterification. Arrhenius equation for the esterification was lnV 0 =14.897-7558.7/T, and the activation energy (Ea) was 62.84 kJ/mol. A high degree of polymerization with an acid value of 48.0±2.5 mg KOH/g was achieved at the optimized conditions (IL load 12%, reaction temperature 140°C, and reaction time 12 h). The effect of reaction variables on the esterification decreased in the order of catalyst loading of IL > reaction temperature > reaction time.

  8. Cu2+ Montmorillonite K10 Clay Catalyst as a Green Catalyst for Production of Stearic Acid Methyl Ester: Optimization Using Response Surface Methodology (RSM)

    OpenAIRE

    Enas A. Almadani; Farah W. Harun; Salina M. Radzi; Syamsul K. Muhamad

    2018-01-01

    Clay catalyst has received much attention to replace the homogeneous catalysts in the esterification reaction to produce fatty acid methyl ester as the source of biodiesel as it is low cost, easily available, as well as environmental friendly. However, the use of unmodified clay, in particular montmorillonite K10 (MMT K10), for the esterification of fatty acids showed that the acid conversion was less than 60% and this is not preferable to the production of biodiesel. In this study, synthesis...

  9. Hydrogenation of Levulinic Acid over Nickel Catalysts Supported on Aluminum Oxide to Prepare γ-Valerolactone

    Directory of Open Access Journals (Sweden)

    Jie Fu

    2015-12-01

    Full Text Available Four types of nickel catalysts supported on aluminum oxide (Ni/Al2O3 with different nickel loadings were synthesized using the co-precipitation method and were used for the hydrogenation of levulinic acid (LA to prepare γ-valerolactone (GVL. The synthesized Ni/Al2O3 catalysts exhibited excellent catalytic activity in dioxane, and the activity of the catalysts was excellent even after being used four times in dioxane. The catalytic activity in dioxane as a solvent was found to be superior to the activity in water. Nitrogen physisorption, X-ray diffraction, and transmission electron microscopy were employed to characterize the fresh and used catalysts. The effects of the nickel loading, temperature, hydrogen pressure, and substrate/catalyst ratio on the catalytic activity were investigated.

  10. Synthesis of a nano-crystalline solid acid catalyst from fly ash and its catalytic performance

    Energy Technology Data Exchange (ETDEWEB)

    Chitralekha Khatri; Ashu Rani [Government P.G. College, Kota (India). Environmental Chemistry Laboratory

    2008-10-15

    The synthesis of nano-crystalline activated fly ash catalyst (AFAC) with crystallite size of 12 nm was carried out by chemical and thermal treatment of fly ash, a waste material generated from coal-burning power plants. Fly ash was chemically activated using sulfuric acid followed by thermal activation at 600{sup o}C. The variation of surface and physico-chemical properties of the fly ash by activation methods resulted in improved acidity and therefore, catalytic activity for acid catalyzed reactions. The AFAC was characterized by X-ray diffraction, FT-IR spectroscopy, N{sub 2}-adsorption-desorption isotherm, scanning electron microscopy, flame atomic absorption spectrophotometry and sulfur content by CHNS/O elemental analysis. It showed amorphous nature due to high silica content (81%) and possessed high BET surface area (120 m{sup 2}/g). The catalyst was found to be highly active solid acid catalyst for liquid phase esterification of salicylic acid with acetic anhydride and methanol giving acetylsalicylic acid and methyl salicylate respectively. A maximum yield of 97% with high purity of acetylsalicylic acid (aspirin) and a very high conversion 87% of salicylic acid to methyl salicylate (oil of wintergreen) was obtained with AFAC. The surface acidity and therefore, catalytic activity in AFAC was originated by increased silica content, hydroxyl content and higher surface area as compared to fly ash. The study shows that coal generated fly ash can be converted into potential solid acid catalyst for acid catalyzed reactions. Furthermore, this catalyst may replace conventional environmentally hazardous homogeneous liquid acids making an ecofriendly; solvent free, atom efficient, solid acid based catalytic process. 27 refs., 5 figs., 2 tabs.

  11. Acidity, oxophilicity and hydrogen sticking probability of supported metal catalysts for hydrodeoxygenation process

    Science.gov (United States)

    Lup, A. Ng K.; Abnisa, F.; Daud, W. M. A. W.; Aroua, M. K.

    2018-03-01

    Hydrodeoxygenation is an oxygen removal process that occurs in the presence of hydrogen and catalysts. This study has shown the importance of acidity, oxophilicity and hydrogen sticking probability of supported metal catalysts in having high hydrodeoxygenation activity and selectivity. These properties are required to ensure the catalyst has high affinity for C-O or C=O bonds and the capability for the adsorption and activation of H2 and O-containing compounds. A theoretical framework of temperature programmed desorption technique was also discussed for the quantitative understanding of these properties. By using NH3-TPD, the nature and abundance of acid sites of catalyst can be determined. By using H2-TPD, the nature and abundance of metallic sites can also be determined. The desorption activation energy could also be determined based on the Redhead analysis of TPD spectra with different heating rates.

  12. Nanocomposite catalyst with palladium nanoparticles encapsulated in a polymeric acid: A model for tandem environmental catalysis

    KAUST Repository

    Isimjan, Tayirjan T.

    2013-04-01

    The synthesis and characterization of a novel hybrid nanocomposite catalyst comprised of palladium nanoparticles embedded in polystyrene sulfonic acid (PSSH) and supported on metal oxides is reported. The catalysts are intended for application in green catalysis, and they are shown to be effective in the hydrolysisreduction sequence of tandem catalytic reactions required for conversion of 2-phenyl-1,3-dioxolane to toluene or of phenol to cyclohexane. The two distinct components in the catalyst, Pd nanoparticles and acidic PSSH, are capable of catalyzing sequential reactions in one pot under mild conditions. This work has demonstrated a powerful approach toward designing highperformance, multifunctional, scalable, and environmentally friendly nanostructured tandem catalysts. © 2013 American Chemical Society.

  13. Hydrogenation of levulinic acid to γ-valerolactone over anatase-supported Ru catalysts : Effect of catalyst synthesis protocols on activity

    NARCIS (Netherlands)

    Piskun, A.s.; Ftouni, J.; Tang, Z.; Weckhuysen, B.m.; Bruijnincx, P.c.a.; Heeres, Hero J.

    2018-01-01

    γ-Valerolactone (GVL) is a value-added renewable chemical with great potential and can be obtained from biomass by the hydrogenation of levulinic acid (LA) using metal-based catalysts, such as Ru/TiO2. We here report an in depth study of the effect of catalyst synthesis parameters on the performance

  14. Formic Acid Modified Co3O4-CeO2 Catalysts for CO Oxidation

    Directory of Open Access Journals (Sweden)

    Ruishu Shang

    2016-03-01

    Full Text Available A formic acid modified catalyst, Co3O4-CeO2, was prepared via facile urea-hydrothermal method and applied in CO oxidation. The Co3O4-CeO2-0.5 catalyst, treated by formic acid at 0.5 mol/L, performed better in CO oxidation with T50 obtained at 69.5 °C and T100 obtained at 150 °C, respectively. The characterization results indicate that after treating with formic acid, there is a more porous structure within the Co3O4-CeO2 catalyst; meanwhile, despite of the slightly decreased content of Co, there are more adsorption sites exposed by acid treatment, as suggested by CO-TPD and H2-TPD, which explains the improvement of catalytic performance.

  15. Highly Selective Hydrogenation of Levulinic Acid to γ-Valerolactone Over Ru/ZrO2 Catalysts

    NARCIS (Netherlands)

    Filiz, B.C.; Gnanakumar, E.S.; Martinez-Arias, A.; Gengler, R.; Rudolf, P.; Rothenberg, G.; Shiju, N.R.

    We studied the catalytic hydrogenation of levulinic acid over zirconia supported ruthenium catalysts. Four different Ru/ZrO2 catalysts were prepared by different pre-treatments and using different zirconium supports (ZrOx(OH)4−2x and ZrO2). Although the final compositions of the catalysts are the

  16. Highly Selective Hydrogenation of Levulinic Acid to gamma-Valerolactone Over Ru/ZrO2 Catalysts

    NARCIS (Netherlands)

    Filiz, Bilge Coskuner; Gnanakumar, Edwin S.; Martinez-Arias, Arturo; Gengler, Regis; Rudolf, Petra; Rothenberg, Gadi; Shiju, N. Raveendran

    We studied the catalytic hydrogenation of levulinic acid over zirconia supported ruthenium catalysts. Four different Ru/ZrO2 catalysts were prepared by different pre-treatments and using different zirconium supports (ZrOx(OH)(4-2x) and ZrO2). Although the final compositions of the catalysts are the

  17. Electrolytes for methanol-air fuel cells. I. The performance of methanol electro-oxidation catalysts in sulphuric acid and phosphoric acid electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Andrew, M.R.; McNicol, B.D.; Short, R.T.; Drury, J.S.

    1977-03-01

    Phosphoric acid and sulphuric acid have been compared as potential electrolytes for methanol-air fuel cells. The performances of typical electro-oxidation catalysts were measured in both electrolytes over a range of concentrations. With all catalysts the activity falls with increasing acid concentration. While this is to some extent due to the decrease in water activity at higher concentrations it seems that with both acids there is significant poisoning of the catalyst. The results can be explained for both electrolytes by assuming that adsorption of undissociated acid poisons the catalyst surfaces and that the reaction rate on the poisoned surfaces is proportional to the water activity.

  18. Reaction kinetics of free fatty acids esterification in palm fatty acid distillate using coconut shell biochar sulfonated catalyst

    Science.gov (United States)

    Hidayat, Arif; Rochmadi, Wijaya, Karna; Budiman, Arief

    2015-12-01

    Recently, a new strategy of preparing novel carbon-based solid acids has been developed. In this research, the esterification reactions of Palm Fatty Acid Distillate (PFAD) with methanol, using coconut shell biochar sulfonated catalyst from biomass wastes as catalyst, were studied. In this study, the coconut shell biochar sulfonated catalysts were synthesized by sulfonating the coconut shell biochar using concentrated H2SO4. The kinetics of free fatty acid (FFA) esterification in PFAD using a coconut shell biochar sulfonated catalyst was also studied. The effects of the mass ratio of catalyst to oil (1-10%), the molar ratio of methanol to oil (6:1-12:1), and the reaction temperature (40-60°C) were studied for the conversion of PFAD to optimize the reaction conditions. The results showed that the optimal conditions were an methanol to PFAD molar ratio of 12:1, the amount of catalyst of 10%w, and reaction temperature of 60°C. The proposed kinetic model shows a reversible second order reaction and represents all the experimental data satisfactorily, providing deeper insight into the kinetics of the reaction.

  19. The utilization of leftover as acid catalyst to catalyse the transesterification and esterification reactions

    Science.gov (United States)

    Leung, K. K.; Yau, Y. H.

    2017-08-01

    Biodiesel (Fatty Acid Methyl Ester, FAME) is a green and renewable energy. It is carbon neutral and produces less air pollutants in combustion. In my project, the selected feedstock of biodiesel production is grease trap oil (GTO). It is extracted from restaurants, and needs pre-treatment. The triglycerides and free fatty acid (FFA) are the main components of GTO. Both triglycerides and free fatty acid can be converted to biodiesel (Fatty Acid Methyl Ester) by transesterification and esterification, through reaction with alcohol (methanol) and catalyst. In the processes, acidic catalyst is chosen to speed up the reactions. The catalyst used In the study, a heterogeneous solid acid is applied. It is waste cooked rice (WCR) collected from leftover. The WCR powder is pyrolysed in 400°C furnace 15 hours and blown with nitrogen gas (incomplete carbonization). The WCR black powder is then mixed with concentrated sulphuric acid and heat in 160°C furnace 15 hours and continuous blown with nitrogen gas (sulphonation). This heterogeneous solid acid is used in the both transesterification and esterification to produce FAME. Moreover, in the optimal reaction conditions, this catalyst offers a stable catalytic effect. After 20 times usage in optimal reaction condition, the catalytic activity remains unchanged.

  20. Efficacy of pretreating oil palm fronds with an acid-base mixture catalyst.

    Science.gov (United States)

    Jung, Young Hoon; Park, Hyun Min; Park, Yong-Cheol; Park, Kyungmoon; Kim, Kyoung Heon

    2017-07-01

    Oil palm fronds are abundant but recalcitrant to chemical pretreatment. Herein, an acid-base mixture was applied as a catalyst to efficiently pretreat oil palm fronds. Optimized conditions for the pretreatment were a 0.1M acidic acid-base mixture and 3min ramping to 190°C and 12min holding. The oil palm fronds pretreated and washed with the acid-base mixture exhibited an enzymatic digestibility of 85% by 15 FPU Accellerase 1000/g glucan after 72h hydrolysis, which was significantly higher than the enzymatic digestibilities obtained by acid or alkali pretreatment alone. This could be attributed to the synergistic actions of the acid and base, producing an 87% glucose recovery with 100% and 40.3% removal of xylan and lignin, respectively, from the solids. Therefore, an acid-base mixture can be a feasible catalyst to deconstruct oil palm fronds for sugar production. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Polystyrene-supported pyridinium chloroaluminate ionic liquid as a new heterogeneous Lewis acid catalyst for selective synthesis of benzimidazoles

    Directory of Open Access Journals (Sweden)

    Parvanak Boroujeni Kaveh

    2013-01-01

    Full Text Available Polystyrene-supported pyridinium chloroaluminate ionic liquid was prepared from the reaction of Merrifield resin with pyridine followed by reaction with aluminium chloride. This catalyst was used as a new chemoselective Lewis acid catalyst for the exclusive synthesis of 2-substituted benzimidazoles from the reaction of aldehydes with o-phenylenediamines. The catalyst is stable (as a bench top catalyst and can be easily recovered and reused without appreciable change in its efficiency.

  2. Sustainable production of acetaldehyde from lactic acid over the carbon catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Congming; Peng, Jiansheng; Li, Xinli; Zhai, Zhanjie; Gao, Hejun; Liao, Yunwen [China West Normal University, Nanchong (China); Bai, Wei; Jiang, Ning [Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu (China)

    2016-01-15

    The synthesis of acetaldehyde from lactic acid over the carbon material catalysts was investigated. The carbon materials were characterized by scanning electron microscopy for morphologic features, by X-ray diffraction for crystal phases, by Fourier transform infrared spectroscopy for functional group structures, by N2 sorption for specific surface area and by ammonia temperature-programed desorption for acidity, respectively. Among the tested carbon catalysts, mesoporous carbon displayed the most excellent catalytic performance. By acidity analysis, the medium acidity is a crucial factor for catalytic performance: more medium acidity favored the formation of acetaldehyde from lactic acid. To verify, we compared the catalytic performance of fresh activated carbon with that of the activated carbon treated by nitric acid. Similarly, the modified activated carbon also displayed better activity due to a drastic increase of medium acidity amount. However, in contrast to fresh carbon nanotube, the treated sample displayed worse activity due to decrease of medium acidity amount. The effect of reaction temperature and time on stream on the catalytic performance was also investigated. Under the optimal reaction conditions, 100% lactic acid conversion and 91.6% acetaldehyde selectivity were achieved over the mesoporous carbon catalyst.

  3. Conversion of bio-feedstocks through acid and basic zeolites and catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Buzzoni, R.; Bosetti, A.; Delledonne, D.; Perego, C. [eni S.p.A. Research Centre for Non-Conventional Energy, Novara (Italy). Ist. eni Donegani

    2012-07-01

    Not far in the future, a significant part of fuels and chemicals will be originated by renewable biomass resources. In this respect, zeolite catalysts may help to develop a new generation of bio-fuel and chemical processes. In the new bio-paradigm not only acid but also basic materials will have an important and dominant role. Just to give some examples, basic zeolites based catalysts have been proposed for transesterification of triglyceride esters of fatty acids to biodiesel, for disrupting the lignin polymer by base catalyzed depolymerisation and for one pot lignin liquefaction by hydrogenation. (orig.)

  4. Magnetic nanoparticle supported phosphotungstic acid: An efficient catalyst for the synthesis of xanthene derivatives

    Science.gov (United States)

    Patel, Nipun; Katheriya, Deepak; Dadhania, Harsh; Dadhania, Abhishek

    2018-05-01

    Magnetic nanoparticle supported phosphotungstic acid (Fe3O4@SiO2-HPW) was applied as a highly efficient catalyst for the synthesis of 14H-dibenzoxanthene derivatives via condensation reaction of 2-naphthol and aryl aldehydes. The catalyst was found highly efficient for the synthesis of xanthene derivatives under solvent free condition. The catalyst showed high activity and stability during the reaction and provided excellent yield of the corresponding products in short reaction time. All the synthesized compounds were characterized through FT-IR, 1H-NMR and 13C-NMR spectroscopic techniques. Furthermore, the catalyst is magnetically recoverable and can be reused several times without significant loss of its catalytic activity.

  5. Methanol oxidation at platinum electrodes in acid solution: comparison between model and real catalysts

    Directory of Open Access Journals (Sweden)

    A. V. TRIPKOVIC

    2006-12-01

    Full Text Available Methanol oxidation in acid solution was studied at platinum single crystals, Pt(hkl, as the model catalyst, and at nanostructural platinum supported on high surface area carbon, Pt/C, as the real catalyst. The linear extrapolation method was used to determine the beginning of hydroxyl anion adsorption. Structural sensitivity of the adsorption was proved and a correlation with the onset of the methanol oxidation current was established at all catalysts. Bisulfate and chloride anions were found to decrease the methanol oxidation rate, but probably did not influence the reaction parth. The specific activity for the reaction increased in the sequence Pt(110 < Pt/C < Pt(111, suggesting that the activity of the supported Pt catalyst can be correlated with the activities of the dominating crystal planes on its surface.

  6. Boric acid as cost-effective and recyclable catalyst for trimethylsilyl protection and deprotection of alcohols and phenols

    Energy Technology Data Exchange (ETDEWEB)

    Rostami, Amin; Akradi, Jamal; Ahmad-Jangi, Firoz, E-mail: a_rostami372@yahoo.co [University of Kurdistan, Sanandaj (Iran, Islamic Republic of). Faculty of Science. Dept. of Chemistry

    2010-07-01

    Boric acid has been used as a green, selective and recyclable catalyst for trimethysilylation of alcohols and phenols using hexamethyldisilazane in acetonitrile. Deprotection of trimethylsilyl ethers to their parent alcohols and phenols was also achieved using this catalyst in water at room temperature. The salient features of this methodology are cheap processing, mild acidity conditions, excellent yields of products and easy availability of the catalyst. (author)

  7. Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

    Science.gov (United States)

    Shan, Junjun; Li, Mengwei; Allard, Lawrence F.; Lee, Sungsik; Flytzani-Stephanopoulos, Maria

    2017-11-01

    An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. We find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolite-supported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. We anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful

  8. Biodiesel production from acid oils and ethanol using a solid basic resin as catalyst

    International Nuclear Information System (INIS)

    Marchetti, J.M.; Errazu, A.F.

    2010-01-01

    In the search of an alternative fuel to substitute diesel fuel, biodiesel appears as one of the most promising sources of energy for diesel engines because of its environmental advantages and also due to the evolution of the petroleum market. Refined oil is the conventional raw material for the production of this biofuel; however, its major disadvantage is the high cost of its production. Therefore, frying oils, waste oils, crude oils and/or acid oils are being tested as alternative raw materials; nevertheless, there will be some problems if a homogeneous basic catalyst (NaOH) is employed due to the high amount of free fatty acid present in the raw oil. In this work, the transesterification reaction of acid oil using solid resin, Dowex monosphere 550 A, was studied as an alternative process. Ethanol was employed to have a natural and sustainable final product. The reaction temperature's effects, the initial amount of free fatty acid, the molar ratio of alcohol/oil and the type of catalyst (homogeneous or heterogeneous) over the main reaction are analyzed and their effects compared. The results obtained show that the solid resin is an alternative catalyst to be used to produce fatty acid ethyl esters (FAEEs) by a transesterification reaction with a final conversion over 90%. On the other hand, the time required to achieve this conversion is bigger than the one required using conventional technology which employs a homogeneous basic catalyst. This reaction time needs to be optimized. (author)

  9. Preparation and application of zirconium sulfate supported on SAPO-34 molecular sieve as solid acid catalyst for esterification

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Dongyan, E-mail: xdy0156@sina.com; Ma, Hong; Cheng, Fei

    2014-05-01

    Graphical abstract: - Highlights: • SAPO-34 supported zirconium sulfate solid acid catalyst was prepared. • Esterification of acetic acid with ethanol can be catalyzed by ZS/SAPO-34. • The hydration of ZS is vital to the acidic property and catalytic performance. • The ZS/SAPO-34 catalyst treated at 200 °C shows good reusability. - Abstract: Zirconium sulfate (ZS) was supported on SAPO-34 molecular sieve by using an incipient wetness impregnation method with zirconium sulfate as the precursor. The as-prepared catalysts were used as solid acid catalyst for esterification reaction of acetic acid with ethanol. The influence of calcination temperature on the acidic property, catalytic activity, and reusability of ZS/SAPO-34 catalysts were mainly investigated. FT-IR, SEM, EDS and TG analysis have been carried out to demonstrate the characteristics of ZS/SAPO-34 catalysts. It was found that the 30 wt%ZS/SAPO-34 catalysts display the property of superacid irrespective of calcination temperature. The ZS/SAPO-34 catalyst treated at 200 °C can enhance the interaction between the supported ZS and SAPO-34 and keep the catalyst remaining substantially active after several reaction cycles. However, further increasing calcination temperature will cause the transfer of ZS from hydrate to anhydrous phase, and thus the decrease of activity.

  10. Preparation and application of zirconium sulfate supported on SAPO-34 molecular sieve as solid acid catalyst for esterification

    International Nuclear Information System (INIS)

    Xu, Dongyan; Ma, Hong; Cheng, Fei

    2014-01-01

    Graphical abstract: - Highlights: • SAPO-34 supported zirconium sulfate solid acid catalyst was prepared. • Esterification of acetic acid with ethanol can be catalyzed by ZS/SAPO-34. • The hydration of ZS is vital to the acidic property and catalytic performance. • The ZS/SAPO-34 catalyst treated at 200 °C shows good reusability. - Abstract: Zirconium sulfate (ZS) was supported on SAPO-34 molecular sieve by using an incipient wetness impregnation method with zirconium sulfate as the precursor. The as-prepared catalysts were used as solid acid catalyst for esterification reaction of acetic acid with ethanol. The influence of calcination temperature on the acidic property, catalytic activity, and reusability of ZS/SAPO-34 catalysts were mainly investigated. FT-IR, SEM, EDS and TG analysis have been carried out to demonstrate the characteristics of ZS/SAPO-34 catalysts. It was found that the 30 wt%ZS/SAPO-34 catalysts display the property of superacid irrespective of calcination temperature. The ZS/SAPO-34 catalyst treated at 200 °C can enhance the interaction between the supported ZS and SAPO-34 and keep the catalyst remaining substantially active after several reaction cycles. However, further increasing calcination temperature will cause the transfer of ZS from hydrate to anhydrous phase, and thus the decrease of activity

  11. Homogeneous and Supported Niobium Catalysts as Lewis Acid and Radical Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wayne Tikkanen

    2006-12-31

    The synthesis of tetrachlorotetraphenylcyclopentadienyl group 5 metal complexes has been accomplished through two routes, one a salt metathesis with lithiumtetraphenylcyclopentadiende and the other, reaction with trimethyltintetraphenylcyclopentadiene. The reactants and products have been characterized by {sup 1}H and {sup 13}C({sup 1}H) NMR spectroscopy. The niobium complex promotes the silylcyanation of butyraldehyde. The grafting of metal complexes to silica gel surfaces has been accomplished using tetrakisdimethylamidozirconium as the metal precursor. The most homogeneous binding as determined by CP-MAS {sup 13}C NMR and infrared spectroscopy was obtained with drying at 500 C at 3 mtorr vacuum. The remaining amido groups can be replaced by reaction with alcohols to generate surface bound metal alkoxides. These bound catalysts promote silylcyanation of aryl aldehydes and can be reused three times with no loss of activity.

  12. Functionalized carbon nanofibers as solid acid catalysts for transesterification

    NARCIS (Netherlands)

    Stellwagen, D.R.; van der Klis, Frits; van Es, D.S.; de Jong, K.P.; Bitter, J.H.

    2013-01-01

    Carbon nanofibers (CNFs) were functionalized with aryl sulfonic acid groups using in situ diazonium coupling. The use of diazonium coupling yielded an acidic carbon material, in which the introduced acidic groups are readily accessible to the triglyceride substrate. The material is an efficient

  13. Functionalized carbon nanofibers as solid-acid catalysts for transesterification

    NARCIS (Netherlands)

    Stellwagen, D.R.; Klis, van der F.; Es, van D.S.; Jong, de K.P.; Bitter, J.H.

    2013-01-01

    Carbon nanofibers (CNFs) were functionalized with aryl sulfonic acid groups using in situ diazonium coupling. The use of diazonium coupling yielded an acidic carbon material, in which the introduced acidic groups are readily accessible to the triglyceride substrate. The material is an efficient

  14. Aluminium and titanium modified mesoporous TUD-1: A bimetal acid catalyst for Biginelli reaction

    Science.gov (United States)

    Pasupathi, M.; Santhi, N.; Pachamuthu, M. P.; Alamelu Mangai, G.; Ragupathi, C.

    2018-05-01

    Using a simple, non-surfactant template triethanolamine (TEA), bimetal (Al3+ and Ti4+ ions) incorporated mesoporous catalyst AlTiTUD-1 (Si/Al+Ti = 50) was synthesized. The catalyst was characterized by XRD (Low and High angle), N2 Sorption, FTIR, SEM, TEM, DR UV Visible, and pyridine adsorbed FT-IR techniques. The XRD and N2 sorption studies confirmed its amorphous, mesoporous nature, which possessed a BET surface area of 590 m2 g-1 and pore diameter of 4.4 nm. The Al3+ and Ti4+ co-ordination within the TUD-1 was evaluated by DR UV-Vis. Pyridine adsorbed FTIR revealed both Bronsted (B) and Lewis (L) acidity, which is responsible for the catalytic activity. The acid catalyst showed a good catalytic performance in Biginelli type multicomponent coupling reaction for the substituted aldehydes, ethyl acetoacetate and thiourea to yield about 70% in reflux condition.

  15. Effect of Pretreatment with Sulfuric Acid on Catalytic Hydrocracking of Fe/AC Catalysts

    Directory of Open Access Journals (Sweden)

    Ruiyu Wang

    2017-01-01

    Full Text Available Activated carbon (AC was modified by H2SO4 and used as a support for catalyst. The Fe2S3/AC-T catalyst was prepared by deposition-precipitation method and used to catalyze hydrocracking of coal-related model compound, di(1-naphthylmethane (DNM. The properties of catalyst were studied by N2 adsorption-desorption, X-ray diffraction, and scanning electron microscopy. The result showed that ferric sulfate and acidic centers had synergetic effect on hydrocracking of DNM when using Fe2S3/AC-T as catalyst, the optimal loading of Fe is 9 wt.%. Hydroconversion of the extraction residue from Guizhou bituminous coal was also studied using Fe2S3/AC-T as the catalyst. The reaction was conducted in cyclohexane under 0.8 Mpa of initial hydrogen pressure at 310°C. The reaction mixture was extracted with petroleum ether and analyzed by GC/MS. Amounts of organic compounds which fall into the categories of homologues of benzene and naphthalene were detected. It suggested that the catalyst could effectively catalyze the cleavage of C-C-bridged bonds.

  16. Highly Selective Liquid-Phase Benzylation of Anisole with Solid-Acid Zeolite Catalysts

    DEFF Research Database (Denmark)

    Poreddy, Raju; Shunmugavel, Saravanamurugan; Riisager, Anders

    2015-01-01

    Zeolites were evaluated as solid acid catalysts for the liquid-phase benzylation of anisole with benzyl alcohol, benzyl bromide, and benzyl chloride at 80 °C. Among the examined zeolites, H-mordenite-10 (H-MOR-10) demonstrated particular high activity (>99 %) and excellent selectivity (>96...

  17. Solid Silica-based Sulphonic Acid as an Efficient Green Catalyst for ...

    African Journals Online (AJOL)

    NJD

    Solid Silica-based Sulphonic Acid as an Efficient Green. Catalyst for the Selective Oxidation of Sulphides to. Sulphoxides using NaCIO in Aqueous Media. Ali Amoozadeh* and Firouzeh Nemati. Department of Chemistry, Faculty of Science, Semnan University, Semnan, Iran. Received 21 October 2008, revised 6 December ...

  18. Sulfuric acid baking and leaching of spent Co-Mo/Al2O3 catalyst.

    Science.gov (United States)

    Kim, Hong-In; Park, Kyung-Ho; Mishra, Devabrata

    2009-07-30

    Dissolution of metals from a pre-oxidized refinery plant spent Co-Mo/Al(2)O(3) catalyst have been tried through low temperature (200-450 degrees C) sulfuric acid baking followed by mild leaching process. Direct sulfuric acid leaching of the same sample, resulted poor Al and Mo recoveries, whereas leaching after sulfuric acid baking significantly improved the recoveries of above two metals. The pre-oxidized spent catalyst, obtained from a Korean refinery plant found to contain 40% Al, 9.92% Mo, 2.28% Co, 2.5% C and trace amount of other elements such as Fe, Ni, S and P. XRD results indicated the host matrix to be poorly crystalline gamma- Al(2)O(3). The effect of various baking parameters such as catalyst-to-acid ratio, baking temperature and baking time on percentage dissolutions of metals has been studied. It was observed that, metals dissolution increases with increase in the baking temperature up to 300 degrees C, then decreases with further increase in the baking temperature. Under optimum baking condition more than 90% Co and Mo, and 93% Al could be dissolved from the spent catalyst with the following leaching condition: H(2)SO(4)=2% (v/v), temperature=95 degrees C, time=60 min and Pulp density=5%.

  19. Boric acid as a mild and efficient catalyst for one-pot synthesis of 1

    Indian Academy of Sciences (India)

    Abstract. An efficient green chemistry method has been developed for the synthesis of 1-amidoalkyl-2-naphthol derivatives via a one-pot three-component condensation of 2-naphthol, aldehydes and amide in the presence of boric acid as a mild catalyst.

  20. Elaboration and characterisation of acids catalyst for the obtention of amines

    International Nuclear Information System (INIS)

    Khemaissia, S.; Zaoui, B.; Nibou, D.

    1997-04-01

    The nuclear energy has shown the interest of aminated substances as solvents for removal and purification. These extractants are generally used in uranium ores treatment processes and several technology fields, specially, in organic and pharmaceutical industries. The present work deals with elaboration and characterization of acidic solid catalyst used in aminated extractants obtaining

  1. Silica Sulfuric Acid: An Eco-Friendly and Reusable Catalyst for Synthesis of Benzimidazole Derivatives

    Directory of Open Access Journals (Sweden)

    Bahareh Sadeghi

    2013-01-01

    Full Text Available Silica sulfuric acid (SiO2-OSO3H as an eco-friendly, readily available, and reusable catalyst is applied to benzimidazole derivatives synthesis under reflux in ethanol. The procedure is very simple and the products are isolated with an easy workup in good-to-excellent yields.

  2. Dehydration of D-xylose to furfural using acid-functionalized MWCNTs catalysts

    Science.gov (United States)

    Termvidchakorn, Chompoopitch; Itthibenchapong, Vorranutch; Songtawee, Siripit; Chamnankid, Busaya; Namuangruk, Supawadee; Faungnawakij, Kajornsak; Charinpanitkul, Tawatchai; Khunchit, Radchadaporn; Hansupaluk, Nanthiya; Sano, Noriaki; Hinode, Hirofumi

    2017-09-01

    Acid-functionalized multi-wall carbon nanotubes (MWCNTs) catalysts were prepared by a wet chemical sonication with various acid solutions, i.e. H2SO4, H3PO4, HNO3, and HCl. Sulfonic groups and carboxyl groups were detected on MWCNTs with H2SO4 treatment (s-MWCNTs), while only carboxyl groups were presented from other acid treatments. The catalytic dehydration of D-xylose into furfural was evaluated using a batch reactor at 170 °C for 3 h under N2 pressure of 15 bar. The highest furfural selectivity was achieved around 57% by s-MWCNTs catalyst, suggesting a positive role of the sulfonic functionalized groups. The effect of Co species was related to their Lewis acid property resulting in the enhancement of xylose conversion with low selectivity to furfural product. Invited talk at 5th Thailand International Nanotechnology Conference (Nano Thailand-2016), 27-29 November 2016, Nakhon Ratchasima, Thailand.

  3. Catalyst evaluation for oxygen reduction reaction in concentrated phosphoric acid at elevated temperatures

    Science.gov (United States)

    Hu, Yang; Jiang, Yiliang; Jensen, Jens Oluf; Cleemann, Lars N.; Li, Qingfeng

    2018-01-01

    Phosphoric acid is the common electrolyte for high-temperature polymer electrolyte fuel cells (HT-PEMFCs) that have advantages such as enhanced CO tolerance and simplified heat and water management. The currently used rotating disk electrode technique is limited to tests in dilute solutions at low temperatures and hence is not suitable for catalyst evaluation for HT-PEMFCs. In this study, we have designed and constructed a half-cell setup to measure the intrinsic activities of catalysts towards the oxygen reduction reaction (ORR) in conditions close to HT-PEMFC cathodes. By optimization of the hydrophobic characteristics of electrodes and the catalyst layer thickness, ORR activities of typical Pt/C catalysts are successfully measured in concentrated phosphoric acid at temperatures above 100 °C. In terms of mass-specific activities, the catalyst exhibits about two times higher activity in the half-cell electrode than that observed in fuel cells, indicating the feasibility of the technique as well as the potential for further improvement of fuel cell electrode performance.

  4. STARCH SULFURIC ACID: AN ALTERNATIVE, ECO-FRIENDLY CATALYST FOR BIGINELLI REACTION

    Directory of Open Access Journals (Sweden)

    Ramin Rezaei

    2013-12-01

    Full Text Available The one-pot multicomponent synthesis of 3,4-dihydropyrimidinone derivatives using starch sulfuric acid as an environmentally friendly biopolymer-based solid acid catalyst from aldehydes, β-keto esters and urea/ thiourea without solvent is described. Compared with classical Biginelli reaction conditions, this new method has the advantage of minimizing the cost operational hazards and environmental pollution, good yields, shorter reaction times and simple work-up.

  5. Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Coan, Patrick D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Ellis, Lucas D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Griffin, Michael B. [National Bioenergy Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Schwartz, Daniel K. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Medlin, J. Will [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States

    2018-03-01

    Cooperative catalysts containing a combination of noble metal hydrogenation sites and Bronsted acid sites are critical for many reactions, including the deoxygenation (DO) of biomass-derived oxygenates in the upgrading of pyrolysis oil. One route toward the design of cooperative catalysts is to tether two different catalytically active functions so that they are in close proximity while avoiding undesirable interactions that can block active sites. Here, we deposited carboxylic acid (CA)-functionalized organophosphonate monolayers onto Al2O3-supported Pd nanoparticle catalysts to prepare bifunctional catalysts containing both Bronsted acid and metal sites. Modification with phosphonic acids (PAs) improved activity and selectivity for gas-phase DO reactions, but the degree of improvement was highly sensitive to both the presence and positioning of the CA group, suggesting a significant contribution from both the PA and CA sites. Short spacer lengths of 1-2 methylene groups between the phosphonate head and CA tail were found to yield the best DO rates and selectivities, whereas longer chains performed similarly to self-assembled monolayers having alkyl tails. Results from a combination of density functional theory and Fourier transform infrared spectroscopy suggested that the enhanced catalyst performance on the optimally positioned CAs was due to the generation of strong acid sites on the Al2O3 support adjacent to the metal. Furthermore, the high activity of these sites was found to result from a hydrogen-bonded cyclic structure involving cooperativity between the phosphonate head group and CA tail function. More broadly, these results indicate that functional groups tethered to supports via organic ligands can influence catalytic chemistry on metal nanoparticles.

  6. Improved synthesis of isostearic acid using zeolite catalysts

    Science.gov (United States)

    Isostearic acids are unique and important biobased products with superior properties. Unfortunately, they are not widely utilized in industry because they are produced as byproducts from a process called clay-catalyzed oligomerization of tall oil fatty acids. Generally, this clay method results in...

  7. Aerobic Oxidation of Xylose to Xylaric acid in Water over Pt Catalysts.

    Science.gov (United States)

    Saha, Basudeb; Sadula, Sunitha

    2018-05-02

    Energy-efficient catalytic conversion of biomass intermediates to functional chemicals can enable bio-products viable. Herein, we report an efficient and low temperature aerobic oxidation of xylose to xylaric acid, a promising bio-based chemical for the production of glutaric acid, over commercial catalysts in water. Among several heterogeneous catalysts investigated, Pt/C exhibits the best activity. Systematic variation of reaction parameters in the pH range of 2.5 to 10 suggests that the reaction is fast at higher temperatures but high C-C scission of intermediate C5-oxidized products to low carbon carboxylic acids undermines xylaric acid selectivity. The C-C cleavage is also high in basic solution. The oxidation at neutral pH and 60 C achieves the highest xylaric acid yield (64%). O2 pressure and Pt-amount have significant influence on the reactivity. Decarboxylation of short chain carboxylic acids results in formation of CO2, causing some carbon loss; however such decarboxylation is slow in the presence of xylose. The catalyst retained comparable activity, in terms of product selectivity, after five cycles with no sign of Pt leaching. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Study on the Hydrolysis Kinetics of Xylan on Different Acid Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Na, Byeong-Il; Lee, Jae-Won [Chonnam National University, Gwangju (Korea, Republic of)

    2014-04-15

    In this study, we investigated kinetic model for the acid-catalyzed xylan hydrolysis at temperature 120-150 .deg. C. Also, we analyzed the kinetic parameters for xylose production and furfural decomposition. The hydrolysis of xylan and the degradation of xylose were promoted by high reaction temperature and acid concentration. The optimal hydrolysis condition for the highest reaction rate constants (k{sub 1}) was different depending on the acid catalysts. Among sulfuric, oxalic and maleic acid, the xylan reaction rate constants (k{sub 1}) to xylose had the highest value of 0.0241 min{sup -1} when 100 mM sulfuric acid was used at 120 .deg. C. However, sulfuric acid induced more xylose degradation compared to oxalic and maleic acid hydrolysis. The activation energy for xylan degradation was the highest when sulfuric acid was used.

  9. Furfural production in biphasic media using an acidic ionic liquid as a catalyst.

    Science.gov (United States)

    Peleteiro, Susana; Santos, Valentín; Parajó, Juan C

    2016-11-20

    Ionic liquids are valuable tools for biorefineries. This study provides an experimental assessment on the utilization of an acidic ionic liquid (1-butyl-3-methylimidazolium hydrogen sulfate) as a catalyst for furfural production in water/solvent media. The substrates employed in experiments were commercial xylose (employed as a reference compound) or hemicellulosic saccharides obtained by hydrothermal processing of Eucalyptus globulus wood (which were employed as produced, after membrane concentration or after freeze-drying). A variety of reaction conditions (defined by temperature, reaction time and type of organic solvent) were considered. The possibility of recycling the catalyst was assessed in selected experiments. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Acid properties of catalysts as studied by CO adsorption

    International Nuclear Information System (INIS)

    Knozinger, H.

    1992-01-01

    CO is a soft base and can therefore, be used as a highly specific probe for acid sites on oxide surfaces. Relative acidity sequences of Bronsted sites can be established based on the IR-hydroxyl frequency shifts when CO is adsorbed by H-bonding at 77 K. Coordination of CO onto coordinately unsaturated cation sites (Lewis acid sites) leads to cation-sensitive carbonyl stretching frequency shifts. The CO stretching band postions can be correlated with the electric field strength exerted by the cation. A universal correlation seems to exist. Applications of these principles for the study of binary oxides; zeolites, supported oxides and sulfides will be discussed in this paper

  11. Synthesis of bio-based methacrylic acid by decarboxylation of itaconic acid and citric acid catalyzed by solid transition-metal catalysts

    NARCIS (Netherlands)

    Notre, le J.E.L.; Witte-van Dijk, S.C.M.; Haveren, van J.; Scott, E.L.; Sanders, J.P.M.

    2014-01-01

    Methacrylic acid, an important monomer for the plastics industry, was obtained in high selectivity (up to 84%) by the decarboxylation of itaconic acid using heterogeneous catalysts based on Pd, Pt and Ru. The reaction takes place in water at 200–2508C without any external added pressure, conditions

  12. Characterization and Design of Zeolite Catalysts Solid Acidity, Shape Selectivity and Loading Properties

    CERN Document Server

    Niwa, Miki; Okumura, Kazu

    2010-01-01

    Zeolites are microporous, aluminosilicate minerals commonly used as commercial adsorbents. Zeolite-based catalysts are used by industrial chemical companies in the interconversion of hydrocarbons and the alkylation of aromatic compounds. The current book deals with the characterization of specific properties of Zeolites and calculations for the design of catalysts. Measurements and utilization of solid acidity, shape selectivity, and loading properties, that are three prominent properties of a Zeolite catalyst, are treated in detail. These features concern chemical vapor deposition of silica, shape selectivity, loading properties, solid activity, Brønsted or Lewis character, ammonia temperature programmed desorption, control of the pore-opening size by chemical vapor deposition of silica and XAFS analysis of metals being highly dispersed inside and outside a framework.

  13. Nano carbon supported platinum catalyst interaction behavior with perfluorosulfonic acid ionomer and their interface structures

    DEFF Research Database (Denmark)

    Andersen, Shuang Ma

    2016-01-01

    behavior of Nafion ionomer on platinized carbon nano fibers (CNFs), carbon nano tubes (CNTs) and amorphous carbon (Vulcan). The interaction is affected by the catalyst surface oxygen groups as well as porosity. Comparisons between the carbon supports and platinized equivalents are carried out. It reveals......The interaction between perfluorosulfonic acid ionomer and supported platinum catalyst is essential. It directly influences platinum accessibility, stability of carbon support and platinum, proton conductivity and electron conductivity in an electrode. In this study, we compare the adsorption...... that the platinization step modifies the surface nature of the carbon supports in terms of specific surface area, crystallinity and especially porosity; therefore, ionomer adsorption over carbon is not always representative for the ionomer adsorption over carbon supported catalyst, though indicative. Moreover...

  14. Catalyst Degradation in High Temperature Proton Exchange Membrane Fuel Cells Based on Acid Doped Polybenzimidazole Membranes

    DEFF Research Database (Denmark)

    Cleemann, Lars Nilausen; Buazar, F.; Li, Qingfeng

    2013-01-01

    and multi‐walled carbon nanotubes were used as supports for electrode catalysts and evaluated in accelerated durability tests under potential cycling at 150 °C. Measurements of open circuit voltage, area specific resistance and hydrogen permeation through the membrane were carried out, indicating little...... contribution of the membrane degradation to the performance losses during the potential cycling tests. As the major mechanism of the fuel cell performance degradation, the electrochemical active area of the cathodic catalysts showed a steady decrease in the cyclic voltammetric measurements, which was also......Degradation of carbon supported platinum catalysts is a major failure mode for the long term durability of high temperature proton exchange membrane fuel cells based on phosphoric acid doped polybenzimidazole membranes. With Vulcan carbon black as a reference, thermally treated carbon black...

  15. Esterification of phenyl acetic acid with p-cresol using metal cation exchanged montmorillonite nanoclay catalysts.

    Science.gov (United States)

    Bhaskar, M; Surekha, M; Suma, N

    2018-02-01

    The liquid phase esterification of phenyl acetic acid with p -cresol over different metal cation exchanged montmorillonite nanoclays yields p -cresyl phenyl acetate. Different metal cation exchanged montmorillonite nanoclays (M n +  = Al 3+ , Zn 2+ , Mn 2+ , Fe 3+ , Cu 2+ ) were prepared and the catalytic activity was studied. The esterification reaction was conducted by varying molar ratio of the reactants, reaction time and catalyst amount on the yield of the ester. Among the different metal cation exchanged catalysts used, Al 3+ -montmorillonite nanoclay was found to be more active. The characterization of the material used was studied under different techniques, namely X-ray diffraction, scanning electron microscopy and thermogravimetric analysis. The product obtained, p -cresyl phenyl acetate, was identified by thin-layer chromotography and confirmed by Fourier transform infrared, 1 H NMR and 13 C NMR. The regeneration activity of used catalyst was also investigated up to fourth generation.

  16. ESTERIFICATION OF FATTY ACID FROM PALM OIL WASTE (SLUDGE OIL BY USING ALUM CATALYST

    Directory of Open Access Journals (Sweden)

    Thamrin Usman

    2010-06-01

    Full Text Available Esterification of fatty acids from palm oil waste (sludge oil as biodiesel liquid base has been done by using alum [Al2(SO43.14H2O] catalyst. Some reaction variables like reaction time, catalyst quantity, and molar ratio of sample-reactant was applied for optimal reaction. Yield of 94.66% was obtained at reaction condition 65 °C, 5 h, sample-reactant ratio 1:20, and catalyst quantity 3% (w/w. GC-MS analysis request showed that composition of methyl esters biodiesel are methyl caproic (0.67%, methyl lauric (0.21%, methyl miristic (1.96%, methyl palmitic (49.52%, methyl oleic (41.51%, and methyl stearic (6.13%. Physical properties of synthesized product (viscosity, refraction index and density are similar with those of commercial product.   Keywords: alum, biodiesel, esterification, sludge oil

  17. Two-step microalgal biodiesel production using acidic catalyst generated from pyrolysis-derived bio-char

    International Nuclear Information System (INIS)

    Dong, Tao; Gao, Difeng; Miao, Chao; Yu, Xiaochen; Degan, Charles; Garcia-Pérez, Manuel; Rasco, Barbara; Sablani, Shyam S.; Chen, Shulin

    2015-01-01

    Highlights: • Highly active catalyst was prepared using bio-char co-produced in Auger pyrolysis. • Catalyst inhibitors in crude oil were effectively removed by a practical refinery process. • Free fatty acids (FFA) content in refined microalgal oil was reduced to less than 0.5%. • A total fatty acid methyl ester (FAME) yield of 99% was obtained via a two-step process. • The inexpensive bio-char catalyst is superior to Amberlyst-15 in pre-esterification. - Abstract: An efficient process for biodiesel production from fast-refined microalgal oil was demonstrated. A low cost catalyst prepared from pyrolysis-derived bio-char, was applied in pre-esterification to reduce free fatty acid (FFA) content. Results showed that the bio-char catalyst was highly active in esterification; however, the performance of the catalyst significantly reduced when crude microalgal oil was used as feedstock. To solve the problem caused by catalyst-fouling, a fast and scalable crude oil refinery procedure was carried out to remove chlorophyll and phospholipids that might degrade the catalyst and the quality of biodiesel. The activity and reusability of bio-char catalyst were remarkably improved in the fast-refined oil. FFA content in the refined microalgal oil was reduced to less than 0.5% after pre-esterification. The bio-char catalyst could be reused for 10 cycles without dramatic loss in activity. The pre-esterification fits the first-order kinetic reaction with activation energy of 42.16 kJ/mol. The activity of bio-char catalyst was superior to commercial Amberlyst-15 under the same reaction condition. A total fatty acid methyl ester (FAME, namely biodiesel) yield of 99% was obtained following the second-step CaO-catalyzed transesterification. The cost-effective bio-char catalyst has great potential for biodiesel production using feedstocks having high FFA content.

  18. Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Karakalos, Stavros; Luo, Langli; Qiao, Zhi; Xie, Xiaohong; Wang, Chongmin; Su, Dong; Shao, Yuyan; Wu, Gang (BNL); (Oregon State U.); (SC); (PNNL); (Buffalo)

    2017-09-26

    It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μgPt/cm2). Enhanced stability

  19. 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.

  20. The Comparison of Hydrochloric Acid and Phosphoric Acid Treatments in the Preparation of Montmorillonite Catalysts for RNA Synthesis

    Science.gov (United States)

    Aldersley, Michael Frank; Joshi, Prakash C.; Huang, Yixing

    2017-09-01

    The treatment of clay minerals with a preliminary acid wash and titration to pH 7 has proven to generate catalysts for the most interesting of oligomerization reactions in which activated RNA-nucleotides generate oligomers up to 40-mers. Significantly, not all clay minerals become catalytic following this treatment and none are catalytic in the absence of such treatment. The washing procedure has been modified and explored further using phosphoric acid and the outcomes are compared to those obtained when clay samples are prepared following a hydrochloric acid wash.

  1. The Comparison of Hydrochloric Acid and Phosphoric Acid Treatments in the Preparation of Montmorillonite Catalysts for RNA Synthesis.

    Science.gov (United States)

    Aldersley, Michael Frank; Joshi, Prakash C; Huang, Yixing

    2017-09-01

    The treatment of clay minerals with a preliminary acid wash and titration to pH 7 has proven to generate catalysts for the most interesting of oligomerization reactions in which activated RNA-nucleotides generate oligomers up to 40-mers. Significantly, not all clay minerals become catalytic following this treatment and none are catalytic in the absence of such treatment. The washing procedure has been modified and explored further using phosphoric acid and the outcomes are compared to those obtained when clay samples are prepared following a hydrochloric acid wash.

  2. Self-Assembled Nanocomposite Organic Polymers with Aluminum and Scandium as Heterogeneous Water-Compatible Lewis Acid Catalysts.

    Science.gov (United States)

    Miyamura, Hiroyuki; Sonoyama, Arisa; Hayrapetyan, Davit; Kobayashi, Shū

    2015-09-01

    While water-compatible Lewis acids have great potential as accessible and environmentally benign catalysts for various organic transformations, efficient immobilization of such Lewis acids while keeping high activity and without leaching of metals even under aqueous conditions is a challenging task. Self-assembled nanocomposite catalysts of organic polymers, carbon black, aluminum reductants, and scandium salts as heterogeneous water-compatible Lewis acid catalysts are described. These catalysts could be successfully applied to various C-C bond-forming reactions without leaching of metals. Scanning transmission electron microscopy analyses revealed that the nanocomposite structure of Al and Sc was fabricated in these heterogeneous catalysts. It is noted that Al species, which are usually decomposed rapidly in the presence of water, are stabilized under aqueous conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Preparation of Copper (II) Containing Phosphomolybdic Acid Salt as Catalyst for the Synthesis of Biodiesel by Esterification.

    Science.gov (United States)

    Cai, Jie; Zhang, Qiu-Yun; Wei, Fang-Fang; Huang, Jin-Shu; Feng, Yun-Mei; Ma, Hai-Tao; Zhang, Yutao-

    2018-04-01

    Copper (II) containing phosphomolybdic acid (PMA) catalysts were synthesized by ion exchange method and characterization using various physico-chemical techniques such as X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), thermogravimetric (TG) and scanning electron microscopy (SEM). The characterization results showed that the Keggin ions were retained in the catalysts and possessed well thermal stability. The catalytic esterification of lauric acid with methanol could be easily achieved about 78.7% conversion under optimum condition, the catalyst also contributed to the stability of the catalyst in which it can be reused for a certain time. This study demonstrated an alternative approach to biodiesel production with high efficiency by Cu (II) ion exchanged phosphomolybdic acid catalyst in the esterification catalytic.

  4. Effects of Weight Hourly Space Velocity and Catalyst Diameter on Performance of Hybrid Catalytic-Plasma Reactor for Biodiesel Synthesis over Sulphated Zinc Oxide Acid Catalyst

    Directory of Open Access Journals (Sweden)

    Luqman Buchori

    2017-05-01

    Full Text Available Biodiesel synthesis through transesterification of soybean oil with methanol on hybrid catalytic-plasma reactor over sulphated zinc oxide (SO42-/ZnO active acid catalyst was investigated. This research was aimed to study effects of Weight Hourly Space Velocity (WHSV and the catalyst diameter on performance of the hybrid catalytic-plasma reactor for biodiesel synthesis. The amount (20.2 g of active sulphated zinc oxide solid acid catalysts was loaded into discharge zone of the reactor. The WHSV and the catalyst diameter were varied between 0.89 to 1.55 min-1 and 3, 5, and 7 mm, respectively. The molar ratio of methanol to oil as reactants of 15:1 is fed to the reactor, while operating condition of the reactor was kept at reaction temperature of 65 oC and ambient pressure. The fatty acid methyl ester (FAME component in biodiesel product was identified by Gas Chromatography - Mass Spectrometry (GC-MS. The results showed that the FAME yield decreases with increasing WHSV. It was found that the optimum FAME yield was achieved of 56.91 % at WHSV of 0.89 min-1 and catalyst diameter of 5 mm and reaction time of 1.25 min. It can be concluded that the biodiesel synthesis using the hybrid catalytic-plasma reactor system exhibited promising the FAME yield. Copyright © 2017 BCREC Group. All rights reserved Received: 15th November 2016; Revised: 24th December 2016; Accepted: 16th February 2017 How to Cite: Buchori, L., Istadi, I., Purwanto, P. (2017. Effects of Weight Hourly Space Velocity and Catalyst Diameter on Performance of Hybrid Catalytic-Plasma Reactor for Biodiesel Synthesis over Sulphated Zinc Oxide Acid Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (2: 227-234 (doi:10.9767/bcrec.12.2.775.227-234 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.2.775.227-234

  5. Cellulose sulphuric acid as a biodegradable catalyst for conversion ...

    Indian Academy of Sciences (India)

    This article describes simple and efficient method for the diazotization and azidation of different aromatic amines over cellulose sulphuric acid, sodium nitrite and sodium azide under mild conditions at room temperature. Various aryl amines possessing electron-withdrawing groups or electron-donating groups have been ...

  6. Transformation of Unsaturated Fatty Acids/Esters to Corresponding Keto Fatty Acids/Esters by Aerobic Oxidation with Pd(II)/Lewis Acid Catalyst.

    Science.gov (United States)

    Senan, Ahmed M; Zhang, Sicheng; Zeng, Miao; Chen, Zhuqi; Yin, Guochuan

    2017-08-16

    Utilization of renewable biomass to partly replace the fossil resources in industrial applications has attracted attention due to the limited fossil feedstock with the increased environmental concerns. This work introduced a modified Wacker-type oxidation for transformation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, in which Cu 2+ cation was replaced with common nonredox metal ions, that is, a novel Pd(II)/Lewis acid (LA) catalyst. It was found that adding nonredox metal ions can effectively promote Pd(II)-catalyzed oxidation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, even much better than Cu 2+ , and the promotional effect is highly dependent on the Lewis acidity of added nonredox metal ions. The improved catalytic efficiency is attributed to the formation of heterobimetallic Pd(II)/LA species, and the oxidation mechanism of this Pd(II)/LA catalyst is also briefly discussed.

  7. Kinetics study of levulinic acid production from corncobs by tin tetrachloride as catalyst.

    Science.gov (United States)

    Qing, Qing; Guo, Qi; Wang, Pengbo; Qian, Hongjia; Gao, Xiaohang; Zhang, Yue

    2018-07-01

    Levulinic acid (LA) is an ideal platform chemical that can be produced through acid-catalyzed dehydration and hydrolysis of hexose sugars obtained from lignocellulosic materials. In this study, SnCl 4 was identified as an efficient catalyst for LA production and the reaction kinetics was investigated in a single water phase under different reaction conditions. The Box-Behnken design response surface methodology (RSM) was applied to determine the optimized reaction conditions and three individual variables including reaction temperature, duration, and catalyst concentration were evaluated. An appealing LA yield of 76.0% was achieved at 193 °C and 17 min with 82 mM SnCl 4 catalyst. A kinetics model was developed to predict the yields of glucose, HMF, and LA, which are tally with the experimental results. The analysis of the related kinetic parameters and the results of the RSM experiment helped to provide insights into the interplay between various reaction steps with SnCl 4 as catalysts. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. 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

    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...

  9. Insight into the Effect of Sn on CO and Formic Acid Oxidation at PtSn Catalysts

    DEFF Research Database (Denmark)

    Stevanović, S.; Tripković, D.; Tripkovic, Vladimir

    2014-01-01

    The role of Sn on the catalytic activity for CO and formic acid oxidation is studied by comparing the activities of differently treated PtSn/C and Pt/C catalysts. The catalysts are prepared by a microwave-assisted polyol synthesis method. As revealed by scanning tunneling and transmission electron...

  10. Enhancement of Biodiesel Production from Marine Alga, Scenedesmus sp. through In Situ Transesterification Process Associated with Acidic Catalyst

    Directory of Open Access Journals (Sweden)

    Ga Vin Kim

    2014-01-01

    Full Text Available The aim of this study was to increase the yield of biodiesel produced by Scenedesmus sp. through in situ transesterification by optimizing various process parameters. Based on the orthogonal matrix analysis for the acidic catalyst, the effects of the factors decreased in the order of reaction temperature (47.5% > solvent quantity (26.7% > reaction time (17.5% > catalyst amount (8.3%. Based on a Taguchi analysis, the effects of the factors decreased in the order of solvent ratio (34.36% > catalyst (28.62% > time (19.72% > temperature (17.32%. The overall biodiesel production appeared to be better using NaOH as an alkaline catalyst rather than using H2SO4 in an acidic process, at 55.07 ± 2.18% (based on lipid weight versus 48.41 ± 0.21%. However, in considering the purified biodiesel, it was found that the acidic catalyst was approximately 2.5 times more efficient than the alkaline catalyst under the following optimal conditions: temperature of 70°C (level 2, reaction time of 10 hrs (level 2, catalyst amount of 5% (level 3, and biomass to solvent ratio of 1 : 15 (level 2, respectively. These results clearly demonstrated that the acidic solvent, which combined oil extraction with in situ transesterification, was an effective catalyst for the production of high-quantity, high-quality biodiesel from a Scenedesmus sp.

  11. Enhancement of Biodiesel Production from Marine Alga, Scenedesmus sp. through In Situ Transesterification Process Associated with Acidic Catalyst

    Science.gov (United States)

    Kim, Ga Vin; Choi, WoonYong; Kang, DoHyung; Lee, ShinYoung; Lee, HyeonYong

    2014-01-01

    The aim of this study was to increase the yield of biodiesel produced by Scenedesmus sp. through in situ transesterification by optimizing various process parameters. Based on the orthogonal matrix analysis for the acidic catalyst, the effects of the factors decreased in the order of reaction temperature (47.5%) > solvent quantity (26.7%) > reaction time (17.5%) > catalyst amount (8.3%). Based on a Taguchi analysis, the effects of the factors decreased in the order of solvent ratio (34.36%) > catalyst (28.62%) > time (19.72%) > temperature (17.32%). The overall biodiesel production appeared to be better using NaOH as an alkaline catalyst rather than using H2SO4 in an acidic process, at 55.07 ± 2.18% (based on lipid weight) versus 48.41 ± 0.21%. However, in considering the purified biodiesel, it was found that the acidic catalyst was approximately 2.5 times more efficient than the alkaline catalyst under the following optimal conditions: temperature of 70°C (level 2), reaction time of 10 hrs (level 2), catalyst amount of 5% (level 3), and biomass to solvent ratio of 1 : 15 (level 2), respectively. These results clearly demonstrated that the acidic solvent, which combined oil extraction with in situ transesterification, was an effective catalyst for the production of high-quantity, high-quality biodiesel from a Scenedesmus sp. PMID:24689039

  12. Structure and acidity of individual Fluid Catalytic Cracking catalyst particles studied by synchrotron-based infrared micro-spectroscopy

    NARCIS (Netherlands)

    Buurmans, I.L.C.; Soulimani, F.; Ruiz Martinez, J.; van der Bij, H.E.; Weckhuysen, B.M.

    2013-01-01

    A synchrotron-based infrared micro-spectroscopy study has been conducted to investigate the structure as well as the Brønsted and Lewis acidity of Fluid Catalytic Cracking (FCC) catalyst particles at the individual particle level. Both fresh and laboratory-deactivated catalyst particles have been

  13. Zirconyl (IV Nitrate as Efficient and Reusable Solid Lewis Acid Catalyst for the Synthesis of Benzimidazole Derivatives

    Directory of Open Access Journals (Sweden)

    Pratapsinha B. Gorepatil

    2013-01-01

    Full Text Available The present paper introduces a simple and efficient method for the synthesis of substituted benzimidazoles by heterocyclization of different o-phenylenediamines and substituted aromatic carboxylic acid/aldehyde in the presence of zirconyl nitrate as catalyst in ethanol under reflux, which produced excellent yield of corresponding benzimidazoles in a short reaction time with reusability of catalyst.

  14. Enhancement of biodiesel production from marine alga, Scenedesmus sp. through in situ transesterification process associated with acidic catalyst.

    Science.gov (United States)

    Kim, Ga Vin; Choi, Woonyong; Kang, Dohyung; Lee, Shinyoung; Lee, Hyeonyong

    2014-01-01

    The aim of this study was to increase the yield of biodiesel produced by Scenedesmus sp. through in situ transesterification by optimizing various process parameters. Based on the orthogonal matrix analysis for the acidic catalyst, the effects of the factors decreased in the order of reaction temperature (47.5%) > solvent quantity (26.7%) > reaction time (17.5%) > catalyst amount (8.3%). Based on a Taguchi analysis, the effects of the factors decreased in the order of solvent ratio (34.36%) > catalyst (28.62%) > time (19.72%) > temperature (17.32%). The overall biodiesel production appeared to be better using NaOH as an alkaline catalyst rather than using H2SO4 in an acidic process, at 55.07 ± 2.18% (based on lipid weight) versus 48.41 ± 0.21%. However, in considering the purified biodiesel, it was found that the acidic catalyst was approximately 2.5 times more efficient than the alkaline catalyst under the following optimal conditions: temperature of 70 °C (level 2), reaction time of 10 hrs (level 2), catalyst amount of 5% (level 3), and biomass to solvent ratio of 1 : 15 (level 2), respectively. These results clearly demonstrated that the acidic solvent, which combined oil extraction with in situ transesterification, was an effective catalyst for the production of high-quantity, high-quality biodiesel from a Scenedesmus sp.

  15. Esterification of Palmitic Acid with Methanol in the Presence of Macroporous Ion Exchange Resin as Catalyst

    Directory of Open Access Journals (Sweden)

    Amelia Qarina Yaakob and Subhash Bhatia

    2012-10-01

    Full Text Available The esterification of palmitic acid with methanol was studied in a batch reactor using macro porous ion exchange resin Amberlyst 15 as a catalyst. Methyl palmitate was produced from the reaction between palmitic acid and methanol in the presence of catalyst. The effects of processing parameters, molar ratio of alcohol to acid M, (4-10, catalyst loading (0-10 g cat/liter, water inhibition (0-2 mol/liter, agitator speed (200-800 rpm and reaction temperature (343-373K were studied. The experimental kinetic data were correlated using homogenous as well as heterogeneous models (based on single as well as dual site mechanisms. The activation energy of the reaction was 11.552 kJ/mol for forward reaction whilst 5.464 kJ/mol for backward reaction. The experimental data fitted well with the simulated data obtained from the kinetic models. Keywords: Palmitic Acid, Methanol, Esterification, Ion Exchange Resin, Kinetics.

  16. Recovery of vanadium (V) from spent catalysts used in sulfuric acid production units by acid or alkaline leaching

    International Nuclear Information System (INIS)

    Abdulbaki, M.; Stas, J.; Shino, O.; Asaad, K.; Al-Kassemi, H.; Al-Qabani, F.

    2008-01-01

    The present paper, studies the recovery of vanadium from the spent catalyst by using acidic or alkaline leaching technique. The optimal conditions of spent catalyst leaching have been studied. It has been shown that 20%(w/w) of sulfuric acid is the most suitable for leaching process at 70 Centigrade. The precipitation of vanadium using some alkaline media (Na 2 CO 3 , (NH 4 )CO 3 and NH 4 OH) has been also studied, it has been shown that ammonium hydroxide was the best at 60 degree, and iron was co-precipitated with vanadium which pollute the obtained red cake. So it is necessary to use liquid-liquid extraction technique for the separation between vanadium and iron and to have iron free red cake. (author)

  17. Esterification of Glycerol with Acetic Acid over Highly Active and Stable Alumina-based Catalysts: A Reaction Kinetics Study

    OpenAIRE

    Rane, S. A.; Pudi, S. M.; Biswas, P.

    2016-01-01

    The catalytic activity of Cu- or Ni monometallic and Cu-Ni bimetallic (Cu/Ni ratio = 3, 1, 0.33) catalysts supported on γ-Al2O3 and SO42–/γ-Al2O3 catalysts were evaluated for esterification of glycerol. The reactions were performed in a batch reactor under reflux at standard reaction conditions: temperature 110 °C, atmospheric pressure, glycerol to acetic acid molar ratio 1:9, and catalyst loading 0.25 g. The best catalytic activity was observed over 2 M SO42–/γ-Al2O3 catalyst, which showed t...

  18. Biodiesel production from esterification of free fatty acid over PA/NaY solid catalyst

    International Nuclear Information System (INIS)

    Liu, Wei; Yin, Ping; Zhang, Jiang; Tang, Qinghua; Qu, Rongjun

    2014-01-01

    Highlights: • Biodiesel production from esterification of oleic acid was catalyzed by PA/NaY. • The influences of the process operating parameters were studied. • RSM was employed to optimize the experimental conditions. • The kinetic equation of the esterification reaction was investigated. - Abstract: Because of the incitements from increasing petroleum prices, diminishing petroleum reserves and the environmental consequences of exhaust gases from petroleum fueled engines, biodiesel has been used as a substitute of the regular diesel in recent years. In this paper, biodiesel production from the esterification of the free fatty oil oleic acid with ethanol catalyzed by PA/NaY (PA = organic phosphonic acid) was investigated, and the effect of reaction conditions such as PA loading, catalyst amount, molar ratio of alcohol to acid, reaction temperature and reaction time on the esterification reaction was examined. The process optimization using response surface methodology (RSM) was performed and the interactions between the operational variables were elucidated. The optimum values for maximum conversion ratio of oleic acid could be obtained by using a Box–Behnken center-united design with a minimum of experimental work. The oleic acid conversion reached 79.51 ± 0.68% with the molar ratio of alcohol to oleic acid being 7:1 and 1.7 g PA/NaY catalyst (20 ml of PA loading) at 105 °C for 7 h. Moreover, a kinetic model for the esterification catalyzed by PA/NaY catalyst was established. By fitting the kinetic model with the experimental results, the reaction order n = 2, activation energy of the positive reaction Ea + = 43.41 kJ/mol and that of the reverse reaction Ea − = 59.74 kJ/mol were obtained

  19. Nature of the activates places of the acid solid catalysts of the sulphated metallic oxides type

    International Nuclear Information System (INIS)

    Gomez, Miguel A; Fontalvo Javier

    1998-01-01

    In this revision the state of the knowledge is presented with respect to the understanding of the nature of the active places for the strongly acid solid catalysts of the type sulphated metallic oxides. The results presented by means of models are based on the characterization of the properties physicochemical carried out by means of technical as XPS, to GO, NMR etc., and the evaluation of the catalytic activity in different applications

  20. Pd/C Synthesized with Citric Acid: An Efficient Catalyst for Hydrogen Generation from Formic Acid/Sodium Formate

    Science.gov (United States)

    Wang, Zhi-Li; Yan, Jun-Min; Wang, Hong-Li; Ping, Yun; Jiang, Qing

    2012-01-01

    A highly efficient hydrogen generation from formic acid/sodium formate aqueous solution catalyzed by in situ synthesized Pd/C with citric acid has been successfully achieved at room temperature. Interestingly, the presence of citric acid during the formation and growth of the Pd nanoparticles on carbon can drastically enhance the catalytic property of the resulted Pd/C, on which the conversion and turnover frequency for decomposition of formic acid/sodium formate system can reach the highest values ever reported of 85% within 160 min and 64 mol H2 mol−1 catalyst h−1, respectively, at room temperature. The present simple, low cost, but highly efficient CO-free hydrogen generation system at room temperature is believed to greatly promote the practical application of formic acid system on fuel cells. PMID:22953041

  1. Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hanguang [Department; Hwang, Sooyeon [Center; Wang, Maoyu [School; Feng, Zhenxing [School; Karakalos, Stavros [Department; Luo, Langli [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Qiao, Zhi [Department; Xie, Xiaohong [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wang, Chongmin [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Su, Dong [Center; Shao, Yuyan [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wu, Gang [Department

    2017-09-26

    To significantly reduce the cost of proton exchange membrane (PEM) fuel cells, current Pt must be replaced by platinum-metal-group (PGM)-free catalysts for the oxygen reduction reaction (ORR) in acid. We report here a new class of high-performance atomic iron dispersed carbon catalysts through controlled chemical doping of iron ions into zinc-zeolitic imidazolate framework (ZIF), a type of metal-organic framework (MOF). The novel synthetic chemistry enables accurate size control of Fe-doped ZIF catalyst particles with a wide range from 20 to 1000 nm without changing chemical properties, which provides a great opportunity to increase the density of active sites that is determined by the particle size. We elucidated the active site formation mechanism by correlating the chemical and structural changes with thermal activation process for the conversion from Fe-N4 complex containing hydrocarbon networks in ZIF to highly active FeNx sites embedded into carbon. A temperature of 800oC was identified as the critical point to start forming pyridinic nitrogen doping at the edge of the graphitized carbon planes. Further increasing heating temperature to 1100oC leads to increase of graphitic nitrogen, generating possible synergistic effect with FeNx sites to promote ORR activity. The best performing catalyst, which has well-defined particle size around 50 nm and abundance of atomic FeNx sites embedded into carbon structures, achieve a new performance milestone for the ORR in acid including a half-wave potential of 0.85 V vs RHE and only 20 mV loss after 10,000 cycles in O2 saturated H2SO4 electrolyte. The new class PGM-free catalyst with approaching activity to Pt holds great promise for future PEM fuel cells.

  2. The glmS ribozyme cofactor is a general acid-base catalyst.

    Science.gov (United States)

    Viladoms, Júlia; Fedor, Martha J

    2012-11-21

    The glmS ribozyme is the first natural self-cleaving ribozyme known to require a cofactor. The d-glucosamine-6-phosphate (GlcN6P) cofactor has been proposed to serve as a general acid, but its role in the catalytic mechanism has not been established conclusively. We surveyed GlcN6P-like molecules for their ability to support self-cleavage of the glmS ribozyme and found a strong correlation between the pH dependence of the cleavage reaction and the intrinsic acidity of the cofactors. For cofactors with low binding affinities, the contribution to rate enhancement was proportional to their intrinsic acidity. This linear free-energy relationship between cofactor efficiency and acid dissociation constants is consistent with a mechanism in which the cofactors participate directly in the reaction as general acid-base catalysts. A high value for the Brønsted coefficient (β ~ 0.7) indicates that a significant amount of proton transfer has already occurred in the transition state. The glmS ribozyme is the first self-cleaving RNA to use an exogenous acid-base catalyst.

  3. Comparison of sulfuric and hydrochloric acids as catalysts in hydrolysis of Kappaphycus alvarezii (cottonii).

    Science.gov (United States)

    Meinita, Maria Dyah Nur; Hong, Yong-Ki; Jeong, Gwi-Taek

    2012-01-01

    In this study, hydrolysis of marine algal biomass Kappaphhycus alvarezii using two different acid catalysts was examined with the goal of identifying optimal reaction conditions for the formation of sugars and by-products. K. alvarezii were hydrolyzed by autoclave using sulfuric acid or hydrochloric acid as catalyst with different acid concentrations (0.1-1.0 M), substrate concentrations (1.0-13.5%), hydrolysis time (10-90 min) and hydrolysis temperatures (100-130 (°)C). A difference in galactose, glucose, reducing sugar and total sugar content was observed under the different hydrolysis conditions. Different by-product compounds such as 5-hydroxymethylfurfural and levulinic acid were also observed under the different reaction conditions. The optimal conditions for hydrolysis were achieved at a sulfuric acid concentration, temperature and reaction time of 0.2 M, 130 °C and 15 min, respectively. These results may provide useful information for the development of more efficient systems for biofuel production from marine biomass.

  4. Green synthesis of 3,4-dihydropyrimidinones using nano Fe3O4@meglumine sulfonic acid as a new efficient solid acid catalyst under microwave irradiation

    Directory of Open Access Journals (Sweden)

    Leila Moradi

    2018-01-01

    Full Text Available Design, synthesis and characterization of nano Fe3O4@meglumine sulfonic acid as a new solid acid catalyst for the simple and green one pot multicomponent synthesis of 3,4-dihydropyrimidin-2(1H-ones/thiones was studied. New solid acid catalyst was prepared through a clean and simple protocol and characterized using FTIR, VSM, TGA, SEM, elemental analysis (CHN and XRD techniques. Heterogenization of homogeneous catalyst as a green approach is a useful method for enhancing the efficiency of catalyst. Presented study was a new method for attachment of homogeneous highly soluble catalyst (meglumine sulfate to the magnetite nanoparticle surfaces for preparing a heterogeneous and effective catalyst. Obtained heterogeneous and reusable solid acid catalyst has high performance in the synthesis of Biginelli compounds. The reaction was performed under microwave irradiation as a rapid and green condition. Easy work up as well as excellent yield (90–98% of products in short reaction times (40–200 s and reusable catalyst are the main advantages of presented procedure. Reaction products were characterized in details using physical and chemical techniques such as melting point, 1H NMR, 13C NMR and FTIR.

  5. Liquefaction of kraft lignin by hydrocracking with simultaneous use of a novel dual acid-base catalyst and a hydrogenation catalyst.

    Science.gov (United States)

    Wang, Jindong; Li, Wenzhi; Wang, Huizhen; Ma, Qiaozhi; Li, Song; Chang, Hou-Min; Jameel, Hasan

    2017-11-01

    In this study, a novel catalyst, S 2 O 8 2- -KNO 3 /TiO 2 , which has active acidic and basic sites, was prepared and used in lignin hydrocracking with a co-catalyst, Ru/C. Ru/C is an efficient hydrogenation catalyst and S 2 O 8 2- -KNO 3 /TiO 2 is a dual catalyst, which could efficiently degrade lignin. This catalytic hydrogenation system can reduce solid products to less than 1%, while giving a high liquid product yield of 93%. Catalytic hydrocracking of kraft lignin at 320°C for 6h gave 93% liquid product with 0.5% solid product. Most of this liquid product was soluble in petroleum ether (60% of 93%), which is a clear liquid and comprises mainly of monomeric and dimeric degradation products. These results demonstrated that the combination of the two catalysts is an efficient catalyst for liquefaction of lignin, with little char formation (∼1%). This concept has the potential to produce valuable chemicals and fuels from lignin under moderate conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Deep desulfurization of diesel via peroxide oxidation using phosphotungstic acid as phase transfer catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Sachdeva, T.O.; Pant, K.K. [Department of Chemical Engineering, Indian Institute of Technology, Delhi, New Delhi, 110016 (India)

    2010-09-15

    High sulfur level in diesel fuel has been identified as a major contributor to air pollutant in term of sulfur dioxide (SO{sub x}) through diesel fueled vehicles. The main aim of the present work is to develop a promising methodology for ultra deep desulfurization of diesel fuel using oxidation followed by phase transfer of oxidized sulfur. Experiments were carried out in a batch reactor using n-decane as the model diesel compound and also using commercial diesel feedstock. To remove sulfur tetraoctylammonium bromide, phosphotungstic acid, and hydrogen peroxide were used as phase transfer agent, catalyst and oxidant respectively. The percent sulfur removal increases with increasing the initial concentration of sulfur in fuel and with increasing the reaction temperature. Similar trends were observed when commercial diesel was used to carry out desulfurization studies. The amphiphilic catalyst serves as a catalyst and also as an emulsifying agent to stabilize the emulsion droplets. The effects of temperature, agitation speed, quantity of catalyst and the phase transfer agent were studied to estimate the optimal conditions for the reactions. The sulfur removal from a commercial diesel by phase transfer catalysis has been found effective and removal efficiency was more than 98%. Kinetic experiments carried out for the desulfurization revealed that the sulfur removal results are best fitted to a pseudo first order kinetics and the apparent activation energy of desulfurization was 30.6 kJ/mol. (author)

  7. Deep desulfurization of diesel via peroxide oxidation using phosphotungstic acid as phase transfer catalyst

    International Nuclear Information System (INIS)

    Sachdeva, T.O.; Pant, K.K.

    2010-01-01

    High sulfur level in diesel fuel has been identified as a major contributor to air pollutant in term of sulfur dioxide (SO x ) through diesel fueled vehicles. The main aim of the present work is to develop a promising methodology for ultra deep desulfurization of diesel fuel using oxidation followed by phase transfer of oxidized sulfur. Experiments were carried out in a batch reactor using n-decane as the model diesel compound and also using commercial diesel feedstock. To remove sulfur tetraoctylammonium bromide, phosphotungstic acid, and hydrogen peroxide were used as phase transfer agent, catalyst and oxidant respectively. The percent sulfur removal increases with increasing the initial concentration of sulfur in fuel and with increasing the reaction temperature. Similar trends were observed when commercial diesel was used to carry out desulfurization studies. The amphiphilic catalyst serves as a catalyst and also as an emulsifying agent to stabilize the emulsion droplets. The effects of temperature, agitation speed, quantity of catalyst and the phase transfer agent were studied to estimate the optimal conditions for the reactions. The sulfur removal from a commercial diesel by phase transfer catalysis has been found effective and removal efficiency was more than 98%. Kinetic experiments carried out for the desulfurization revealed that the sulfur removal results are best fitted to a pseudo first order kinetics and the apparent activation energy of desulfurization was 30.6 kJ/mol. (author)

  8. Gas-phase Dehydration of Glycerol over Supported Silicotungstic Acids Catalysts

    International Nuclear Information System (INIS)

    Kim, Yong Tae; Park, Eun Duck; Jung, Kwang Deog

    2010-01-01

    The gas-phase dehydration of glycerol to acrolein was carried out over 10 wt % HSiW catalysts supported on different supports, viz. γ-Al 2 O 3 , SiO 2 -Al 2 O 3 , TiO 2 , ZrO 2 , SiO 2 , AC, CeO 2 and MgO. The same reaction was also conducted over each support without HSiW for comparison. Several characterization techniques, N 2 -physisorption, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), the temperature-programmed desorption of ammonia (NH 3 - TPD), temperature-programmed oxidation (TPO) with mass spectroscopy and CHNS analysis were employed to characterize the catalysts. The glycerol conversion generally increased with increasing amount of acid sites. Ceria showed the highest 1-hydroxyacetone selectivity at 315 .deg. C among the various metal oxides. The supported HSiW catalyst showed superior catalytic activity to that of the corresponding support. Among the supported HSiW catalysts, HSiW/ZrO 2 and HSiW/SiO 2 -Al 2 O 3 showed the highest acrolein selectivity. In the case of HSiW/ZrO 2 , the initial catalytic activity was recovered after the removal of the accumulated carbon species at 550 .deg. C in the presence of oxygen

  9. 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 

  10. Preparation and characterization of nanocomposite of graphitic carbon nitride and TiO2 as a porous support for nano catalyst for desulfurization process

    Directory of Open Access Journals (Sweden)

    Ezzat Rafiee

    2017-12-01

    Full Text Available A novel heterogeneous nanocatalyst H3PW12O40/TiO2/g-C3N4 (PW/TiO2/CN was successfully synthesized by immobilization of PW on TiO2/CN nanocomposite, and characterized by SEM, BET, FT-IR, XRD, EDX, TEM and ICP. Catalytic performance of the as-prepared catalyst was investigated for the selective oxidation of sulfides to sulfoxides and sulfones in the presence of H2O2 as oxidant with good conversion and high selectivity. The main factors influencing the ability for selective oxidation of sulfides were studied, including reaction temperature, amounts of the catalyst, H2O2 and type of the reaction solvent. Catalytic oxidation of the different model oils containing dibenzothiophene (DBT, benzothiophene (BT and thiophene (T into corresponding sulfone was also studied. Effects of different extractive solvents, aromatics, alkenes and nitrogen compounds on the oxidative desulfurization processes (ODS were also studied. In addition, reducing the level of sulfur content in real oil was investigated. The recyclability of the PW/TiO2/CN nanocatalyst for various cycles without a significant loss of activity was proved. The heterogeneity of the as-prepared catalyst was confirmed by leaching tests. Keywords: Graphitic carbon nitride, Extraction, Tetrabutyl titanate, Heteropoly acid, Oxidative desulfurization, Oil

  11. Recovery of iron oxides from acid mine drainage and their application as adsorbent or catalyst.

    Science.gov (United States)

    Flores, Rubia Gomes; Andersen, Silvia Layara Floriani; Maia, Leonardo Kenji Komay; José, Humberto Jorge; Moreira, Regina de Fatima Peralta Muniz

    2012-11-30

    Iron oxide particles recovered from acid mine drainage represent a potential low-cost feedstock to replace reagent-grade chemicals in the production of goethite, ferrihydrite or magnetite with relatively high purity. Also, the properties of iron oxides recovered from acid mine drainage mean that they can be exploited as catalysts and/or adsorbents to remove azo dyes from aqueous solutions. The main aim of this study was to recover iron oxides with relatively high purity from acid mine drainage to act as a catalyst in the oxidation of dye through a Fenton-like mechanism or as an adsorbent to remove dyes from an aqueous solution. Iron oxides (goethite) were recovered from acid mine drainage through a sequential precipitation method. Thermal treatment at temperatures higher than 300 °C produces hematite through a decrease in the BET area and an increase in the point of zero charge. In the absence of hydrogen peroxide, the solids adsorbed the textile dye Procion Red H-E7B according to the Langmuir model, and the maximum amount adsorbed decreased as the temperature of the thermal treatment increased. The decomposition kinetics of hydrogen peroxide is dependent on the H(2)O(2) concentration and iron oxides dosage, but the second-order rate constant normalized to the BET surface area is similar to that for different iron oxides tested in this and others studies. These results indicate that acid mine drainage could be used as a source material for the production of iron oxide catalysts/adsorbents, with comparable quality to those produced using analytical-grade reagents. Copyright © 2012 Elsevier Ltd. All rights reserved.

  12. Oxidation of ethoxylated fatty alcohols to alkylpolyglycol carboxylic acids using noble metals as catalysts

    Directory of Open Access Journals (Sweden)

    Sagredos, Angelos

    2009-09-01

    Full Text Available The conversion of ethoxylated fatty alcohols to the corresponding carboxylic acids through dehydrogenation/ oxidation using noble-metal catalysts has been studied. Ethoxylated primary aliphatic alcohols, ethoxylated random secondary aliphatic alcohols and ethoxylated alkylphenols have been converted to the corresponding acids in the presence of a base. The noble metal catalysts Palladium and Platinum were used without significant degradation of the ethoxyl chain in yields that exceeded 90%. On the other hand, the catalysts Rhodium and Ruthenium gave yields of about 80% and 60% respectively.La conversión de alcoholes grasos etoxilados a los correspondientes ácidos carboxílicos por deshidrogenación/ oxidación con metales nobles como catalizador ha sido estudiada. Alcoholes primarios alifáticos etoxilados, alcoholes alifáticos secundarios etoxilados al azar y alquilfenoles etoxilados han sido convertidos a los correspondientes ácidos en presencia de base. Los catalizadores paladio y platino fueron usados sin degradación significativa de las cadenas etoxiladas con un rendimiento que excedió del 90%. Por otra parte catalizadores de rodio y rutenio produjeron rendimientos del 80 y 60%, respectivamente.

  13. Solid phosphoric acid oligomerisation: Manipulating diesel selectivity by controlling catalyst hydration

    International Nuclear Information System (INIS)

    Prinsloo, Nicolaas M.

    2006-01-01

    Solid phosphoric acid (SPA) catalyst is traditionally used in crude oil refineries to produce unhydrogenated motor-gasoline by propene and butene oligomerisation. SPA is also used in High-Temperature Fischer-Tropsch refineries (HTFT) to produce synthetic fuels albeit with a different emphasis. The petrol/diesel ratio of an HTFT refinery is very different from crude refining and it is often necessary to shift this ratio depending on market requirements. The influence of hydration was investigated as a means of improving diesel selectivity. This was achieved by studying SPA over a hydration range of 99-110% H 3 PO 4 , a temperature range of 140-230 o C and using C 3 -C 6 model and synthetic FT-derived olefinic feedstocks. A direct correlation was found between the selectivity towards diesel range products and the distribution of the phosphoric acid species viz. H 3 PO 4 , H 4 P 2 O 7 and H 5 P 3 O 10 . For various olefinic feedstocks, diesel selectivity increased with decreasing catalyst hydration with a maximum around 108% H 3 PO 4 for propene oligomerisation. Commercial tests confirmed the increase in diesel selectivity with lowered catalyst hydration. (author)

  14. Microwave-assisted degradation of acid orange using a conjugated polymer, polyaniline, as catalyst

    Directory of Open Access Journals (Sweden)

    Ufana Riaz

    2014-01-01

    Full Text Available Microwave-assisted photocatalytic degradation of dyes is one of the emerging technologies for waste water remediation. Microwave effectively accelerates photocatalytic degradation, when microwave electrodeless lamp (MEL substitutes traditional UV lamp as light source. This setup can be extremely simplified if MEL and photocatalyst can be replaced by a catalyst which can work under microwave irradiation in the absence of any light source. The present work reports for the first time degradation of acid orange 7 (AO under microwave irradiation using polyaniline (PANI as catalyst in the absence of any UV lamp as light source. The degradation/decolourization was carried out in neutral acidic and basic media and was monitored spectrophotometrically to evaluate the ability of microwave irradiation to degrade AO. Microwave irradiation showed excellent performance as it completely decolourizes AO dye solution in 10 min. With the advantages of low cost and rapid processing, this novel catalyst is expected to gain promising application in the treatment of various dyestuff wastewaters on a large scale.

  15. Cu2+ Montmorillonite K10 Clay Catalyst as a Green Catalyst for Production of Stearic Acid Methyl Ester: Optimization Using Response Surface Methodology (RSM

    Directory of Open Access Journals (Sweden)

    Enas A. Almadani

    2018-01-01

    Full Text Available Clay catalyst has received much attention to replace the homogeneous catalysts in the esterification reaction to produce fatty acid methyl ester as the source of biodiesel as it is low cost, easily available, as well as environmental friendly. However, the use of unmodified clay, in particular montmorillonite K10 (MMT K10, for the esterification of fatty acids showed that the acid conversion was less than 60% and this is not preferable to the production of biodiesel. In this study, synthesis of stearic acid methyl ester using Cu2+-MMT K10 (Cu-MMT K10 was successfully optimized via response surface methodo-logy (RSM based on 3-variable of Box-Behnken design (BB. The parameters were; reaction time (5-180 minutes, reaction temperature (80-120 oC and concentration of Cu2+ in MMT K10 (0.25-1 M. The use of RSM in optimizing the conversion of stearic acid was successfully developed as the actual experimental conversion of stearic acid was found similar to the actual values under the optimum conditions. The model equation predicted that the following conditions would generate the maximum conversion of stearic acid (87.05 %reaction time of 62 minutes, a reaction temperature of 80 oC and catalyst used is 1.0 M Cu-MMT K10. This finding can be considered as green catalytic process as it worked at moderate reaction temperature using low cost clay catalyst with a short reaction time. Copyright © 2018 BCREC Group. All rights reserved Received: 26th July 2017; Revised: 13rd January 2018; Accepted: 13rd January 2018; Available online: 22nd January 2018; Published regularly: 2nd April 2018 How to Cite: Almadani, E.A., Harun, F.W., Radzi, S.M., Muhamad, S.K. (2018. Cu2+ Montmorillonite K10 Clay Catalyst as a Green Catalyst for Production of Stearic Acid Methyl Ester: Optimization Using Response Surface Methodology (RSM. Bulletin of Chemical Reaction Engineering & Catalysis, 13 (1: 187-195 (doi:10.9767/bcrec.13.1.1397.187-195

  16. Theoretical Study on Free Fatty Acid Elimination Mechanism for Waste Cooking Oils to Biodiesel over Acid Catalyst.

    Science.gov (United States)

    Wang, Kai; Zhang, Xiaochao; Zhang, Jilong; Zhang, Zhiqiang; Fan, Caimei; Han, Peide

    2016-05-01

    A theoretical investigation on the esterification mechanism of free fatty acid (FFA) in waste cooking oils (WCOs) has been carried out using DMol(3) module based on the density functional theory (DFT). Three potential pathways of FFA esterification reaction are designed to achieve the formation of fatty acid methyl ester (FAME), and calculated results show that the energy barrier can be efficiently reduced from 88.597kcal/mol to 15.318kcal/mol by acid catalyst. The molar enthalpy changes (ΔrHm°) of designed pathways are negative, indicating that FFA esterification reaction is an exothermic process. The obtained favorable energy pathway is: H(+) firstly activates FFA, then the intermediate combines with methanol to form a tetrahedral structure, and finally, producing FAME after removing a water molecule. The rate-determining step is the combination of the activated FFA with methanol, and the activation energy is about 11.513kcal/mol at 298.15K. Our results should provide basic and reliable theoretical data for further understanding the elimination mechanism of FFA over acid catalyst in the conversion of WCOs to biodiesel products. Copyright © 2016 Elsevier Inc. All rights reserved.

  17. Gold nanoparticles stabilized by starch polymer and their use as catalyst in homocoupling of phenylboronic acid

    Directory of Open Access Journals (Sweden)

    Kittiyaporn Wongmanee

    2017-10-01

    Full Text Available In this study, gold nanoparticles (Au NPs stabilized by a starch polymer have been successfully prepared and characterized via a number of techniques including X-ray photoelectron spectroscopy (XPS, X-ray diffraction (XRD, UV-visible spectroscopy (UV-vis, transmission electron microscopy (TEM, and dynamic light scattering (DLS measurements. The catalytic activity of starch-stabilized Au NPs was also examined toward the homocoupling of phenylboronic acid in water using oxygen in air as oxidant at an ambient temperature (25 ± 1 °C. Several parameters including the catalyst loading, base equivalent (eq., base type, and reaction time were studied. This study offers a simple, inexpensive and environmentally friendly procedure for the stabilization of colloidal gold catalysts using a hydroxyl-rich structure of starch polymer with a great promise through potential applications in related fields.

  18. Transesterification of waste oil to biodiesel using Brønsted acid ionic liquid as catalyst

    Directory of Open Access Journals (Sweden)

    C. Xie

    2013-05-01

    Full Text Available Brønsted acid ionic liquids were employed for the preparation of biodiesel using waste oil as the feedstock. It was found that IL 1–(3–sulfonic acidpropyl–3–methylimidazole hydrosulfate–[HO3S-pmim]HSO4 was an efficient catalyst for the reaction under the optimum conditions: n(oil:n(methanol 1:12, waste oil 15.0 g, ionic liquid 2.0 g, reaction temperature 120 oC and reaction time 8 h, the yield of biodiesel was more than 96%. The reusability of the ionic liquid was also investigated. When the ionic liquid was repeatedly used for five times, the yield of product was still more than 93%. Therefore, an efficient and environmentally friendly catalyst was provided for the synthesis of biodiesel from waste oils.

  19. Kinetic Study on the Esterification of Palm Fatty Acid Distillate (PFAD) Using Heterogeneous Catalyst

    Science.gov (United States)

    Rofiqah, U.; Djalal, R. A.; Sutrisno, B.; Hidayat, A.

    2018-05-01

    Esterification with heterogeneous catalysts is believed to have advantages compared to homogeneous catalysts. Palm Fatty Acid Distillate (PFAD) was esterified by ZrO2 -SO4 2-/natural zeolite at temperature variation of 55°C, 60°C, and 65°C to produce biodiesel. Determination of reaction kinetics was done by experiment and modeling. Kinetic study was approached using pseudo-homogeneous model of first order. For experiment, reaction kinetics were 0.0031 s-1, 0.0054 s-1, and 0.00937 s-1 for a temperature of 55 °C, 60 °C and 65 °C, respectively. For modelling, reaction kinetics were 0.0030 s-1, 0.0055 s-1, and 0.0090 s-1 for a temperature of 55°C, 60°C and 65°C, respectively. Rate and conversion of reaction are getting increased by increasing temperature.

  20. Synthesis of bio-based methacrylic acid by decarboxylation of itaconic acid and citric acid catalyzed by solid transition-metal catalysts.

    Science.gov (United States)

    Le Nôtre, Jérôme; Witte-van Dijk, Susan C M; van Haveren, Jacco; Scott, Elinor L; Sanders, Johan P M

    2014-09-01

    Methacrylic acid, an important monomer for the plastics industry, was obtained in high selectivity (up to 84%) by the decarboxylation of itaconic acid using heterogeneous catalysts based on Pd, Pt and Ru. The reaction takes place in water at 200-250 °C without any external added pressure, conditions significantly milder than those described previously for the same conversion with better yield and selectivity. A comprehensive study of the reaction parameters has been performed, and the isolation of methacrylic acid was achieved in 50% yield. The decarboxylation procedure is also applicable to citric acid, a more widely available bio-based feedstock, and leads to the production of methacrylic acid in one pot in 41% selectivity. Aconitic acid, the intermediate compound in the pathway from citric acid to itaconic acid was also used successfully as a substrate. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Isolation and characterization of interacted heteropoly complexes of vanadium with molybdenum and tungsten

    International Nuclear Information System (INIS)

    Roy, S.K.; Jha, P.P.

    1980-01-01

    The nature and conditions of formation of two new interacted heteropoly vanadomolybdate and vanadotungstate of the compositions, (NH 4 ) 10 (MoV 12 O 38 ) 20H 2 O and (NH 4 ) 2 (WV 6 O 19 )11H 2 O, respectively, have been studied with the help of pH and thermometric titrations. From X-ray crystal diffraction studies, the unit cell dimensions and the number of unit cells have been determined. On the basis of these data the molecular weights of the compounds are found to be 1828 and 998 respectively. (author)

  2. Catalytic hydroprocessing of simulated coal tars. 2. Effect of acid catalysts on the hydroconversion of model compounds on a sulphided Ni-Mo/Al/sub 2/O/sub 3/ catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Lemberton, J.L.; Touzeyidio, M.; Guisnet, M. (Laboratoire de Catalyse en Chimie Organique CNRS, Poitiers (France))

    1989-09-15

    Acid catalysts were added to sulphided Ni-Mo/Al/sub 2/O/sub 3/ catalyst in order to obtain a higher hydrocracking activity. The hydroconversion of phenanthrene, alone or in the presence of carbazole and/or 1-naphthol, was chosen as a model reaction. The presence of acid catalysts greatly increases the conversion of phenanthrene and allows significant amounts of light products to be obtained. In the presence of carbazole or of 1-naphthol, acid catalysts create a small increase in phenanthrene conversion, but light products are no longer obtained as the acid sites are poisoned either by adsorption of ammonia from carbazole decomposition, or by extensive coke deposition generated from 1-naphthol. In the presence of carbazole and 1-naphthol, there is no longer any effect of the acid catalysts on the hydroconversion of phenanthrene, owing to complete inhibition of the acid sites. 12 refs., 5 tabs.

  3. Support Screening Studies on the Hydrogenation of Levulinic Acid to γ-Valerolactone in Water Using Ru Catalysts

    Directory of Open Access Journals (Sweden)

    Anna Piskun

    2016-08-01

    Full Text Available γ-Valerolactone (GVL has been identified as a sustainable platform chemical for the production of carbon-based chemicals. Here we report a screening study on the hydrogenation of levulinic acid (LA to GVL in water using a wide range of ruthenium supported catalysts in a batch set-up (1 wt. % Ru, 90 °C, 45 bar of H2, 2 wt. % catalyst on LA. Eight monometallic catalysts were tested on carbon based(C, carbon nanotubes (CNT and inorganic supports (Al2O3, SiO2, TiO2, ZrO2, Nb2O5 and Beta-12.5. The best result was found for Ru/Beta-12.5 with almost quantitative LA conversion (94% and 66% of GVL yield after 2 h reaction. The remaining product was 4-hydroxypentanoic acid (4-HPA. Catalytic activity for a bimetallic RuPd/TiO2 catalyst was by far lower than for the monometallic Ru catalyst (9% conversion after 2 h. The effects of relevant catalyst properties (average Ru nanoparticle size, Brunauer-Emmett-Teller (BET surface area, micropore area and total acidity on catalyst activity were assessed.

  4. UTILIZATION OF CASSAVA WASTE IN THE PRODUCTION OF PLYWOOD ADHESIVE EKSTENDER WITH DEXTRIN (WITH ACID CATALYST

    Directory of Open Access Journals (Sweden)

    Piyantina Rukmini

    2017-10-01

    Full Text Available Abstract- Require of manihot Esculinta Crantz in Indonesia rises in every year as growth of Indonesian people, bioethanol industry,and animal food. Raw material that use in this research is cassava wastes. This research aimed to know the utilization of cassava waste, the optimum condition process of dextrin, and to know the variable that influent the utilization of cassava waste in the production of adhesive ekstender ( catalyst concentration and time. The dekstrin process need beaker glass, stirrer, electric stove with oilbatch heater, thermometer, screening 80 mesh. Cassava wastes that keep on several days is burned without water at 800 C for 1 hours. Then drops acid catalyst ion the beaker glass with different concentration. Then the temperature is raised until 1100C for 1 hour. After the drying process, make it cool then screen it in to screener 80 mesh. The results show that on the higher concentration of acid, dextrin will get on the higher concentration. At the certain concentration of acid, dekstrin will not get in the high concentration. Maximum efficiency of the concentration of acid is 0,8 N. Keeping long day for cassava waste can make lower the concentration of dextrin. The best keeping day is the first day until four day.

  5. UTILIZATION OF CASSAVA WASTE IN THE PRODUCTION OF PLYWOOD ADHESIVE EKSTENDER WITH DEXTRIN (WITH ACID CATALYST

    Directory of Open Access Journals (Sweden)

    Piyantina Rukmini

    2017-10-01

    Full Text Available Require of manihot Esculinta Crantz in Indonesia rises in every year as growth of Indonesian people, bioethanol industry,and animal food. Raw material that use in this research is cassava wastes. This research aimed to know the utilization of cassava waste, the optimum condition process of dextrin, and to know the variable that influent the utilization of cassava waste in the production of adhesive ekstender ( catalyst concentration and time. The dekstrin process need beaker glass, stirrer, electric stove with oilbatch heater, thermometer, screening 80 mesh. Cassava wastes that keep on several days is burned without water at 800 C for 1 hours. Then drops acid catalyst ion the beaker glass with different concentration. Then the temperature is raised until 1100C for 1 hour. After the drying process, make it cool then screen it in to screener 80 mesh. The results show that on the higher concentration of acid, dextrin will get on the higher concentration. At the certain concentration of acid, dekstrin will not get in the high concentration. Maximum efficiency of the concentration of acid is 0,8 N. Keeping long day for cassava waste can make lower the concentration of dextrin. The best keeping day is the first day until four day.

  6. Thiophene Conversion and Ethanol Oxidation on SiO2-Supported 12-PMoV-Mixed Heteropoly Compounds

    Czech Academy of Sciences Publication Activity Database

    Spojakina, A. A.; Kostova, N. G.; Sow, Bineta; Stamenova, M. W.; Jirátová, Květa

    2001-01-01

    Roč. 65, 2-4 (2001), s. 315-321 ISSN 0920-5861 Institutional research plan: CEZ:AV0Z4072921 Keywords : thiophene conversion * ethanol oxidation * mixed heteropoly compounds Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.333, year: 2001

  7. Microwave assisted esterification of free fatty acid over a heterogeneous catalyst for biodiesel production

    International Nuclear Information System (INIS)

    Liu, Wei; Yin, Ping; Liu, Xiguang; Chen, Wen; Chen, Hou; Liu, Chunping; Qu, Rongjun; Xu, Qiang

    2013-01-01

    Highlights: • Microwave assisted esterification of stearic acid with ethanol was catalyzed by D418. • D418 exhibited remarkable catalytic performance for ethyl stearate formation. • It proved possible to prepare biodiesel rapidly and with good conversions by microwave heating. • The relative catalytic kinetics study has been conducted and modeled. - Abstract: Biodiesel fuel is gaining significant attention in recent years because of its environmental benefits and the growing interest in finding new resources and alternatives for conventional fuels. Biodiesel production from waste cooking oil with high free fatty acids usually requires esterification step to produce fatty acid methyl/ethyl ester. In the present work, the heterogeneous catalyst aminophosphonic acid resin D418 has been successfully utilized in the energy-efficient microwave-assisted esterification reaction of fatty acid ethyl ester (FAEE) from free fatty acid (FFA) stearic acid with short-chain alcohol ethanol. Under the reaction conditions of 9 wt% D418 and 11: 1 M ratio of ethanol to stearic acid at 353 K and atmospheric pressure, more than 90% conversion of the esterification was achieved in 7 h by microwave heating, while it took about 12 h by conventional heating. Moreover, the kinetics of this esterification reaction has been studied, and the relevant values of activation energy and pre-exponential factor were obtained

  8. Recent progress in synthesis and surface functionalization of mesoporous acidic heterogeneous catalysts for esterification of free fatty acid feedstocks: A review

    International Nuclear Information System (INIS)

    Soltani, Soroush; Rashid, Umer; Al-Resayes, Saud Ibrahim; Nehdi, Imededdine Arbi

    2017-01-01

    Highlights: • Mesoporous catalysts have potential to esterify the wastes feedstocks. • Surface area of mesoporous catalysts depends on materials synthesis methods. • Hydrophobic surface of sulfonated catalyst causes adsorption on FFA particles. • Mesoporous catalysts have large active sites to trap free fatty acids particles. • Recyclability of mesoporous catalyst is a key feature for biodiesel production. - Abstract: Biodiesel is considered as a sulfur free, non-toxic and biodegradable source of energy and its burning provide less pollution than petroleum based fuels. In case of using fried waste oils, animal’s fats and waste cultivated oil which contain high free fatty acid (FFA), esterification is taking place. Through esterification reaction, catalyst is an integral part which accelerates the FFA conversion to the methyl ester (ME) in shorter reaction time. Although, most of the current catalysts have some defect such as poor recyclability, less surface area and poor porosity. Mesoporous materials have been recently attracted remarkable interests because of its desirable properties, such as large and harmonized surface area, tuneable mesoporous channels with flexible pore size, excellent thermal stability, and post-functionalization surface characteristics. The combination of remarkable physico-chemical and textural properties as well as high activity has proposed them as advanced materials. In this review, it has been attempted to present the details of fundamental properties of mesoporous catalysts, various synthetic methods and formation mechanisms, and surface functionalization methodologies. The effects of various factors (such as surface area, porosity, acidity, post-calcination temperature, and reaction parameters) on esterification of different feedstocks are discussed in detail. Furthermore, the kinetic study of esterification reaction in the presence of mesoporous catalysts is also elaborated. At the end, remarkable challenges and outlooks

  9. Supported zirconium sulfate on carbon nanotubes as water-tolerant solid acid catalyst

    International Nuclear Information System (INIS)

    Juan, Joon Ching; Jiang Yajie; Meng Xiujuan; Cao Weiliang; Yarmo, Mohd Ambar; Zhang Jingchang

    2007-01-01

    A new solid acid of zirconium sulfate (CZ) was successfully supported on carbon nanotube (CNT) for esterification reaction. Preparation conditions of the supported CZ have been investigated, to obtain highest catalytic activity for esterification reaction. XRD, TEM, BET, X-ray photoelectron spectra (XPS) and in situ FTIR analysis has also been carried out to understand the characteristics of the catalyst. In the esterification of acrylic acid with n-octanol, the supported CZ exhibited high catalytic activity and stability. The catalytic activity was nearly unchanged during four times of reuse. XRD and TEM analysis indicated that CZ was finely dispersed on CNT. XPS analysis shows that the CZ species was preserved and the chemical environment of the CZ has changed after loaded on CNT. This finding show that CNT as CZ support is an efficient water-tolerant solid acid

  10. The kinetics and mechanism of methanol oxidation on Pt and PtRu catalysts in alkaline and acid media

    Directory of Open Access Journals (Sweden)

    JELENA LOVIC

    2007-07-01

    Full Text Available The kinetic of methanol electrochemical oxidation for a series of platinum and platinum–ruthenium catalysts was investigated. A correlation between the beginning of OHad adsorption and methanol oxidation was demonstarated on Pt single crystals and Pt nanocatalyst. The activity of the nano-structured Pt catalyst was compared with single crystal platinum electrodes assuming the Kinoshita model of nanoparticles. The ruthenium-containing catalysts shifted the onset of methanol oxidation to more negative potentials. The effect was more pronounced in acid than in alkaline media. Based on the established diagnostic criteria, the reaction between COad and OHad species according to the Langmuir–Hinshelwood mechanism was proposed as the rate determining step in alkaline and acid media on Pt and PtRu catalysts.

  11. Cationic mononuclear ruthenium carboxylates as catalyst prototypes for self-induced hydrogenation of carboxylic acids.

    Science.gov (United States)

    Naruto, Masayuki; Saito, Susumu

    2015-08-28

    Carboxylic acids are ubiquitous in bio-renewable and petrochemical sources of carbon. Hydrogenation of carboxylic acids to yield alcohols produces water as the only byproduct, and thus represents a possible next generation, sustainable method for the production of these alternative energy carriers/platform chemicals on a large scale. Reported herein are molecular insights into cationic mononuclear ruthenium carboxylates ([Ru(OCOR)](+)) as prototypical catalysts for the hydrogenation of carboxylic acids. The substrate-derived coordinated carboxylate was found to function initially as a proton acceptor for the heterolytic cleavage of dihydrogen, and subsequently also as an acceptor for the hydride from [Ru-H](+), which was generated in the first step (self-induced catalysis). The hydrogenation proceeded selectively and at high levels of functional group tolerance, a feature that is challenging to achieve with existing heterogeneous/homogeneous catalyst systems. These fundamental insights are expected to significantly benefit the future development of metal carboxylate-catalysed hydrogenation processes of bio-renewable resources.

  12. Enhanced catalytic performance of Pd catalyst for formic acid electrooxidation in ionic liquid aqueous solution

    Science.gov (United States)

    Feng, Yuan-Yuan; Yin, Qian-Ying; Lu, Guo-Ping; Yang, Hai-Fang; Zhu, Xiao; Kong, De-Sheng; You, Jin-Mao

    2014-12-01

    A protic ionic liquid (IL), n-butylammonium nitrate (N4NO3), is prepared and employed as the electrolyte for formic acid electrooxidation reaction (FAOR) on Pd catalysts. The oxidation peak potential of FAOR in the IL solution shows about a 200 mV negative shift as compared with those in traditional H2SO4/HClO4 electrolytes, suggesting that FAOR can be more easily carried out on Pd catalysts in IL media. The catalytic properties of Pd toward FAOR are not only dependent on the concentration of IL, as a consequence of the varied electronic conductivity of the IL solution, but also on the high potential limit of the cyclic voltammograms. When the Pd catalyst is cycled up to 1.0 V (vs. SCE), which induces a significant oxidation of Pd, it shows ca. 4.0 times higher activity than that not subjected to the Pd oxidation (up to 0.6 V). The Pd oxides, which are more easily formed in IL solution than in traditional H2SO4/HClO4 electrolytes, may play a crucial role in increasing the catalytic activities of Pd toward FAOR. Our work would shed new light on the mechanism of FAOR and highlight the potential applications of IL as green and environment-friendly electrolytes in fuel cells and other technologies.

  13. Esterification free fatty acid in sludge palm oil using ZrO2/SO42- - rice husk ash catalyst

    Science.gov (United States)

    Hidayat, Arif; Sutrisno, Bachrun

    2017-05-01

    Indonesia, as one of the biggest palm oil producers and exporters in the world, is producing large amounts of low-grade oil such as sludge palm oil (SPO) from palm oil industries. The use of SPO can lower the cost of biodiesel production significantly, which makes SPO a highly potential alternative feedstock for biodiesel production. In this paper, the esterification of free fatty acid on sludge palm oil was studied using rice husk ash as heterogeneous solid catalysts. Heterogeneous solid catalysts offer significant advantages of eliminating separation, corrosion, toxicity and environmental problems. In this paper the esterification of SPO, a by-product from palm oil industry, in the presence of modified rice husk ash catalysts was studied. The rice husk ash catalysts were synthesized by impregnating of Zirconia (Zr) on rice husk ash followed by sulfonation. The rice husk ash catalysts were characterized by using different techniques, such as FT-IR, XRD, and porous analysis. The effects of the mass ratio of catalyst to oil (1 - 10%), the molar ratio of methanol to oil (4:1 - 10:1), and the reaction temperature (40 - 60°C) were studied for the conversion of free fatty acids (FFAs) to optimize the reaction conditions. The results showed that the optimal conditions were an methanol to oil molar ratio of 10:1, the amount of catalyst of 10%w, and reaction temperature of 60°C.

  14. Sulfonated reduced graphene oxide as a highly efficient catalyst for direct amidation of carboxylic acids with amines using ultrasonic irradiation.

    Science.gov (United States)

    Mirza-Aghayan, Maryam; Tavana, Mahdieh Molaee; Boukherroub, Rabah

    2016-03-01

    Sulfonated reduced graphene oxide nanosheets (rGO-SO3H) were prepared by grafting sulfonic acid-containing aryl radicals onto chemically reduced graphene oxide (rGO) under sonochemical conditions. rGO-SO3H catalyst was characterized by Fourier-transform infrared (FT-IR) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS). rGO-SO3H catalyst was successfully applied as a reusable solid acid catalyst for the direct amidation of carboxylic acids with amines into the corresponding amides under ultrasonic irradiation. The direct sonochemical amidation of carboxylic acid takes place under mild conditions affording in good to high yields (56-95%) the corresponding amides in short reaction times. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Hydrodeoxygenation of phenol over Pd catalysts by in-situ generated hydrogen from aqueous reforming of formic acid

    DEFF Research Database (Denmark)

    Zeng, Ying; Wang, Ze; Lin, Weigang

    2016-01-01

    Hydrodeoxygenation of phenol, as model compound of bio-oil, was investigated over Pd catalysts, using formic acid as a hydrogen donor. The order of activity for deoxygenation of phenol with Pd catalysts was found to be: Pd/SiO2 > Pd/MCM-41 > Pd/CA > Pd/Al2O3 > Pd/HY approximate to Pd/ZrO2 ≈ Pd...

  16. Solvent-Free Esterification of Carboxylic Acids Using Supported Iron Oxide Nanoparticles as an Efficient and Recoverable Catalyst

    Directory of Open Access Journals (Sweden)

    Fatemeh Rajabi

    2016-07-01

    Full Text Available Supported iron oxide nanoparticles on mesoporous materials (FeNP@SBA-15 have been successfully utilized in the esterification of a variety carboxylic acids including aromatic, aliphatic, and long-chain carboxylic acids under convenient reaction conditions. The supported catalyst could be easily recovered after reaction completion and reused several times without any loss in activity after up to 10 runs.

  17. Feasibility study of various sulphonation methods for transforming carbon nanotubes into catalysts for the esterification of palm fatty acid distillate

    International Nuclear Information System (INIS)

    Shuit, Siew Hoong; Tan, Soon Huat

    2014-01-01

    Highlights: • First report on the production of biodiesel from low-value industrial by-product using sulphonated MWCNTs as catalyst. • Various sulphonation methods were used to transform MWCNTs into catalysts. • SO 3 H were successfully grafted on the surface of MWCNTs, which resulted in a high biodiesel yield and reuse capacity. • The maximum FAME yield by sulphonated MWCNTs was higher than for other popular solid acid catalysts. - Abstract: Sulphonated multi-walled carbon nanotubes were synthesised and utilised as catalysts to transform palm fatty acid distillate, the low-value by-product of palm oil refineries, into the more valuable product of biodiesel. The most common method to prepare carbon-based solid acid catalysts is thermal treatment with concentrated sulphuric acid, which is a time-consuming and energy-intensive process. Therefore, the feasibility of other sulphonation methods, such as the in situ polymerisation of acetic anhydride and sulphuric acid, the thermal decomposition of ammonium sulphate and the in situ polymerisation of poly(sodium4-styrenesulphonate), were examined in this study. The esterification reaction was performed at 170 °C for 3 h at a methanol to palm fatty acid distillate ratio of 20 and catalyst loading of 2 wt% in a pressurised reactor. The fatty acid methyl esters yields achieved by the sulphonated multi-walled carbon nanotubes prepared via thermal treatment with concentrated sulphuric acid, the in situ polymerisation of acetic anhydride and sulphuric acid, the thermal decomposition of ammonium sulphate and the in situ polymerisation of poly(sodium4-styrenesulphonate) were 78.1%, 85.8%, 88.0% and 93.4%, respectively. All catalysts could maintain a high catalytic activity even during the fifth cycle. Among the sulphonation methods, the in situ polymerisation of poly(sodium4-styrenesulphonate) produced the catalyst with the highest acid group density. In addition, the resonance structures of the benzenesulphonic acid

  18. Citric acid induced promoted dispersion of Pt on the support and enhanced catalytic activities for a Pt-based catalyst

    Science.gov (United States)

    Cheng, Tianqiong; Wang, Jianli; Wang, Suning; Cui, Yajuan; Zhang, Hailong; Yan, Shuang; Yuan, Shandong; Chen, Yaoqiang

    2017-12-01

    Citric acid (CA), as the chelating agent, was introduced to obtain the enhanced Pt dispersion and catalytic activities for the Pt-based catalysts supported on oxygen-storage material. The role and content of CA were investigated systematically. It was found that the citric acid-assisted catalysts showed better Pt dispersion and smaller nanoparticle size of Pt. Thus, the catalyst had lower reduction temperature, preferable thermostability and possessed more oxidation state of Pt species under the oxidation atmosphere. The citric acid-induced fresh catalysts were excellent to convert CO and the corresponding aged ones exhibited higher activities for the elimination of all the target pollutants. Among the aged catalysts, P2-a (the mole ratio of Pt/CA is 2:1) presented the best performance. Particularly, compared with the reference sample (Pc-a), the light-off temperatures (T50) of NO, HC and CO for P2-a decreased by 39 °C, 42 °C and 72 °C, respectively, and the full-conversion temperatures (T90) of NO, HC and CO for P2-a decreased by 44 °C, 44 °C and 48 °C, respectively. Therefore, this work provides a facile and valid method to manufacture advanced catalysts for purification of the vehicle exhaust in the future.

  19. 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.

  20. 31P NMR Chemical Shifts of Phosphorus Probes as Reliable and Practical Acidity Scales for Solid and Liquid Catalysts.

    Science.gov (United States)

    Zheng, Anmin; Liu, Shang-Bin; Deng, Feng

    2017-10-11

    Acid-base catalytic reaction, either in heterogeneous or homogeneous systems, is one of the most important chemical reactions that has provoked a wide variety of industrial catalytic processes for production of chemicals and petrochemicals over the past few decades. In view of the fact that the catalytic performances (e.g., activity, selectivity, and reaction mechanism) of acid-catalyzed reactions over acidic catalysts are mostly dictated by detailed acidic features, viz. type (Brønsted vs Lewis acidity), amount (concentration), strength, and local environments (location) of acid sites, information on and manipulation of their structure-activity correlation are crucial for optimization of catalytic performances as well as innovative design of novel effective catalysts. This review aims to summarize recent developments on acidity characterization of solid and liquid catalysts by means of experimental 31 P nuclear magnetic resonance (NMR) spectroscopy using phosphorus probe molecules such as trialkylphosphine (TMP) and trialkylphosphine oxides (R 3 PO). In particular, correlations between the observed 31 P chemical shifts (δ 31 P) of phosphorus (P)-containing probes and acidic strengths have been established in conjuction with density functional theory (DFT) calculations, rendering practical and reliable acidity scales for Brønsted and Lewis acidities at the atomic level. As illustrated for a variety of different solid and liquid acid systems, such as microporous zeolites, mesoporous molecular sieves, and metal oxides, the 31 P NMR probe approaches were shown to provide important acid features of various catalysts, surpassing most conventional methods such as titration, pH measurement, Hammett acidity function, and some other commonly used physicochemical techniques, such as calorimetry, temperature-programmed desorption of ammonia (NH 3 -TPD), Fourier transformed infrared (FT-IR), and 1 H NMR spectroscopies.

  1. Gallium-containing polymer brush film as efficient supported Lewis acid catalyst in a glass microreactor

    Directory of Open Access Journals (Sweden)

    Rajesh Munirathinam

    2013-08-01

    Full Text Available Polystyrene sulfonate polymer brushes, grown on the interior of the microchannels in a microreactor, have been used for the anchoring of gallium as a Lewis acid catalyst. Initially, gallium-containing polymer brushes were grown on a flat silicon oxide surface and were characterized by FTIR, ellipsometry, and X-ray photoelectron spectroscopy (XPS. XPS revealed the presence of one gallium per 2–3 styrene sulfonate groups of the polymer brushes. The catalytic activity of the Lewis acid-functionalized brushes in a microreactor was demonstrated for the dehydration of oximes, using cinnamaldehyde oxime as a model substrate, and for the formation of oxazoles by ring closure of ortho-hydroxy oximes. The catalytic activity of the microreactor could be maintained by periodic reactivation by treatment with GaCl3.

  2. A practical and catalyst-free trifluoroethylation reaction of amines using trifluoroacetic acid

    Science.gov (United States)

    Andrews, Keith G.; Faizova, Radmila; Denton, Ross M.

    2017-06-01

    Amines are a fundamentally important class of biologically active compounds and the ability to manipulate their physicochemical properties through the introduction of fluorine is of paramount importance in medicinal chemistry. Current synthesis methods for the construction of fluorinated amines rely on air and moisture sensitive reagents that require special handling or harsh reductants that limit functionality. Here we report practical, catalyst-free, reductive trifluoroethylation reactions of free amines exhibiting remarkable functional group tolerance. The reactions proceed in conventional glassware without rigorous exclusion of either moisture or oxygen, and use trifluoroacetic acid as a stable and inexpensive fluorine source. The new methods provide access to a wide range of medicinally relevant functionalized tertiary β-fluoroalkylamine cores, either through direct trifluoroethylation of secondary amines or via a three-component coupling of primary amines, aldehydes and trifluoroacetic acid. A reduction of in situ-generated silyl ester species is proposed to account for the reductive selectivity observed.

  3. Esterification of fatty acids using sulfated zirconia and composites activated carbon/sulfated zirconia catalysts

    International Nuclear Information System (INIS)

    Brum, Sarah S.; Santos, Valeria C. dos; Destro, Priscila; Guerreiro, Mario Cesar

    2011-01-01

    In this work sulfated zirconia (SZr) and activated carbon/SZr composites produced by impregnation method with or without heating treatment step (CABC/SZr-I and CABC/SZr-I SC) and by the method of synthesis of SZr on the carbon (CABC/SZr-S) was used as catalysts in the esterification reactions of fatty acids. The SZr presented very active, conversions higher than 90% were obtained after 2 h of reaction. The activity of the composite CABC/SZr-I20%SC was up to 92%, however, this was directly related to time and temperature reactions. CABC/SZr-I and CABC/SZr-S were less active in esterification reactions, what could be attributed to its low acidity. (author)

  4. Electrocatalytic properties of carbon-supported Pt-Ru catalysts with the high alloying degree for formic acid electrooxidation

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yu.; Zhou, Yiming; Tang, Yawen; Lu, Tianhong [College of Chemistry and Environmental Science, Nanjing Normal University, Nanjing 210097 (China)

    2010-07-01

    A series of carbon-supported bimetallic Pt-Ru catalysts with high alloying degree and different Pt/Ru atomic ratio have been prepared by a chemical reduction method in the H{sub 2}O/ethanol/tetrahydrofuran (THF) mixture solvent. The structural and electronic properties of catalysts are characterized using X-ray reflection (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM). The electrooxidation of formic acid on these Pt-Ru nanoparticles are investigated by using cyclic voltammetry, chronoamperometry and CO-stripping measurements. The results of electrochemical measurements illustrate that the alloying degree and Pt/Ru atomic ratio of Pt-Ru catalyst play an important role in the electrocatalytic activity of the Pt-Ru/C catalyst for formic acid electrooxidation due to the bifunctional mechanism and the electronic effect. Since formic acid is an intermediate in the methanol electrooxidation on Pt electrode in acidic electrolyte, the observation provides an additional fundamental understanding of the structure-activity relationship of Pt-Ru catalyst for methanol electrooxidation. (author)

  5. Comparison of Tungsten and Molybdenum Carbide Catalysts for the Hydrodeoxygenation of Oleic Acid

    NARCIS (Netherlands)

    Hollak, S.A.W.; Gosselink, R.J.A.; Es, van D.S.; Bitter, J.H.

    2013-01-01

    Group 6 (W, Mo) metal carbide catalysts are promising alternatives to hydrodesulfurization (NiMo, CoMo) catalysts and group 10 (Pd) type catalysts in the deoxygenation of vegetable fats/oils. Herein, we report a comparison of carbon nanofiber-supported W2C and Mo2C catalysts on activity,

  6. Synthesis of biodiesel from waste vegetable oil with large amounts of free fatty acids using a carbon-based solid acid catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Shu, Qing; Gao, Jixian; Nawaz, Zeeshan; Liao, Yuhui; Wang, Dezheng; Wang, Jinfu [Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084 (China)

    2010-08-15

    A carbon-based solid acid catalyst was prepared by the sulfonation of carbonized vegetable oil asphalt. This catalyst was employed to simultaneously catalyze esterification and transesterification to synthesis biodiesel when a waste vegetable oil with large amounts of free fatty acids (FFAs) was used as feedstock. The physical and chemical properties of this catalyst were characterized by a variety of techniques. The maximum conversion of triglyceride and FFA reached 80.5 wt.% and 94.8 wt.% after 4.5 h at 220 C, when using a 16.8 M ratio of methanol to oil and 0.2 wt.% of catalyst to oil. The high catalytic activity and stability of this catalyst was related to its high acid site density (-OH, Broensted acid sites), hydrophobicity that prevented the hydration of -OH species, hydrophilic functional groups (-SO{sub 3}H) that gave improved accessibility of methanol to the triglyceride and FFAs, and large pores that provided more acid sites for the reactants. (author)

  7. A phenyl-sulfonic acid anchored carbon-supported platinum catalyst for polymer electrolyte fuel cell electrodes

    International Nuclear Information System (INIS)

    Selvarani, G.; Sahu, A.K.; Choudhury, N.A.; Sridhar, P.; Pitchumani, S.; Shukla, A.K.

    2007-01-01

    A method, to anchor phenyl-sulfonic acid functional groups with the platinum catalyst supported onto a high surface-area carbon substrate, is reported. The use of the catalyst in the electrodes of a polymer electrolyte fuel cell (PEFC) helps enhancing its performance. Characterization of the catalyst by Fourier transform infra red (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and point-of-zero-charge (PZC) studies suggests that the improvement in performance of the PEFC is facilitated not only by enlarging the three-phase boundary in the catalyst layer but also by providing ionic-conduction paths as well as by imparting negative charge to platinum sites with concomitant oxidation of sulfur present in the carbon support. It is argued that the negatively charged platinum sites help repel water facilitating oxygen to access the catalyst sites. The PEFC with modified carbon-supported platinum catalyst electrodes exhibits 40% enhancement in its power density as compared to the one with unmodified carbon-supported platinum catalyst electrodes

  8. In-Water and Neat Batch and Continuous-Flow Direct Esterification and Transesterification by a Porous Polymeric Acid Catalyst

    OpenAIRE

    Heeyoel Baek; Maki Minakawa; Yoichi M. A. Yamada; Jin Wook Han; Yasuhiro Uozumi

    2016-01-01

    A porous phenolsulphonic acid?formaldehyde resin (PAFR) was developed. The heterogeneous catalyst PAFR was applied to the esterification of carboxylic acids and alcohols, affording the carboxylic acid esters in a yield of up to 95% where water was not removed from the reaction mixture. Surprisingly, the esterification in water as a solvent proceeded to afford the desired esters in high yield. PAFR provided the corresponding esters in higher yield than other homogeneous and heterogeneous catal...

  9. Hydrolysis of Pentosan for Furfural Preparing Using Sulfuric Acid Catalyst to Improve Diesel Engine Fuel Quality

    International Nuclear Information System (INIS)

    Setyadji, Moch

    2007-01-01

    The investigation on furfural preparation from peanut shell using sulfuric acid catalyst has been done. Furfural is an organic solvent used in industry especially petroleum industry. The purpose of this investigation is to know the effects of sulfuric acid concentration and solvent feed ratio towards furfural resulted and the reaction kinetics. The experiment was performed in the batch reactor. The result of this investigation showed that the process optimum condition was reached at sulfuric acid concentration of 7% and the solvent feed ratio of 12.5. The result at the optimum condition above was 5.97% of furfural. The relation between percentage of furfural resulted (Y) and sulfuric acid concentration (X) is Y = 0.893 X 1.7023 . e -0.2554X with average deviation of 5.880 %. The relation between percentage of furfural resulted (Y) and solvent feed ratio (X) is Y = -53.0411 + 9.4137 X - 0.3780 X 2 with average deviation 5.154 %. The relation between reaction rate constant (Y) and sulfuric acid concentration (X) is Y = 3.1916 . 10 -3 + 8.2432 . 10 -3 X - 5.2324 . 10 -4 X 2 with average deviation 8.024 %. (author)

  10. Wet oxidation of glycerol into fine organic acids: catalyst selection and kinetic evaluation

    Directory of Open Access Journals (Sweden)

    J. E. N. Brainer

    2014-12-01

    Full Text Available The liquid phase oxidation of glycerol was performed producing fine organic acids. Catalysts based on Pt, Pd and Bi supported on activated carbon were employed to perform the conversion of glycerol into organic acids at 313 K, 323 K and 333 K, under atmospheric pressure (1.0 bar, in a mechanically agitated slurry reactor (MASR. The experimental results indicated glycerol conversions of 98% with production of glyceric, tartronic and glycolic acids, and dihydroxyacetone. A yield of glyceric acid of 69.8%, and a selectivity of this compound of 70.6% were reached after 4 h of operation. Surface mechanisms were proposed and rate equations were formulated to represent the kinetic behavior of the process. Selective formation of glyceric acid was observed, and the kinetic parameter values indicated the lowest activation energy (38.5 kJ/mol for its production reaction step, and the highest value of the adsorption equilibrium constant of the reactant glycerol (10-4 dm³/mol.

  11. Deoxygenation of Plant Fatty Acid using NiSnK/ SiO2 as Catalyst

    International Nuclear Information System (INIS)

    Chiam, L.T.; Tye, C.T.

    2013-01-01

    Environmental friendly bio-oil which offers supply reliability as a potential alternative fuel, has spurred to rapid development of bio fuels technology. Palm oil is a potential renewable energy source for bio fuels production in the future and Malaysia is one of the world largest palm oil producers. However, undesired oxygen content in the plant fatty acid that contributes to low energy density, high viscosity, and low stability, makes the palm oil not effective to be used as bio fuels directly. In the present study, the performance of silica supported trimetal catalyst, NiSnK/ SiO 2 , on deoxygenation of used palm oil was evaluated. In addition, the effects of operating parameters, such as reaction temperature and weight hourly space velocity were investigated. Conversion of palmitic acid as high as 90 % was achieved in deoxygenation of used palm oil at reaction temperature 350 degree Celsius. In order to have a better understanding on the deoxygenation reaction, model compound system using the major saturated fatty acid in the used palm oil, palmitic acid was also carried out. Palmitic acid was found mainly decarboxylated into n-pentadecane with some decarboxylation and isomerization products. (author)

  12. Catalytic conversion of xylose and corn stalk into furfural over carbon solid acid catalyst in γ-valerolactone.

    Science.gov (United States)

    Zhang, Tingwei; Li, Wenzhi; Xu, Zhiping; Liu, Qiyu; Ma, Qiaozhi; Jameel, Hasan; Chang, Hou-min; Ma, Longlong

    2016-06-01

    A novel carbon solid acid catalyst was synthesized by the sulfonation of carbonaceous material which was prepared by carbonization of sucrose using 4-BDS as a sulfonating agent. TEM, N2 adsorption-desorption, elemental analysis, XPS and FT-IR were used to characterize the catalyst. Then, the catalyst was applied for the conversion of xylose and corn stalk into furfural in GVL. The influence of the reaction time, temperature and dosage of catalyst on xylose dehydration were also investigated. The Brønsted acid catalyst exhibited high activity in the dehydration of xylose, with a high furfural yield of 78.5% at 170°C in 30min. What's more, a 60.6% furfural yield from corn stalk was achieved in 100min at 200°C. The recyclability of the sulfonated carbon catalyst was perfect, and it could be reused for 5times without the loss of furfural yields. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Effect of thermal treatment conditions on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid

    International Nuclear Information System (INIS)

    Gorshkova, T.P.; Tarasova, D.V.; Olen'kova, I.P.; Andrushkevich, T.V.; Nikoro, T.A.

    1984-01-01

    The effect of thermal treatment conditions (temperature and gas medium) on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid is investigated. It is shown that active and selective catalysts are formed in the course of thermal decomposition of the drying product of ammonium metavanadate and paramolybdate under the conditions ensuring the vanadium ion reduction up to tetravalent state with conservation of molybdenum oxidation degree equal to 6. It is possible to realize it either by treatment of the catalyst calcinated in the air flow at 300 deg by the reaction mixture at the activation stage or by gas-reducer flow treatment at 280 deg. Thermal treatment in the reducing medium of the oxidized catalyst does not lead to complete regeneration of its properties

  14. Synthesis of Alkylpoly glucoside from Dextrose-Decanol in the Presence of Silicotungstic Acid Sol-Gel Catalyst

    International Nuclear Information System (INIS)

    Izazi Azzahidah Amin; Mohd Ambar Yarmo; Nik Idris Nik Yusoff

    2013-01-01

    The purpose of this study is to synthesis alkylpoly glucoside via condensation of decanol with dextrose in the presence of heterogenous catalyst. In this study, silicotungstic acid sol-gel (STSG) prepared using sol-gel was used as solid acid catalyst. The catalyst was characterized using BET surface area measurement, X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) surface analysis. The final product was easy to be separated from catalyst without the need of a further neutralization. Silicotungstic acid sol-gel has been found efficient to be solid catalyst for synthesis alkylpoly glucosides. Condensation reaction was carried out 8 hours at 110-120 degree Celsius under vacuum condition at 10 mmHg. The determination of decyl glucoside has been achieved by LC/ ESI-MS/ MS (ToF) giving a mass peak at m/z = 343.2 correspond to the m/z of [M+Na] + . Alkylpoly glucoside produced was analysed by FTIR, 1 H and 13 C NMR spectrometric technique. (author)

  15. Studies of catalyst material for the electro-oxidation of methanol, ethanol, formaldehyde and formic acid

    International Nuclear Information System (INIS)

    Bajwa, S.Z.; Ahmed, R.

    2007-01-01

    Fuel cell is an electrochemical device that converts the chemical energy of reaction directly into the electrical energy. It is highly efficient and environment friendly device. Normally used fuel in fuel cells is hydrogen, but due to the convenience in handling some other liquid fuels are also used and now direct methanol fuel cells are available in the market. Rapid electro-oxidation of the fuel at the fuel cell electrode is necessary for its optimum use. In addition to the methanol, other liquid fuels can also be used in the fuel cell. In this work, cyclic voltammetric studies have been done for the electro-oxidation of the methanol, ethanol, formic acid and formaldehyde on fuel cell catalyst. Platinum electrode is characterized by the measurement of active surface area and roughness factor. Classical electrochemical equations have been employed to find out rate constants for electro-oxidation of methanol fuel and calculations have been carried out to find out thermodynamic parameters. Exchange current density has been evaluated with reference to catalyst by drawing polarization curves. (author)

  16. Direct conversion of cellulose to glycolic acid with a phosphomolybdic acid catalyst in a water medium

    KAUST Repository

    Zhang, Jizhe; Liu, Xin; Sun, Miao; Ma, Xiaohua; Han, Yu

    2012-01-01

    Direct conversion of cellulose to fine chemicals has rarely been achieved. We describe here an eco-benign route for directly converting various cellulose-based biomasses to glycolic acid in a water medium and oxygen atmosphere in which

  17. Determination of arsenate and organic arsenic via potentiometric titration of its heteropoly anions.

    Science.gov (United States)

    Metelka, R; Slavíková, S; Vytras, K

    2002-08-16

    Determination of arsenate based on its conversion to molybdoarsenate heteropoly anions followed by potentiometric titration is described. The titration is realized on the ion-pairing principle using cetylpyridinium chloride (or an analogous titrant containing a lipophilic cation), and is monitored by a carbon paste electrode, although other liquid-polymeric membrane-based electrodes can also be used. Calibration plots of the titrant end-point consumption versus concentration of arsenic were constructed and used to evaluate the content of arsenic in aqueous samples. The method could be applied in the analyses of samples with quite low arsenic content (amounts approximately 10 mug As in 50 cm(3) could be titrated). Organic arsenic was determined analogously after the Schöniger combustion of the sample and conversion of its arsenic to arsenate.

  18. An introduction to catalyst

    International Nuclear Information System (INIS)

    Jeon, Hak Je

    1988-11-01

    This book explains basic conception of catalyst such as definition, velocity of chemical reaction and velocity of catalyst reaction, absorption with absorption energy and chemical absorption, pore structure with the role of pore and measurement of pore structure, catalyst activity on solid structure, electrical property on catalyst activity, choice and design of catalyst, catalytic reaction with reaction velocity and chemical equilibrium and reaction velocity model, measurement of reaction velocity and material analysis, catalyst for mixed compound, catalyst for solid acid and catalyst for supported metal.

  19. Influence of Catalyst Acid/Base Properties in Acrolein Production by Oxidative Coupling of Ethanol and Methanol.

    Science.gov (United States)

    Lilić, Aleksandra; Bennici, Simona; Devaux, Jean-François; Dubois, Jean-Luc; Auroux, Aline

    2017-05-09

    Oxidative coupling of methanol and ethanol represents a new route to produce acrolein. In this work, the overall reaction was decoupled in two steps, the oxidation and the aldolization, by using two consecutive reactors to investigate the role of the acid/base properties of silica-supported oxide catalysts. The oxidation of a mixture of methanol and ethanol to formaldehyde and acetaldehyde was performed over a FeMoO x catalyst, and then the product mixture was transferred without intermediate separation to a second reactor, in which the aldol condensation and dehydration to acrolein were performed over the supported oxides. The impact of the acid/base properties on the selectivity towards acrolein was investigated under oxidizing conditions for the first time. The acid/base properties of the catalysts were investigated by NH 3 -, SO 2 -, and methanol-adsorption microcalorimetry. A MgO/SiO 2 catalyst was the most active in acrolein production owing to an appropriate ratio of basic to acidic sites. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Hydrodeoxygenation of phenols as lignin models under acid-free conditions with carbon-supported platinum catalysts.

    Science.gov (United States)

    Ohta, Hidetoshi; Kobayashi, Hirokazu; Hara, Kenji; Fukuoka, Atsushi

    2011-11-28

    Carbon-supported Pt catalysts are highly active and reusable for the aqueous-phase hydrodeoxygenation of phenols as lignin models without adding any acids. It is suggested that Pt/carbon facilitates the hydrogenation of phenols and the hydrogenolysis of the resulting cyclohexanols.

  1. Catalytic hydrodeoxygenation and hydrocracking of Alcell (R) lignin in alcohol/formic acid mixtures using a Ru/C catalyst

    NARCIS (Netherlands)

    Kloekhorst, Arjan; Shen, Yu; Yie, Yao; Fang, Ma; Heeres, Hero Jan

    The catalytic conversion of Alcell (R) lignin in iso-propanol/formic acid mixtures (1: 1 mass ratio) was explored in a batch set-up using Ru/C as the catalyst (673 K, 4 h, 28% mass lignin intake on solvent). Lignin oils were obtained in good yields (71% mass yields on lignin input) and shown to

  2. 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.

  3. Support screening studies on the hydrogenation of levulinic acid to γ‐valerolactone in water using RU catalysts

    NARCIS (Netherlands)

    Piskun, Anna; Winkelman, Jozef G M; Tang, Zhenchen; Heeres, Hero Jan

    2016-01-01

    γ-Valerolactone (GVL) has been identified as a sustainable platform chemical for the production of carbon-based chemicals. Here we report a screening study on the hydrogenation of levulinic acid (LA) to GVL in water using a wide range of ruthenium supported catalysts in a batch set-up (1 wt. % Ru,

  4. Biomass to fuels : Upgrading of flash pyrolysis oil by reactive distillation using a high boiling alcohol and acid catalysts

    NARCIS (Netherlands)

    Mahfud, F.H.; Melian Cabrera, I.V.; Manurung, R.M.; Heeres, H.J.

    We here report our studies on the upgrading of flash pyrolysis oil using an improved alcohol treatment method. The method consists of treating pyrolysis oil with a high boiling alcohol like n-butanol in the presence of a (solid) acid catalyst at 323-353 K under reduced pressure (<10 kPa). Using this

  5. Synthesis and Characterization of Silicotungstic Acid Nanoparticles Via Sol Gel Technique as a Catalyst in Esterification Reaction

    International Nuclear Information System (INIS)

    Wan Nor Roslam Wan Ishak; Manal Ismail

    2011-01-01

    The purpose of this work is to study the synthesis, characterization and catalytic performance of silicotungstic acid-silica sol gel (STA-SG) as acid catalyst in esterification reaction. The activity and selectivity of STA-SG have been investigated and compared to the STA bulk (STAB) and sulphuric acid (H 2 SO 4 ). The synthesized catalysts were characterized by various techniques shown that the STA-SG catalyst is relatively high in surface area compared to STAB of 460.11 m 2 /g and 0.98 m 2 /g, respectively. From the XPS analyses, there was a significant formation of W-O-Si, W-O-W and Si-O-Si bonding in STA-SG compared to that in STAB. Both the H 2 SO 4 and the STAB gave high conversion of 100 % and 98 %, while lower selectivity of glycerol monooleate (GMO) with 81.6 % and 89.9 %, respectively. On the contrary, the STA-SG enabled a conversion of 94 %, while significantly higher GMO selectivity of 95 % rendering it the more efficient acid catalyst. (author)

  6. Antisolvent Precipitation for the Synthesis of Monodisperse Mesoporous Niobium Oxide Spheres as Highly Effective Solid Acid Catalysts

    KAUST Repository

    Li, Cheng Chao; Dou, Jian; Chen, Luwei; Lin, Jianyi; Zeng, Hua Chun

    2012-01-01

    We have developed a low-cost reaction protocol to synthesize mesoporous Nb 2O 5-based solid acid catalysts with external shape control. In the synthesis, monodisperse glycolated niobium oxide spheres (GNOS) were prepared by means of a simple antisolvent precipitation approach and subsequently converted to mesoporous niobium oxide spheres (MNOS) with a large surface area of 312m 2g -1 by means of the hydrothermal treatment. The antisolvent acetone used to obtain GNOS was recovered through distillation at high purity. The obtained mesoporous MNOS were functionalized further with sulfate anions at different temperatures or incorporated with tungstophosphoric acid to obtain recyclable solid acid catalysts. These MNOS-based catalysts showed excellent performance in a wide range of acid-catalyzed reactions, such as Friedel-Crafts alkylation, esterification, and hydrolysis of acetates. As they are monodisperse spheres with diameters in the submicrometer range, the catalysts can be easily separated and reused. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Antisolvent Precipitation for the Synthesis of Monodisperse Mesoporous Niobium Oxide Spheres as Highly Effective Solid Acid Catalysts

    KAUST Repository

    Li, Cheng Chao

    2012-03-20

    We have developed a low-cost reaction protocol to synthesize mesoporous Nb 2O 5-based solid acid catalysts with external shape control. In the synthesis, monodisperse glycolated niobium oxide spheres (GNOS) were prepared by means of a simple antisolvent precipitation approach and subsequently converted to mesoporous niobium oxide spheres (MNOS) with a large surface area of 312m 2g -1 by means of the hydrothermal treatment. The antisolvent acetone used to obtain GNOS was recovered through distillation at high purity. The obtained mesoporous MNOS were functionalized further with sulfate anions at different temperatures or incorporated with tungstophosphoric acid to obtain recyclable solid acid catalysts. These MNOS-based catalysts showed excellent performance in a wide range of acid-catalyzed reactions, such as Friedel-Crafts alkylation, esterification, and hydrolysis of acetates. As they are monodisperse spheres with diameters in the submicrometer range, the catalysts can be easily separated and reused. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Sulfuric acid functional zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts for alkylation of phenol with tert-butyl alcohol

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Tingshun, E-mail: tshjiang@mail.ujs.edu.cn; Cheng, Jinlian; Liu, Wangping; Fu, Lie; Zhou, Xuping; Zhao, Qian; Yin, Hengbo

    2014-10-15

    Several zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts (SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48) were prepared by the impregnation method and their physicochemical properties were characterized by means of XRD, FT-IR, TEM, NH{sub 3}-TPD and N{sub 2} physical adsorption. Also, the catalytic activities of these solid acid catalysts were evaluated by the alkylation of phenol with tert-butyl alcohol. The effect of weight hour space velocity (WHSV), reaction time and reaction temperature on catalytic properties was also studied. The results show that the SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 still have good mesoporous structure and long range ordering. Compared with the Zr (or Al)–MCM-48 samples, SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 solid acid catalysts have strong acidity and exhibit high activities in alkylation reaction of phenol with tert-butyl alcohol. The SO{sub 4}{sup 2−}/Zr-MCM-48-25 (molar ratio of Si/Zr=0.04) catalyst was found to be the most promising and gave the highest phenol conversion among all catalysts. A maximum phenol conversion of 91.6% with 4-tert-butyl phenol (4-TBP) selectivity of 81.8% was achieved when the molar ratio of tert-butyl alcohol:phenol is 2:1, reaction time is 2 h, the WHSV is 2 h{sup −1} and the reaction temperature is 140 °C. - Highlights: • Sulfuric acid functional mesoporous solid acid catalysts were prepared via impregnation method. • The alkylation of phenol with tert-butyl alcohol was carried out over these solid acid catalysts. • The catalytic activity of SO{sub 4}{sup 2−}/Zr-MCM-48-25 catalyst is much higher than that of the others. • A maximum phenol conversion of 91.6% was achieved under optimum reaction conditions for SO{sub 4}{sup 2−}/Zr-MCM-48-25.

  9. Sulfuric acid functional zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts for alkylation of phenol with tert-butyl alcohol

    International Nuclear Information System (INIS)

    Jiang, Tingshun; Cheng, Jinlian; Liu, Wangping; Fu, Lie; Zhou, Xuping; Zhao, Qian; Yin, Hengbo

    2014-01-01

    Several zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts (SO 4 2− /Zr-MCM-48 and SO 4 2− /Al-MCM-48) were prepared by the impregnation method and their physicochemical properties were characterized by means of XRD, FT-IR, TEM, NH 3 -TPD and N 2 physical adsorption. Also, the catalytic activities of these solid acid catalysts were evaluated by the alkylation of phenol with tert-butyl alcohol. The effect of weight hour space velocity (WHSV), reaction time and reaction temperature on catalytic properties was also studied. The results show that the SO 4 2− /Zr-MCM-48 and SO 4 2− /Al-MCM-48 still have good mesoporous structure and long range ordering. Compared with the Zr (or Al)–MCM-48 samples, SO 4 2− /Zr-MCM-48 and SO 4 2− /Al-MCM-48 solid acid catalysts have strong acidity and exhibit high activities in alkylation reaction of phenol with tert-butyl alcohol. The SO 4 2− /Zr-MCM-48-25 (molar ratio of Si/Zr=0.04) catalyst was found to be the most promising and gave the highest phenol conversion among all catalysts. A maximum phenol conversion of 91.6% with 4-tert-butyl phenol (4-TBP) selectivity of 81.8% was achieved when the molar ratio of tert-butyl alcohol:phenol is 2:1, reaction time is 2 h, the WHSV is 2 h −1 and the reaction temperature is 140 °C. - Highlights: • Sulfuric acid functional mesoporous solid acid catalysts were prepared via impregnation method. • The alkylation of phenol with tert-butyl alcohol was carried out over these solid acid catalysts. • The catalytic activity of SO 4 2− /Zr-MCM-48-25 catalyst is much higher than that of the others. • A maximum phenol conversion of 91.6% was achieved under optimum reaction conditions for SO 4 2− /Zr-MCM-48-25

  10. Cassava Pulp Hydrolysis under Microwave Irradiation with Oxalic Acid Catalyst for Ethanol Production

    Directory of Open Access Journals (Sweden)

    Euis Hermiati

    2014-07-01

    Full Text Available Microwave irradiation is an alternative method of starch hydrolysis that offers a rapid process. The aim of this research was to improve microwave-assisted hydrolysis of cassava pulp by using oxalic acid as a catalyst. Suspension of cassava pulp in 0.5% oxalic acid (1 g/20 mL was subjected to microwave irradiation at 140-230 °C for 5 minutes, with 4 minutes of pre-heating. One gram of fractured activated carbon made of coconut shell was added into a number of suspensions that were subjected to the same conditions of microwave irradiation. The soluble fraction of the hydrolysates was analyzed for its total soluble solids, malto-oligomer distribution, glucose content, pH value, and formation of brown compounds. The effects of the combined severity parameter at a substrate concentration of 5-12.5% on the glucose yield were also evaluated. The highest glucose yield (78% of dry matter was obtained after hydrolysis at 180 °C without activated carbon addition. Heating above 180 °C reduced the glucose yield and increased the pH and the formation of brown compounds. The use of activated carbon in microwave-assisted acid hydrolysis of cassava pulp reduced the glucose yield, but suppressed the formation of brown compounds. The highest glucose yield (70-80% of dry matter was attained at a severity parameter of 1.3-1.5.

  11. Acidity Tunable Ionic Liquids as Catalysts for Conversion of Agar into Mixed Sugars

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Churl; Kim, Hoon Sik [Kyung Hee Univ., Seoul (Korea, Republic of); Ryu, Hyun Jin; Kim, Sang Hyoun; Yoon, Jeong Jun; Kim, Yong Jin [Korea Institute of Industrial Technology, Cheonan (Korea, Republic of)

    2010-02-15

    To summarize, various factors affecting yields of Gal, AG, and 5-HMF formation during saccharification were investigated using agar as a substrate in the presence of several bisulfate-based acidic ionic liquids as catalysts. The result was compared with employing sulfuric acid from the viewpoint of sugar yields and 5-HMF formation. [Bmim][HSO{sub 4}], [Hmim][HSO{sub 4}], [Morph] [HSO{sub 4}], [Bu{sub 4}N][HSO{sub 4}], [Bu{sub 4}P][HSO{sub 4}], [Chol][HSO{sub 4}] showed moderate to high yields of Gal and AG with a remarkable decrease in 5-HMF formation compared with sulfuric acid. Among them, [Chol][HSO{sub 4}] ionic liquid was found to exhibit the highest yield of sugars with an acceptable concentration of 5-HMF that does not inhibit the fermentation process. Generally, there are five major bottom lines for a bioethanol process to be economically viable: the feedstock must be plentiful, inexpensive, in high energy conversion rate, in low demand for food industry, and finally, has to be cultivated in sustainable systems.

  12. Application of isotopic substitution for studing thermal decomposition of silico-12-tungstic acid

    International Nuclear Information System (INIS)

    Khakhinov, V.V.; Pinchuk, I.N.; Tumurova, L.V.; Mokhosoev, M.V.

    1987-01-01

    Using the methods of thermal analysis and isotopic substitution, the mechanism of dehydration and decomposition of silico-12-tungstic acid hydrate is studied. It is found that H-D exchange leads to elevation of temperature of heteropoly acid decomposition. The observed isotopic effect shows that proton transfer is the limiting stage of the reaction

  13. Synthesis and Characterization of Tin (IV Tungstate Nanoparticles – A Solid Acid Catalyst

    Directory of Open Access Journals (Sweden)

    Manoj Sadanandan

    2012-12-01

    Full Text Available Tin (IV tungstate, a tetravalent metal acid salt was synthesized in the nanoform by chemical coprecipitation method using EDTA as capping agent. The material was found to be stable in mineral acids, bases and organic solvents except  in HF and aquaregia. The material was characterized using EDS, TG/DTA, FTIR, XRD, SEM, HRTEM and BET surface area measurement. The molecular formula of the compound is 2SnO2 3WO3.5H2O determined from elemental analysis using TG/DTA. Surface morphology and particle size were obtained using SEM and HRTEM. The surface area was found to be 205-225m2/g. The Na+ exchange capacity found to be 3.8 meq/g, indicates the presence of surface hydroxyl group and hence the presence of Bronsted acid sites. The catalytic activity of the material was tested by using esterification and oxidation as model reactions. For the esterification of different alcohols, the percentage yield was found to be high for n-alcohol compared to isomeric alcohols. Oxidation of benzyl alcohol gives benzaldehyde and benzoic acid as the only products. Copyright © 2012 by BCREC UNDIP. All rights reservedReceived: 12nd June 2012, Revised: 23rd July 2012, Accepted: 29th July 2012[How to Cite: S. Manoj, R. Beena, (2012. Synthesis and Characterization of tin(IV Tungstate Nanoparticles – A Solid Acid Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (2: 105-111. doi:10.9767/bcrec.7.2.3622.105-111] [How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.2.3622.105-111 ] | View in 

  14. Catalytic upgrading of oleic acid into biofuel using Mo modified zeolite supported Ni oxalate catalyst functionalized with fluoride ion

    International Nuclear Information System (INIS)

    Ayodele, O.B.; Abbas, Hazzim F.; Daud, Wan Mohd Ashri Wan

    2014-01-01

    Highlights: • Modification of zeolite with freshly prepared molybdenum oxalate. • Functionalization of Ni oxalate with HF and incorporation into Mo modified zeolite. • Characterization of synthesized Mo modified zeolite supported Ni oxalate catalyst. • Deoxygenation of oleic acid with the synthesized zeolite supported catalyst. • Reusability study on the synthesized zeolite supported catalyst. - Abstract: In this study, fluoride ion functionalized nickel oxalate supported on molybdenum modified zeolite (NiMoFOx/Zeol) catalyst was synthesized, characterized and tested on the hydrodeoxygenation (HDO) of oleic acid (OA) into paraffinic fuel. The NiMoFOx/Zeol characterization results confirmed the presence of both Ni and Mo as well as the formation of NiMoO 4 which is a highly HDO reactive specie at 2θ value of 43.6° according to the XRD result. NiMoFOx/Zeol also showed loss in crystallinity and reduction in the average particle size leading to increase in the pore volume and specific surface area due to the combined effects of fluoride ion presence, oxalic acid functionalization and calcination. The effect of temperature, pressure and NiMoFOx/Zeol loading studied showed that initial increase in their values increased the yield of the target fractions until some points where reduction was observed. The best observed experimental conditions to hydrodeoxygenate 40 g (∼45 mL) of OA into 75% n-C 18 and 23% i-C 18 were 360 °C, 30 mg NiMoFOx/Zeol loading and 20 bar using 100 mL H 2 /min. The presence of i-C 18 was due to the functionalization of the catalyst with fluoride ion. The catalyst reusability result displayed excellent qualities with marginal loss of only 2% in activity after third reuse due to the improved synthesis protocol that employed organometallic precursor. The results are strongly encouraging for further studies toward industrialization of HDO process

  15. Studies on the decomposition of oxalic acid by nitric acid in presence of catalysts

    International Nuclear Information System (INIS)

    Noronha, D.M.; Pius, I.C.; Chaudhury, S.

    2015-01-01

    Impure Plutonium oxalate generated from the recovery of plutonium from waste solutions may require further purification via anion exchange. Conventionally, plutonium oxalate is converted to oxide in a furnace and the oxide is dissolved in Conc. HNO 3 containing HF and purified by anion exchange route. Studies initiated on the decomposition of oxalic acid with Conc. HNO 3 to facilitate direct dissolution of plutonium oxalate and quantitative destruction of oxalate are discussed in this paper. (author)

  16. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

    Science.gov (United States)

    Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

    2018-01-10

    Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

    International Nuclear Information System (INIS)

    Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P.; Yang, Bin

    2017-01-01

    Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.

  18. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Current address: Center of Biomass Engineering/College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 PR China; Wang, Huamin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Kuhn, Eric [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

    2017-11-14

    Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.

  19. Effective depolymerization of concentrated acid hydrolysis lignin using a carbon-supported ruthenium catalyst in ethanol/formic acid media.

    Science.gov (United States)

    Kristianto, Ivan; Limarta, Susan Olivia; Lee, Hyunjoo; Ha, Jeong-Myeong; Suh, Dong Jin; Jae, Jungho

    2017-06-01

    Lignin isolated by two-step concentrated acid hydrolysis of empty fruit bunch (EFB) was effectively depolymerized into a high-quality bio-oil using formic acid (FA) as an in-situ hydrogen source and Ru/C as a catalyst in supercritical ethanol. A bio-oil yield of 66.3wt% with an average molecular weight of 822g/mol and an aromatic monomer content of 6.1wt% was achieved at 350°C and a FA-to-lignin mass ratio of 3 after a reaction time of 60min. The combination of Ru/C and FA also resulted in a significant reduction in the oxygen content of the bio-oil by ∼60% and a corresponding increase in the higher heating value (HHV) to 32.7MJ/kg due to the enhanced hydrodeoxygenation activity. An examination of the FA decomposition characteristics revealed that Ru/C provides a greater increase in the rate of hydrogen production from FA, explaining the efficient depolymerization of lignin in a combined system. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Brown algae hydrolysis in 1-n-butyl-3-methylimidazolium chloride with mineral acid catalyst system.

    Science.gov (United States)

    Malihan, Lenny B; Nisola, Grace M; Chung, Wook-Jin

    2012-08-01

    The amenability of three brown algal species, Sargassum fulvellum, Laminaria japonica and Undaria pinnatifida, to hydrolysis were investigated using the ionic liquid (IL), 1-n-butyl-3-methylimidazolium chloride ([BMIM]Cl). Compositional analyses of the brown algae reveal that sufficient amounts of sugars (15.5-29.4 wt.%) can be recovered. Results from hydrolysis experiments show that careful selection of the type of mineral acid as catalyst and control of acid loading could maximize the recovery of sugars. Optimal reaction time and temperature were determined from the kinetic studies on the sequential reducing sugar (TRS) formation and degradation. Optimal reaction times were determined based on the extent of furfurals formation as TRS degradation products. X-ray diffraction and environmental scanning electron microscopy confirmed the suitability of [BMIM]Cl as solvent for the hydrolysis of the three brown algae. Overall results show the potential of brown algae as renewable energy resources for the production of valuable chemicals and biofuels. Copyright © 2012 Elsevier Ltd. All rights reserved.

  1. A novel method for synthesis of phosphomolybdic acid-modified Pd/C catalysts for oxygen reduction reaction

    Science.gov (United States)

    Zhu, Mingyuan; Gao, Xiaoling; Luo, Guangqin; Dai, Bin

    2013-03-01

    This manuscript reports a convenient method for immobilizing phosphomolybdic acid (HPMo) on polyaniline (PAN-) functionalized carbon supports. The obtained HPMo-PAN-C sample is used as the support to prepare a Pd/HPMo-PAN-C catalyst. The samples are characterized by Fourier transform infrared spectroscopy, transmission electron microscopy and X-ray diffraction analysis. The results suggest that HPMo retains its Keggin structure and that the presence of HPMo reduces the average particle size of the Pd nano-particles in the obtained Pd/HPMo-PAN-C catalyst. Electro-chemical measurements in 0.5 M HClO4 solution reveal that the Pd/HPMo-PAN-C catalyst has higher catalytic activity for oxygen reduction reactions than does a Pd/C catalyst prepared using a similar procedure. The stability of the Pd/HPMo-PAN-C catalyst is evaluated by multiple-cycle voltammetry techniques; the mass catalytic activity decreases by only 10% after 100 scanning cycles.

  2. Tailoring the Synergistic Bronsted-Lewis acidic effects in Heteropolyacid catalysts: Applied in Esterification and Transesterification Reactions

    OpenAIRE

    Tao, Meilin; Xue, Lifang; Sun, Zhong; Wang, Shengtian; Wang, Xiaohong; Shi, Junyou

    2015-01-01

    In order to investigate the influences of Lewis metals on acidic properties and catalytic activities, a series of Keggin heteropolyacid (HPA) catalysts, HnPW11MO39 (M = TiIV, CuII, AlIII, SnIV, FeIII, CrIII, ZrIV and ZnII; for Ti and Zr, the number of oxygen is 40), were prepared and applied in the esterification and transesterification reactions. Only those cations with moderate Lewis acidity had a higher impact. Ti Substituted HPA, H5PW11TiO40, posse lower acid content compared with TixH3−4...

  3. A novel mesoporous sulfated zirconium solid acid catalyst for Friedel-Crafts benzylation reaction

    International Nuclear Information System (INIS)

    Miao, Zhichao; Zhou, Jin; Zhao, Jinping; Liu, Dandan; Bi, Xu; Chou, Lingjun; Zhuo, Shuping

    2017-01-01

    Highlights: • A novel mesoporous ZrO_2/SO_4"2"− has been prepared via a facile one-pot EISA strategy. • The M-ZrO_2/SO_4"2"− exhibited excellent textural and acidic properties. • The introduced S species were homogeneously dispersed in mesoporous skeleton. • The M-ZrO_2/SO_4"2"− exhibited excellent catalytic performance and reusability. - Abstract: In this paper, a novel mesoporous sulfated zirconium (M-ZrO_2/SO_4"2"−) has been gotten by one-pot evaporation-induced self-assembly (one-pot EISA) strategy. The SXRD, N_2-physisorption and TEM characterization techniques indicated that M-ZrO_2/SO_4"2"− possessed distinct mesostructure with big specific surface area (133.5 m"2 g"−"1), large pore volume (0.18 cm"3 g"−"1) and narrow pore size distribution (4.90 nm). Moreover, the existing states and the influence in mesostructure of introduced S species were detailedly investigated by the XRD, N_2-physisorption, TEM, TG-DSC, FT-IR and XPS techniques and the results showed that the S species, which existed as the type of SO_4"2"−, improved the textural properties of prepared materials. In addition, the NH_3-TPD and IR spectra of adsorbed pyridine indicated the existence of strong Brønsted and Lewis acid sites in M-ZrO_2/SO_4"2"− even evacuated at 400 °C. Furthermore, the M-ZrO_2/SO_4"2"− was used as a promise solid acid catalyst and displayed excellent catalytic performance and reusability in Friedel-Crafts benzylation reaction.

  4. A smart strategy to fabricate Ru nanoparticle inserted porous carbon nanofibers as highly efficient levulinic acid hydrogenation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ying; Sun, Cheng-Jun; Brown, Dennis E.; Zhang, Liqiang; Yang, Feng; Zhao, Hairui; Wang, Yue; Ma, Xiaohui; Zhang, Xin; Ren, Yang

    2016-01-01

    Herein, we first put forward a smart strategy to in situ fabricate Ru nanoparticle (NP) inserted porous carbon nanofibers by one-pot conversion of Ru-functionalized metal organic framework fibers. Such fiber precursors are skillfully constructed by cooperative assembly of different proportional RuCl3 and Zn(Ac)2·2H2O along with trimesic acid (H3BTC) in the presence of N,N-dimethylformamide. The following high-temperature pyrolysis affords uniform and evenly dispersed Ru NPs (ca. 12-16 nm), which are firmly inserted into the hierarchically porous carbon nanofibers formed simultaneously. The resulting Ru-carbon nanofiber (Ru-CNF) catalysts prove to be active towards the liquid-phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL), a biomass-derived platform molecule with wide applications in the preparation of renewable chemicals and liquid transportation fuels. The optimal GVL yield of 96.0% is obtained, corresponding to a high activity of 9.23 molLAh–1gRu–1, 17 times of that using the commercial Ru/C catalyst. Moreover, the Ru-CNF catalyst is extremely stable, and can be cycled up to 7 times without significant loss of reactivity. Our strategy demonstrated here reveals new possibilities to make proficient metal catalysts, and provides a general way to fabricate metal-carbon nanofiber composites available for other applications.

  5. Effect of Al content on the gas-phase dehydration of glycerol over silica-alumina-supported silicotungstic acid catalysts

    International Nuclear Information System (INIS)

    Kim, Yong Tae; You, Su Jin; Park, Eun Duck; Jung, Kwangdeog

    2012-01-01

    The gas-phase dehydration of glycerol to acrolein was carried out over silicotungstic acid (H 4 SiW 12 O 40 ·xH 2 O, HSiW) catalysts supported on SiO 2 , η-Al 2 O 3 , and silica-alumina with different Al contents. The HSiW catalysts supported on silica-alumina showed higher glycerol conversions and acrolein yields during the initial 2 h at 315.deg.C than did SiO 2 - and η-Al 2 O 3 -supported HSiW catalysts. Among the tested catalysts, HSiW/Si 0.9 Al 0.1Ox exhibited the highest space-time yield during the initial 2 h. The loaded HSiW species can change the acid types and suppress the formation of carbonaceous species on Al-rich silica-alumina. The deactivated HSiW supported on silica-alumina can be fully regenerated after calcination in air at 500.deg.C. As long as the molar ratio between water and glycerol was in the range of 2-11, the acrolein selectivity increased significantly with increasing water content in the feed, while the surface carbon content decreased owing to the suppression of heavy compounds

  6. Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts.

    Science.gov (United States)

    Murahashi, Shun-Ichi

    2011-01-01

    This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. (Communicated by Ryoji Noyori, M.J.A.).

  7. Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts

    Science.gov (United States)

    MURAHASHI, Shun-Ichi

    2011-01-01

    This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. PMID:21558760

  8. A Comparative Study of Basic, Amphoteric, and Acidic Catalysts in the Oxidative Coupling of Methanol and Ethanol for Acrolein Production.

    Science.gov (United States)

    Lilić, Aleksandra; Wei, Tiantian; Bennici, Simona; Devaux, Jean-François; Dubois, Jean-Luc; Auroux, Aline

    2017-09-11

    The impact of acid/base properties (determined by adsorption microcalorimetry) of various catalysts on the cross-aldolization of acetaldehyde and formaldehyde leading to acrolein was methodically studied in oxidizing conditions starting from a mixture of methanol and ethanol. The aldol condensation and further dehydration to acrolein were carried out on catalysts presenting various acid/base properties (MgO, Mg-Al oxides, Mg/SiO 2 , NbP, and heteropolyanions on silica, HPA/SiO 2 ). Thermodynamic calculations revealed that cross-aldolization is always favored compared with self-aldolization of acetaldehyde, which leads to crotonaldehyde formation. The presence of strong basic sites is shown to be necessary, but a too high amount drastically increases CO x production. On strong acid sites, production of acrolein and carbon oxides (CO x ) does not increase with temperature. The optimal catalyst for this process should be amphoteric with a balanced acid/base cooperation of medium strength sites and a small amount (150 kJ mol -1 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Direct catalytic conversion of brown seaweed-derived alginic acid to furfural using 12-tungstophosphoric acid catalyst in tetrahydrofuran/water co-solvent

    International Nuclear Information System (INIS)

    Park, Geonu; Jeon, Wonjin; Ban, Chunghyeon; Woo, Hee Chul; Kim, Do Heui

    2016-01-01

    Highlights: • Furfural was produced by catalytic conversion of macroalgae-derived alginic acid. • 12-Tungstophosphoric acid (H_3PW_1_2O_4_0) showed remarkable catalytic performance. • Tetrahydrofuran (THF) as a reaction medium significantly enhanced production of furfural. - Abstract: Furfural, a biomass-derived platform chemical, was produced by acid-catalyzed reaction of alginic acid extracted from brown seaweed. Three acid catalysts, H_2SO_4, Amberlyst15 and 12-tungstophosphoric acid (H_3PW_1_2O_4_0), were compared to evaluate their catalytic performance for the alginic acid conversion. The H_3PW_1_2O_4_0 catalyst showed the highest catalytic activity, yielding the maximum furfural yield (33.8%) at 180 °C for 30 min in tetrahydrofuran/water co-solvent. Higher reaction temperature promoted the conversion of alginic acid to furfural, but the transformation of furfural to humin was also accelerated. To our knowledge, this is the highest furfural yield among studies about the direct catalytic conversion of alginic acid. Furthermore, products distribution with time-on-stream was investigated in detail, which led us to propose a reaction pathway.

  10. Conversion of polar and non-polar algae oil lipids to fatty acid methyl esters with solid acid catalysts--A model compound study.

    Science.gov (United States)

    Asikainen, Martta; Munter, Tony; Linnekoski, Juha

    2015-09-01

    Bio-based fuels are becoming more and more important due to the depleting fossil resources. The production of biodiesel from algae oil is challenging compared to terrestrial vegetable oils, as algae oil consists of polar fatty acids, such as phospholipids and glycolipids, as well as non-polar triglycerides and free fatty acids common in vegetable oils. It is shown that a single sulphonated solid acid catalyst can perform the esterification and transesterification reactions of both polar and non-polar lipids. In mild reaction conditions (60-70 °C) Nafion NR50 catalyst produces methyl palmitate (FAME) from the palmitic acid derivatives of di-, and tri-glyceride, free fatty acid, and phospholipid with over 80% yields, with the glycolipid derivative giving nearly 40% yields of FAME. These results demonstrate how the polar and non-polar lipid derivatives of algal oil can be utilised as feedstocks for biodiesel production with a single catalyst in one reaction step. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. 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.

  12. Solvent-Free Biginelli Condensation using Tungstate Sulfuric Acid: a Powerful and Reusable Catalyst for Selective Synthesis

    Directory of Open Access Journals (Sweden)

    Rezvan Rezaee Nasab

    2014-07-01

    Full Text Available Tungstate sulfuric acid (TSA has been prepared and used as a recyclable catalyst for the Biginelli syn-thesis of some biologically active quinazolinones/thiones under solvent-free conditions. This method has advantages such as the avoidance of organic solvents, high yield of pure products, short reaction times, and operational simplicity.  © 2014 BCREC UNDIP. All rightsReceived: 28th April 2014; Revised: 15th May 2014; Accepted: 26th May 2014[ How to Cite: Nasab, R.R., Karami, B., Khodabakhshi, S. (2014. Selective Solvent‐free Biginelli Condensation using Tungstate Sulfuric Acid as Powerful and Reusable Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (2: 142-154. (doi:10.9767/bcrec.9.2.6794.148-154][ Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.2.6794.148-154

  13. Formic Acid Oxidation over Hierarchical Porous Carbon Containing PtPd Catalysts

    Directory of Open Access Journals (Sweden)

    Elena Pastor

    2013-10-01

    Full Text Available The use of high surface monolithic carbon as support for catalysts offers important advantage, such as elimination of the ohmic drop originated in the interparticle contact and improved mass transport by ad-hoc pore design. Moreover, the approach discussed here has the advantage that it allows the synthesis of materials having a multimodal porous size distribution, with each pore size contributing to the desired properties. On the other hand, the monolithic nature of the porous support also imposes new challenges for metal loading. In this work, the use of Hierarchical Porous Carbon (HPC as support for PtPd nanoparticles was explored. Three hierarchical porous carbon samples (denoted as HPC-300, HPC-400 and HPC-500 with main pore size around 300, 400 and 500 nm respectively, are used as porous support. PtPd nanoparticles were loaded by impregnation and subsequent chemical reduction with NaBH4. The resulting material was characterized by EDX, XRD and conventional electrochemical techniques. The catalytic activity toward formic acid and methanol electrooxidation was evaluated by electrochemical methods, and the results compared with commercial carbon supported PtPd. The Hierarchical Porous Carbon support discussed here seems to be promising for use in DFAFC anodes.

  14. Green acetylation of solketal and glycerol formal by heterogeneous acid catalysts to form a biodiesel fuel additive.

    Science.gov (United States)

    Dodson, Jennifer R; Leite, Thays d C M; Pontes, Nathália S; Peres Pinto, Bianca; Mota, Claudio J A

    2014-09-01

    A glut of glycerol has formed from the increased production of biodiesel, with the potential to integrate the supply chain by using glycerol additives to improve biodiesel properties. Acetylated acetals show interesting cold flow and viscosity effects. Herein, a solventless heterogeneously catalyzed process for the acetylation of both solketal and glycerol formal to new products is demonstrated. The process is optimized by studying the effect of acetylating reagent (acetic acid and acetic anhydride), reagent molar ratios, and a variety of commercial solid acid catalysts (Amberlyst-15, zeolite Beta, K-10 Montmorillonite, and niobium phosphate) on the conversion and selectivities. High conversions (72-95%) and selectivities (86-99%) to the desired products results from using acetic anhydride as the acetylation reagent and a 1:1 molar ratio with all catalysts. Overall, there is a complex interplay between the solid catalyst, reagent ratio, and acetylating agent on the conversion, selectivities, and byproducts formed. The variations are discussed and explained in terms of reactivity, thermodynamics, and reaction mechanisms. An alternative and efficient approach to the formation of 100% triacetin involves the ring-opening, acid-catalyzed acetylation from solketal or glycerol formal with excesses of acetic anhydride. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Deoxygenation of Palmitic and Lauric Acids over Pt/ZIF-67 Membrane/Zeolite 5A Bead Catalysts.

    Science.gov (United States)

    Yang, Liqiu; Carreon, Moises A

    2017-09-20

    The deoxygenation of palmitic and lauric acids over 0.5 wt % Pt/ZIF-67 membrane/zeolite 5A bead catalysts is demonstrated. Almost complete conversion (% deoxygenation of ≥95%) of these two fatty acids was observed over both fresh and recycled catalyst after a 2 h reaction time. The catalysts displayed high selectivity to pentadecane and undecane via decarboxylation reaction pathway even at low 0.5 wt % Pt loading. Selectivity to pentadecane and undecane as high as ∼92% and ∼94% was observed under CO 2 atmosphere when palmitic and lauric acids were used respectively as reactants. Depending on the reaction gas atmosphere, two distinctive reaction pathways were observed: decarboxylation and hydrodeoxygenation. Specifically, it was found that decarboxylation reaction pathway was more favorable in the presence of helium and CO 2 , while hydrodeoxygenation pathway strongly competed against the decarboxylation pathway when hydrogen was employed during the deoxygenation reactions. Esters were identified as the key reaction intermediates leading to decarboxylation and hydrodeoxygenation pathways.

  16. Preparation of a Carbon-Based Solid Acid Catalyst by Sulfonating Activated Carbon in a Chemical Reduction Process

    Directory of Open Access Journals (Sweden)

    Xiao-Yan Liu

    2010-10-01

    Full Text Available Sulfonated (SO3H-bearing activated carbon (AC-SO3H was synthesized by an aryl diazonium salt reduction process. The obtained material had a SO3H density of 0.64 mmol·g-1 and a specific surface area of 602 m2·g-1. The catalytic properties of AC-SO3H were compared with that of two commercial solid acid catalysts, Nafion NR50 and Amberlyst-15. In a 10-h esterification reaction of acetic acid with ethanol, the acid conversion with AC-SO3H (78% was lower than that of Amberlyst-15 (86%, which could be attributed to the fact that the SO3H density of the sulfonated carbon was lower than that of Amberlyst-15 (4.60 mmol·g-1. However, AC-SO3H exhibited comparable and even much higher catalytic activities than the commercial catalysts in the esterification of aliphatic acids with longer carbon chains such as hexanoic acid and decanoic acid, which may be due to the large specific surface area and mesoporous structures of the activated carbon. The disadvantage of AC-SO3H is the leaching of SO3H group during the reactions.

  17. Continuous synthesis of Oleyl Oleate in supercritical carbon oxide using solid p-Toluenesulfonic Acid as catalyst

    International Nuclear Information System (INIS)

    Ghaziaskar, H.; Ikushima, Y.

    2000-01-01

    Supercritical carbon dioxide (Sc-CO 2 ) was used as solvent to synthesize oleyl oleate as an analog of Jojoba oil from oleic acid and oleyl alcohol with high conversion (100%) of the acid into ester in a short time of 100 min. Utilizing a low cost solid catalyst, p-toluenesulfonic acid monohydrate , the esterification reaction was performed, without any prior preparation step, in a flow mode, at a pressure of 147 bar and a temperature of 60 d eg C. This method seems industrially suitable for the production of oleyl oleate. The solubility of a mixture of oleyl alcohol and oleic acid in Sc-CO 2 were also measured to calculate the alcohol to acid ratio and the esterification yield

  18. Nb-Based Zeolites: Efficient bi-Functional Catalysts for the One-Pot Synthesis of Succinic Acid from Glucose

    Directory of Open Access Journals (Sweden)

    Magdi El Fergani

    2017-12-01

    Full Text Available The one-pot production of succinic acid from glucose was investigated in pure hot water as solvent using Nb (0.02 and 0.05 moles%-Beta zeolites obtained by a post-synthesis methodology. Structurally, they are comprised of residual framework Al-acid sites, extra-framework isolated Nb (V and Nb2O5 pore-encapsulated clusters. The Nb-modified Beta-zeolites acted as bi-functional catalysts in which glucose is dehydrated to levulinic acid (LA which, further, suffers an oxidation process to succinic acid (SA. After the optimization of the reaction conditions, that is, at 180 °C, 18 bar O2, and 12 h reaction time, the oxidation of glucose occurred with a selectivity to succinic acid as high as 84% for a total conversion.

  19. Catalytic Upgrading of bio-oil using 1-octene and 1-butanol over sulfonic acid resin catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhijun; Wang, Qingwen; Tripathi, Prabhat; Pittman, Charles U.

    2011-02-04

    Raw bio-oil from fast pyrolysis of biomass must be refined before it can be used as a transporation fuel, a petroleum refinery feed or for many other fuel uses. Raw bio-oil was upgraded with the neat model olefin, 1-octene, and with 1-octene/1-butanol mixtures over sulfonic acid resin catalysts frin 80 to 150 degrees celisus in order to simultaneously lower water content and acidity and to increase hydrophobicity and heating value. Phase separation and coke formation were key factors limiting the reaction rate during upgrading with neat 1-octene although octanols were formed by 1-octene hydration along with small amounts of octyl acetates and ethers. GC-MS analysis confirmed that olefin hydration, carboxylic acid esterification, acetal formation from aldehydes and ketones and O- and C-alkylations of phenolic compounds occurred simultaneously during upgrading with 1-octene/1-butanol mixtures. Addition of 1-butanol increased olefin conversion dramatically be reducing mass transfer restraints and serving as a cosolvent or emulsifying agent. It also reacted with carboxylic acids and aldehydes/ketones to form esters, and acetals, respectively, while also serving to stabilize bio-oil during heating. 1-Butanol addition also protected the catalysts, increasing catalyst lifetime and reducing or eliminationg coking. Upgrading sharply increased ester content and decreased the amounts of levoglucosan, polyhydric alcohols and organic acids. Upgrading lowered acidity (pH value rise from 2.5 to >3.0), removed the uppleasant ordor and increased hydrocarbon solubility. Water content decreased from 37.2% to < 7.5% dramatically and calorific value increased from 12.6 MJ kg to about 30.0 MJ kg.

  20. Optimization of renewable levulinic acid production from glucose conversion catalyzed by Fe/HY zeolite catalyst in aqueous medium

    International Nuclear Information System (INIS)

    Ramli, Nur Aainaa Syahirah; Amin, Nor Aishah Saidina

    2015-01-01

    Highlights: • Dehydration of glucose as model compound to LA over Fe/HY zeolite catalyst. • RSM coupled with BBD for optimization of LA yield from glucose. • Optimization involving evaluation of four parameters gave 61.8% of optimum LA yield. • Direct conversion of OPF over Fe/HY zeolite yielded 17.6% LA with 54.8% efficiency. • Reusability of Fe/HY zeolite catalyst was tested for five successive cycles. - Abstract: Levulinic acid (LA) is a versatile chemical with numerous applications. In this study, the conversions of glucose and oil palm fronds (OPF) to LA have been conducted over 10% Fe/HY zeolite catalyst. The optimization of LA yield from glucose conversion using Box–Behnken design and response surface methodology reported 61.8% yield, which can be achieved at temperature 173.4 °C, reaction time 3.3 h, 0.93 g of glucose and 0.89 g 10% Fe/HY zeolite. The LA yield from OPF conversion conducted at the optimum conditions was 17.6% with 54.8% process efficiency. It was also observed that Fe leaching from 10% Fe/HY zeolite was insignificant and recycled 10% Fe/HY zeolite gave sufficient performance for five successive cycles. This study emphasizes the potential of Fe/HY zeolite catalyst for catalytic conversion of lignocellulosic biomass to LA

  1. A Single-step Process to Convert Karanja Oil to Fatty Acid Methyl Esters Using Amberlyst15 as a Catalyst

    Directory of Open Access Journals (Sweden)

    Arun K. Gupta

    2018-03-01

    Full Text Available Karanja oil was successfully converted to fatty acid methyl esters (FAME in a single- step process using Amberlyst15 as a catalyst. A methanol to oil ratio of 6 was required to retain the physical structure of the Amberlyst15 catalyst. At higher methanol to oil ratios, the Amberlyst15 catalyst disintegrated. Disintegration of Amberlyst15 caused an irreversible loss in catalytic activity. This loss in activity was due to a decrease in surface area of Amberlyst15, which was caused by a decrease in its mesoporous volume. It appeared that the chemical nature of Amberlyst15 was unaffected. Reuse of Amberlyst15 with a methanol to oil ratio of 6:1 also revealed a loss in FAME yield. However, this loss in activity was recovered by heating the used Amberlyst15 catalyst to 393 K. The kinetic parameters of a power law model were successfully determined for a methanol to oil ratio of 6:1. An activation energy of 54.9 kJ mol–1 was obtained.

  2. A novel mesoporous sulfated zirconium solid acid catalyst for Friedel-Crafts benzylation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Zhichao; Zhou, Jin; Zhao, Jinping; Liu, Dandan; Bi, Xu [School of Chemical Engineering, Shandong University of Technology, Zibo, 255049 (China); Chou, Lingjun, E-mail: ljchou@licp.cas.cn [State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 (China); Zhuo, Shuping, E-mail: zhuosp_academic@yahoo.com [School of Chemical Engineering, Shandong University of Technology, Zibo, 255049 (China)

    2017-07-31

    Highlights: • A novel mesoporous ZrO{sub 2}/SO{sub 4}{sup 2−} has been prepared via a facile one-pot EISA strategy. • The M-ZrO{sub 2}/SO{sub 4}{sup 2−} exhibited excellent textural and acidic properties. • The introduced S species were homogeneously dispersed in mesoporous skeleton. • The M-ZrO{sub 2}/SO{sub 4}{sup 2−} exhibited excellent catalytic performance and reusability. - Abstract: In this paper, a novel mesoporous sulfated zirconium (M-ZrO{sub 2}/SO{sub 4}{sup 2−}) has been gotten by one-pot evaporation-induced self-assembly (one-pot EISA) strategy. The SXRD, N{sub 2}-physisorption and TEM characterization techniques indicated that M-ZrO{sub 2}/SO{sub 4}{sup 2−} possessed distinct mesostructure with big specific surface area (133.5 m{sup 2} g{sup −1}), large pore volume (0.18 cm{sup 3} g{sup −1}) and narrow pore size distribution (4.90 nm). Moreover, the existing states and the influence in mesostructure of introduced S species were detailedly investigated by the XRD, N{sub 2}-physisorption, TEM, TG-DSC, FT-IR and XPS techniques and the results showed that the S species, which existed as the type of SO{sub 4}{sup 2−}, improved the textural properties of prepared materials. In addition, the NH{sub 3}-TPD and IR spectra of adsorbed pyridine indicated the existence of strong Brønsted and Lewis acid sites in M-ZrO{sub 2}/SO{sub 4}{sup 2−} even evacuated at 400 °C. Furthermore, the M-ZrO{sub 2}/SO{sub 4}{sup 2−} was used as a promise solid acid catalyst and displayed excellent catalytic performance and reusability in Friedel-Crafts benzylation reaction.

  3. Methanetrisulfonic Acid: A Highly Efficient Strongly Acidic Catalyst for Wagner-Meerwein Rearrangement, Friedel-Crafts Alkylation and Acylation Reactions. Examples from Vitamin E Synthesis

    Directory of Open Access Journals (Sweden)

    Francesco Pace

    2009-04-01

    Full Text Available Methanetrisulfonic acid had been prepared for the first time over 140 years ago, but it was used only scarcely in chemical transformations. In the course of our activities dealing with key-steps of industrial syntheses of vitamins, e.g. economically important vitamin E (acetate, we found that methanetrisulfonic acid is an extremely effective catalyst in a variety of reactions. Examples of its applications are Wagner-Meerwein rearrangements, Friedel-Crafts alkylations and ring closures, as well as acylation reactions. Use of this catalyst in truly catalytic amounts (0.04-1.0 mol% resulted in highly selective transformations and yields over 95%. (Remark by the authors: We are describing only one example each for the various types of reactions. Therefore, it would be more appropriate to write (here and in the Introduction and in the Conclusion sections: “Wagner-Meerwein rearrangement, Friedel-Crafts alkylation and ring closure, as well as acylation reactions”

  4. Esterification of oleic acid in a three-phase, fixed-bed reactor packed with a cation exchange resin catalyst.

    Science.gov (United States)

    Son, Sung Mo; Kimura, Hiroko; Kusakabe, Katsuki

    2011-01-01

    Esterification of oleic acid was performed in a three-phase fixed-bed reactor with a cation exchange resin catalyst (Amberlyst-15) at high temperature, which was varied from 80 to 120 °C. The fatty acid methyl ester (FAME) yields in the fixed-bed reactor were increased with increases in the reaction temperature, methanol flow rate and bed height. Moreover, the FAME yields were higher than those obtained using a batch reactor due to an equilibrium shift toward the product that resulted from continuous evaporation of the produced water. In addition, there was no catalyst deactivation during the esterification of oleic acid. However, addition of sunflower oil to the oleic acid reduced the FAME yield obtained from simultaneous esterification and transesterification. The FAME yield was 97.5% at a reaction temperature of 100 °C in the fixed-bed with a height of 5 cm when the methanol and oleic acid feed rates were 8.6 and 9.0 mL/h, respectively. Copyright © 2010 Elsevier Ltd. All rights reserved.

  5. 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.)

  6. Statistical Optimization for Acid Hydrolysis of Microcrystalline Cellulose and Its Physiochemical Characterization by Using Metal Ion Catalyst

    Directory of Open Access Journals (Sweden)

    Md. Ziaul Karim

    2014-10-01

    Full Text Available Hydrolyzing the amorphous region while keeping the crystalline region unaltered is the key technology for producing nanocellulose. This study investigated if the dissolution properties of the amorphous region of microcrystalline cellulose can be enhanced in the presence of Fe3+ salt in acidic medium. The process parameters, including temperature, time and the concentration of metal chloride catalyst (FeCl3, were optimized by using the response surface methodology (RSM. The experimental observation demonstrated that temperature and time play vital roles in hydrolyzing the amorphous sections of cellulose. This would yield hydrocellulose with higher crystallinity. The factors that were varied for the production of hydrocellulose were the temperature (x1, time (x2 and FeCl3 catalyst concentration (x3. Responses were measured in terms of percentage of crystallinity (y1 and the yield (y2 of the prepared hydrocellulose. Relevant mathematical models were developed. Analysis of variance (ANOVA was carried out to obtain the most significant factors influencing the responses of the percentage of crystallinity and yield. Under optimum conditions, the percentage of crystallinity and yield were 83.46% and 86.98% respectively, at 90.95 °C, 6 h, with a catalyst concentration of 1 M. The physiochemical characteristics of the prepared hydrocellulose were determined in terms of XRD, SEM, TGA and FTIR analyses. The addition of FeCl3 salt in acid hydrolyzing medium is a novel technique for substantially increasing crystallinity with a significant morphological change.

  7. Poly (Ethylene Glycol)-Bound Sulphonic Acid as a Novel Catalyst for ...

    African Journals Online (AJOL)

    NICO

    reaction is carried out in aqueous solution,36,37 refluxing benzene ... These are of two types; soluble and ... filtration, isolation is easier with polymer-bound catalyst of ..... reaction mixture was cooled to room temperature and the result-.

  8. Cavitation assisted synthesis of fatty acid methyl esters from sustainable feedstock in presence of heterogeneous catalyst using two step process.

    Science.gov (United States)

    Dubey, Sumit M; Gole, Vitthal L; Gogate, Parag R

    2015-03-01

    The present work reports the intensification aspects for the synthesis of fatty acid methyl esters (FAME) from a non-edible high acid value Nagchampa oil (31 mg of KOH/g of oil) using two stage acid esterification (catalyzed by H₂SO₄) followed by transesterification in the presence of heterogeneous catalyst (CaO). Intensification aspects of both stages have been investigated using sonochemical reactors and the obtained degree of intensification has been established by comparison with the conventional approach based on mechanical agitation. It has been observed that reaction temperature for esterification reduced from 65 to 40 °C for the ultrasonic approach whereas there was a significant reduction in the optimum reaction time for transesterification from 4h for the conventional approach to 2.5h for the ultrasound assisted approach. Also the reaction temperature reduced marginally from 65 to 60 °C and yield increased from 76% to 79% for the ultrasound assisted approach. Energy requirement and activation energy for both esterification and transesterification was lower for the ultrasound based approach as compared to the conventional approach. The present work has clearly established the intensification obtained due to the use of ultrasound and also illustrated the two step approach for the synthesis of FAME from high acid value feedstock based on the use of heterogeneous catalyst for the transesterification step. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Reductive dechlorination of trichloroacetic acid (TCAA) by electrochemical process over Pd-In/Al_2O_3 catalyst

    International Nuclear Information System (INIS)

    Liu, Yanzhen; Mao, Ran; Tong, Yating; Lan, Huachun; Zhang, Gong; Liu, Huijuan; Qu, Jiuhui

    2017-01-01

    Highlights: • TCAA was efficiently removed by Pd-In/Al_2O_3 based electro-reductive process. • The active species for TCAA electroreduction involved electron (e"−) and atomic H*. • The atomic H* played a major contribution to TCAA removal. - Abstract: Electrochemical reduction treatment was found to be a promising method for dechlorination of Trichloroacetic acid (TCAA), and acceleration of electron transfer or enhancement of the concentration of atomic H* significantly improve the electrochemical dechlorination process. Bimetallic Pd-based catalysts have the unique property of simultaneously catalyzing the production of atomic H* and reducing target pollutants. Herein, a bimetallic Pd–In electrocatalyst with atomic ratio of 1:1 was evenly deposited on an Al_2O_3 substrate, and the bimetallic Pd-In structure was confirmed via X-ray photoelectron spectroscopy (XPS). Electrochemical removal of trichloroacetic acid (TCAA) by the Pd-In/Al_2O_3 catalyst was performed in a three-dimensional reactor. 94% of TCAA with the initial concentration of 500 μg L"−"1 could be degraded within 30 min under a relatively low current density (0.9 mA cm"−"2). In contrast to the presence of refractory intermediates (dichloroacetic acid (DCAA)) found in the Pd/Al_2O_3 system, TCAA could be thoroughly reduced to monochloroacetic acid (MCAA) using Pd-In/Al_2O_3 catalysts. According to scavenger experiments, an electron transfer process and atomic H* formation function both existed in the TCAA reduction process, and the enhanced indirect atomic H* reduction process (confirmed by ESR signals) played a chief role in the TCAA removal. Moreover, the synergistic effects of Pd and In were proven to be able to enhance both direct electron transfer and indirect atomic H* formation, indicating a promising prospect for bimetallic electrochemical reduction treatment.

  10. Construction of Bifunctional Co/H-ZSM-5 Catalysts for the Hydrodeoxygenation of Stearic Acid to Diesel-range Alkanes.

    Science.gov (United States)

    Wu, Guangjun; Zhang, Nan; Dai, Weili; Guan, Naijia; Li, Landong

    2018-04-27

    Bifunctional Co/H-ZSM-5 zeolites were prepared by surface organometallic chemistry grafting route, namely by the stoichiometric reaction between cobaltocene and the Brønsted acid sites in zeolites, and applied to the model reaction of stearic acid catalytic hydrodeoxygenation. Cobalt species existed in the form of isolated Co2+ ions at exchange positions after grafting, transformed to CoO species on the surface of zeolite and stabilized inside zeolite channels upon calcination in air, and finally reduced to metallic cobalt species of homogeneous clusters of ca. 1.5 nm by hydrogen. During this process, the Brønsted acid sites of H-ZSM-5 zeolites could be preserved with acid strength slightly reduced. The as-prepared bifunctional catalyst exhibited a ~16 times higher activity in stearic acid hydrodeoxygenation (2.11 gSAgcat-1h-1) than the reference catalyst (0.13 gSAgcat-1h-1) prepared by solid-state ion exchange, and a high C18/C17 ratio of ~24 was achieved as well. The remarkable hydrodeoxygenation performance of bifunctional Co/H-ZSM-5 could be explained from the effective synergy between the uniformed metallic cobalt clusters and the Brønsted acid sites in H-ZSM-5 zeolite. The simplified reaction network and kinetics of stearic acid hydrodeoxygenation catalyzed by the as-prepared bifunctional Co/H-ZSM-5 zeolites were also investigated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Catalytic Epoxidation of Limonene

    Directory of Open Access Journals (Sweden)

    E. Herrero

    2000-03-01

    Full Text Available The epoxidation of limonene with hidrogen peroxide was studied over zeolite Tibeta (a large pore material and heteropoly acids on carbono and alumina supported. PW11/C was catalyst the best tested.

  12. Synthesis of mesoporous Cr/ZSM-5 and W-Cr/ZSM-5 zeolite catalysts for oxidation of unsaturated fatty acid

    Directory of Open Access Journals (Sweden)

    Phan Huy Hoang

    2017-10-01

    Full Text Available The mesoporous Cr/ZSM-5 and W-Cr/ZSM-5 zeolites have been successfully synthesized by loading chromium and tungsten on zeolite support. The metal loaded ZSM-5 catalysts were analyzed by several characterizations such as XRD, SEM-EDS, TEM, and BET. The catalytic activities and recycle efficiency were also investigated by applying catalysts for oxidation of oleic acid. These catalysts exhibited the high catalytic efficiency for cleavage of double bond with the use of H2O2. The oleic conversion of 88.7% and 93.3% could be achieved for Cr/ZSM-5 and W-Cr/ZSM-5 catalyst, respectively. Moreover, the modified ZSM-5 catalysts also demonstrated a long life time and high stability.

  13. Metaloxide--ZrO2 catalysts for the esterification and transesterification of free fatty acids and triglycerides to obtain bio-diesel

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Manhoe; Salley, Steven O.; Ng, K. Y. Simon

    2016-09-06

    Mixed metal oxide catalysts (ZnO, CeO, La2O3, NiO, Al203, SiO2, TiO2, Nd2O3, Yb2O3, or any combination of these) supported on zirconia (ZrO2) or hydrous zirconia are provided. These mixed metal oxide catalysts can be prepared via coprecipitation, impregnation, or sol-gel methods from metal salt precursors with/without a Zirconium salt precursor. Metal oxides/ZrO2 catalyzes both esterification and transesterification of oil containing free fatty acids in one batch or in single stage. In particular, these mixed metal oxides supported or added on zirconium oxide exhibit good activity and selectivity for esterification and transesterification. The low acid strength of this catalyst can avoid undesirable side reaction such as alcohol dehydration or cracking of fatty acids. Metal oxides/ZrO2 catalysts are not sensitive to any water generated from esterification. Thus, esterification does not require a water free condition or the presence of excess methanol to occur when using the mixed metal oxide catalyst. The FAME yield obtained with metal oxides/ZrO2 is higher than that obtained with homogeneous sulfuric acid catalyst. Metal oxides/ZrO2 catalasts can be prepared as strong pellets and in various shapes for use directly in a flow reactor. Furthermore, the pellet has a strong resistance toward dissolution to aqueous or oil phases.

  14. Tailoring the Synergistic Bronsted-Lewis acidic effects in Heteropolyacid catalysts: Applied in Esterification and Transesterification Reactions.

    Science.gov (United States)

    Tao, Meilin; Xue, Lifang; Sun, Zhong; Wang, Shengtian; Wang, Xiaohong; Shi, Junyou

    2015-09-16

    In order to investigate the influences of Lewis metals on acidic properties and catalytic activities, a series of Keggin heteropolyacid (HPA) catalysts, HnPW11MO39 (M = Ti(IV), Cu(II), Al(III), Sn(IV), Fe(III), Cr(III), Zr(IV) and Zn(II); for Ti and Zr, the number of oxygen is 40), were prepared and applied in the esterification and transesterification reactions. Only those cations with moderate Lewis acidity had a higher impact. Ti Substituted HPA, H5PW11TiO40, posse lower acid content compared with Ti(x)H(3-4x)PW12O40 (Ti partial exchanged protons in saturated H3PW12O40), which demonstrated that the Lewis metal as an addenda atom (H5PW11TiO40) was less efficient than those as counter cations (Ti(x)H(3-4x)PW12O40). On the other hand, the highest conversion reached 92.2% in transesterification and 97.4% in esterification. Meanwhile, a good result was achieved by H5PW11TiO40 in which the total selectivity of DAG and TGA was 96.7%. In addition, calcination treatment to H5PW11TiO40 make it insoluble in water which resulted in a heterogeneous catalyst feasible for reuse.

  15. Transesterification of Jatropha oil with dimethyl carbonate to produce fatty acid methyl ester over reusable Ca–La–Al mixed-oxide catalyst

    International Nuclear Information System (INIS)

    Syamsuddin, Y.; Murat, M.N.; Hameed, B.H.

    2015-01-01

    Highlights: • Transesterification of Jatropha oil over CaO-based catalyst. • Physicochemical properties of the synthesized catalyst. • Best reaction condition for FAME synthesis. • The catalyst showed high activity and stability for transesterification with Jatropha oil. - Abstract: Jatropha oil (JO) was transesterified with dimethyl carbonate (DMC) to produce fatty acid methyl ester (FAME) over synthesized Ca–La–Al mixed-oxide catalyst. The influence of different parameters on transesterification of Jatropha oil was investigated in a batch reactor. These parameters included reaction temperature (110–160 °C), reaction time (30–240 min), DMC-to-oil molar ratio (4:1–18:1) and catalyst loading amount (1–10 wt.%, based on the oil weight). The mixed-oxide catalyst with a molar ratio of 6:2:1 (Ca–La–Al) showed high catalytic activity for FAME synthesis. More than 90% of FAME was obtained under the following reaction conditions: 150 °C, reaction temperature; 180 min, reaction time; 15:1, DMC-to-oil molar ratio; and 7 wt.% amount of catalyst loading. The catalyst also exhibited high stability and could be reused for up to five cycles with less than 5% yield reduction per cycle.

  16. Efficient hydrolysis of cellulose over a magnetic lignin-derived solid acid catalyst in 1-butyl-3-methylimidazolium chloride

    International Nuclear Information System (INIS)

    Hu, Lei; Wu, Zhen; Xu, Jiaxing; Zhou, Shouyong; Tang, Guodong

    2016-01-01

    A green and efficient strategy for the hydrolysis of cellulose was developed by using a magnetic lignin-derived solid acid catalyst (MLC-SO 3 H) in the presence of ionic liquid 1-butyl-3-methylimidazolium chloride ([BMIM]Cl). The results indicated that reaction temperature, reaction time, catalyst loading and water content have a big influence on the yield of total reducing sugars (TRS). By optimizing these reaction parameters, 69.3% TRS yield was observed at 140 .deg. C for 150 min with the addition of 40 wt% MLC-SO 3 H and 1 wt% water. More importantly, MLC-SO 3 H could be easily separated from the reaction mixture with an external magnet and could be repeatedly used five times without an obvious loss of catalytic activity, demonstrating that it possessed excellent recyclability. Furthermore, a plausible mechanism involving three consecutive processes of dissolution, adsorption and catalysis for the hydrolysis of cellulose in [BMIM]Cl over a catalyst of MLC-SO 3 H was also proposed.

  17. Picolinamide-Based Iridium Catalysts for Dehydrogenation of Formic Acid in Water: Effect of Amide N Substituent on Activity and Stability.

    Science.gov (United States)

    Kanega, Ryoichi; Onishi, Naoya; Wang, Lin; Murata, Kazuhisa; Muckerman, James T; Fujita, Etsuko; Himeda, Yuichiro

    2018-03-01

    To develop highly efficient catalysts for dehydrogenation of formic acid in water, we investigated several Cp*Ir catalysts with various amide ligands. The catalyst with an N-phenylpicolinamide ligand exhibited a TOF of 118 000 h -1 at 60 °C. A constant rate (TOF>35 000 h -1 ) was maintained for six hours, and a TON of 1 000 000 was achieved at 50 °C. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Toward an Active and Stable Catalyst for Oxygen Evolution in Acidic Media: Ti-Stabilized MnO2

    DEFF Research Database (Denmark)

    Frydendal, Rasmus; Paoli, Elisa Antares; Chorkendorff, Ib

    2015-01-01

    Catalysts are required for the oxygen evolution reaction, which are abundant, active, and stable in acid. MnO2 is a promising candidate material for this purpose. However, it dissolves at high overpotentials. Using first-principles calculations, a strategy to mitigate this problem by decorating...... undercoordinated surface sites of MnO2 with a stable oxide is developed here. TiO2 stands out as the most promising of the different oxides in the simulations. This prediction is experimentally verified by testing sputter-deposited thin films of MnO2 and Ti-MnO2. A combination of electrochemical measurements...

  19. Solvent-Free Synthesis of Aryl Iodide Using Nano SiO2/HIO4 as a Reusable Acid Catalyst

    Directory of Open Access Journals (Sweden)

    A. Bamoniri

    2014-07-01

    Full Text Available An efficient and environmentally benign   method for the synthesis of aryl iodides have been developed by diazotization of aromatic amines with NaNO2 and nanosilica periodic acid (nano-SPIA as a green catalyst via grinding followed by a sandmeyer iodination by KI under solvent-free conditions at room temperature. The ensuing aryl diazonium salts supported on nano-SPIA were sufficiently stable to be kept at room temperature in the dry state. This method is a novel, efficient, eco-friendly route for solvent-free synthesis of aryl iodides.

  20. Chiral Pyridinium Phosphoramide as a Dual Brønsted Acid Catalyst for Enantioselective Diels-Alder Reaction.

    Science.gov (United States)

    Nishikawa, Yasuhiro; Nakano, Saki; Tahira, Yuu; Terazawa, Kanako; Yamazaki, Ken; Kitamura, Chitoshi; Hara, Osamu

    2016-05-06

    Chiral pyridinium phosphoramide 1·HX was designed to be a new class of chiral Brønsted acid catalyst in which both the pyridinium proton and the adjacent imide-like proton activated by the electron-withdrawing pyridinium moiety could work cooperatively as strong dual proton donors. The potential of 1·HX was shown in the enantioselective Diels-Alder reactions of 1-amino dienes with various dienophiles including N-unsubstituted maleimide, which has yet to be successfully used in an asymmetric Diels-Alder reaction.

  1. Electrooxidations of ethanol, acetaldehyde and acetic acid using PtRuSn/C catalysts prepared by modified alcohol-reduction process

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Gang [Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208 (United States); Swaidan, Raja [Department of Chemical Engineering, Cooper Union, New York, NY 10003 (United States); Cui, Guofeng [School of Chemistry and Chemical Engineering, Sun-Yat Sen University, Guangzhou 510275 (China)

    2007-10-11

    Well-dispersed ternary PtRuSn catalysts of various atomic ratios (60:30:10, 60:20:20 and 60:10:30) were deposited onto carbon using modified alcohol-reduction process for electrochemical oxidation of ethanol. The alloy phase structure and surface morphology for each variation of the PtRuSn/C catalysts were determined by XRD and HRTEM. In order to evaluate the contributions of Ru and Sn in the different stages of ethanol oxidation, electrochemical oxidations of adsorbed CO, ethanol, acetaldehyde and acetic acid were performed on each PtRuSn/C catalyst. The results indicated that the Ru-rich PtRuSn/C catalyst (60:30:10) exhibited the lowest onset potential for the electrooxidations of adsorbed CO, ethanol and acetaldehyde, revealing that the removal through oxidation of the intermediate C{sub 1} and C{sub 2} species from Pt sites is primarily attributed to the Ru and Pt{sub 3}Sn alloy structures. However, for the overall oxidation of ethanol, the Sn-rich PtRuSn/C catalyst (60:10:30) containing PtSn phase and SnO{sub 2} structure is favorable for the activation of C-C bond breaking, thereby generating higher current density (mass activity) at higher potentials. Moreover, in the electrooxidation of acetic acid, a remarkable improvement for oxidizing acetic acid to C{sub 1} species was observed in the Sn-rich PtRuSn/C catalyst (60:10:30), while the Ru-rich PtRuSn/C catalyst (60:30:10) was almost incapable of breaking the C-C bond to further oxidize acetic acid. The possible reasons for the different reactivities on the studied PtRuSn/C catalysts were discussed based on the removal of intermediates and activation of the C-C bonds on the different surfaces. (author)

  2. Synthesis and characterization of triflic acid-functionalized mesoporous Zr-TMS catalysts: heterogenization of CF3SO3H over Zr-TMS and its catalytic activity

    NARCIS (Netherlands)

    Chidambaram, M.; Curulla Ferre, D.; Singh, A.P.; Anderson, B.G.

    2003-01-01

    Triflic acid-functionalized Zr-TMS (zirconium oxide with a mesostructured framework; TMS, transition metal oxide mesoporous molecular sieves) catalysts have been synthesized by functionalizing triflic acid onto the walls of Zr-TMS via post synthesis method. The synthesized materials were

  3. Properties of Pt/C catalyst modified by chemical vapor deposition of Cr as a cathode of phosphoric acid fuel cell

    International Nuclear Information System (INIS)

    Seo, Sang Joon; Joh, Han-Ik; Kim, Hyun Tae; Moon, Sang Heup

    2006-01-01

    Cr-modified Pt/C catalysts were prepared by the chemical vapour deposition (CVD) of Cr on Pt/C, and their performance as a cathode of phosphoric acid fuel cell (PAFC) was compared with the case of catalysts containing Cr added by impregnation (IMP). The catalyst prepared by CVD showed a higher activity for oxygen reduction reaction (ORR) than one prepared by IMP. There was an optimum amount of Cr that yielded the maximum mass activity of the catalyst because the gain in the intrinsic activity due to the promotional effect of Cr was counterbalanced by the loss of exposed Pt surface area as a result of the Cr introduction. Nevertheless, the activity increase at the optimum amount of Cr was greater for the CVD catalyst than for the IMP catalyst. Also, the optimum amount of Cr to yield the maximum activity was smaller for the former catalyst [Cr/Pt] CVD = 0.6, than for the latter, [Cr/Pt] IMP = 1.0. The enhancement of the Pt catalyst activity by Cr addition is attributed to two factors: changes in the surface Pt-Pt spacing and the electronic modification of the Pt surface. The formation of a Pt-Cr alloy, as confirmed by X-ray diffraction, decreased the lattice parameter of Pt, which was beneficial to the catalyst activity for ORR. X-ray photoelectron spectroscopy results showed that the binding energies of Pt electrons were shifted to higher energies due to Cr modification. Accordingly, the electron density of Pt was lowered and the Pt-O bond became weak on the Cr-modified catalysts, which was also beneficial to the catalyst activity for ORR. The promotion of oxygen reduction on Cr-modified catalysts was confirmed by measuring the cyclic voltammograms of the catalysts. All the above changes were made more effectively for catalysts prepared by CVD than for those prepared by IMP because the former method allowed Cr to interact more closely with the Pt surface than the latter, which was demonstrated by the characterization of catalysts in this study

  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. Aerobic Oxidation of Alcohols over Gold Catalysts: Role of Acid and Base

    DEFF Research Database (Denmark)

    Klitgaard, Søren Kegnæs; DeLa Riva, Andrew T.; Helveg, Stig

    2008-01-01

    Gold nanoparticles are deposited on potassium titanate nanowires and used as heterogeneous catalysts in the aerobic oxidation of benzyl alcohol in methanol to methyl benzoate at ambient conditions. The presence of a catalytic amount of base promotes the reaction and the formation of free benzoic...

  6. From Conventional Lewis Acids to Heterogeneous Montmorillonite K10: Eco-Friendly Plant-Based Catalysts Used as Green Lewis Acids.

    Science.gov (United States)

    Hechelski, Marie; Ghinet, Alina; Louvel, Brice; Dufrénoy, Pierrick; Rigo, Benoît; Daïch, Adam; Waterlot, Christophe

    2018-04-25

    The concept of green chemistry began in the USA in the 1990s. Since the publication of the 12 principles of this concept, many reactions in organic chemistry have been developed, and chemical products have been synthesized under environmentally friendly conditions. Lewis acid mediated synthetic transformations are by far the most numerous and best studied. However, the use of certain Lewis acids may cause risks to environmental and human health. This Review discusses the evolution of Lewis acid catalyzed reactions from a homogeneous liquid phase to the solid phase to yield the expected organic molecules under green, safe conditions. In particular, recent developments and applications of biosourced catalysts from plants are highlighted. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. A molecular molybdenum–schiff base electro-catalyst for generating hydrogen from acetic acid or water

    International Nuclear Information System (INIS)

    Cao, Jie-Ping; Fang, Ting; Zhou, Ling-Ling; Fu, Ling-Zhi; Zhan, Shuzhong

    2014-01-01

    Highlights: • The reaction of ligand, H 2 L and MoCl 5 gives a Mo(VI) complex [MoL(O) 2 ] 1. • Complex 1 is capable of catalyzing hydrogen evolution from acetic acid and water. • TOF reaches a maximum of 68 (DMF) and 356 (buffer, pH 6) moles/h, respectively. • Sustained proton reduction catalysis occurs over a 69 h period and no decomposition of 1. - ABSTRACT: The reaction of 2-pyridylamino-N,N-bis(2-methylene-4-ethyl-6-tert-butylphenol) (H 2 L) and MoCl 5 gives a molybdenum(VI) complex [MoL(O) 2 ] 1, a new molecular electrocatalyst, which has been determined by X-ray crystallography. Electrochemical studies show that complex 1 can catalyze hydrogen evolution from acetic acid or aqueous buffer. Turnover frequency (TOF) reaches a maximum of 68 (in N,N-Dimethylformamide (DMF)) and 356 (in buffer, pH 6.0) moles of hydrogen per mole of catalyst per hour, respectively. Sustained proton reduction catalysis occurs at glassy carbon (GC) electrode to give H 2 over a 69 h electrolysis period and no observable decomposition of the catalyst

  8. Comparative analysis of different whole cell immobilized Aspergillus niger catalysts for gluconic acid fermentation using pretreated cane molasses

    Energy Technology Data Exchange (ETDEWEB)

    Subba Rao, D. (Div. of Biochemical Engineering, Dept. of Chemical Engineering, Indian Inst. of Tech., Madras (India)); Panda, T. (Div. of Biochemical Engineering, Dept. of Chemical Engineering, Indian Inst. of Tech., Madras (India))

    1994-10-01

    To compare the efficiency of various whole cell immobilization techniques for the production of gluconic acid by Aspergillus niger were investigated using potassium ferrocyanide-treated cane molasses as the substrate. The techniques followed were: (1) Calcium alginate entrapment, (2) cross-linking with glutaraldehyde after cell permeabilization with (a) acetone, (b) toluene and (c) isopropanol and (3) development of granular catalyst. A comparative analysis of yield has revealed that calcium alginate entrapment was the most suitable technique as it had given the maximum product yield (0.40 g gluconic acid/g total reducing sugar supplied). The properties of immobilized A. niger in sodium alginate gel have been thoroughly investigated and compared with those of free cells under most suitable conditions of fermentation. (orig.)

  9. Ruthenium water oxidation catalysts containing the non-planar tetradentate ligand, biisoquinoline dicarboxylic acid (biqaH2).

    Science.gov (United States)

    Scherrer, Dominik; Schilling, Mauro; Luber, Sandra; Fox, Thomas; Spingler, Bernhard; Alberto, Roger; Richmond, Craig J

    2016-12-06

    Two ruthenium complexes containing the tetradentate ligand [1,1'-biisoquinoline]-3,3'-dicarboxylic acid, and 4-picoline or 6-bromoisoquinoline as axial ligands have been prepared. The complexes have been fully characterised and initial studies on their potential to function as molecular water oxidation catalysts have been performed. Both complexes catalyse the oxidation of water in acidic media with Ce IV as a stoichiometric chemical oxidant, although turnover numbers and turnover frequencies are modest when compared with the closely related Ru-bda and Ru-pda analogues. Barriers for the water nucleophilic attack and intermolecular coupling pathways were obtained from density functional theory calculations and the crucial influence of the ligand framework in determining the most favourable reaction pathway was elucidated from a combined analysis of the theoretical and experimental results.

  10. Hollow Ag-Pd core–shell nanotubes as highly active catalysts for the electro-oxidation of formic acid

    International Nuclear Information System (INIS)

    Jiang Yuanyuan; Lu Yizhong; Han Dongxue; Zhang Qixian; Niu Li

    2012-01-01

    Ag nanowires are prepared as templates by a polyol reduction process. Then Ag nanotubes coated with a thin layer of Pd are synthesized through sequential reduction accompanied with the galvanic displacement reaction. The products show a hollow core–shell nanotubular structure, as demonstrated by detailed characterizations. The Ag-Pd can significantly improve the electrocatalytic activity towards the electro-oxidation of formic acid and enhance the stability of the Pd component. It is proposed that the enhanced electrochemically active surface area and modulated electron structure of Pd by Ag are responsible for the improvement of electrocatalytic activity and durability. The results obtained in this work are different from those previous reports, in which alloy walls with hollow interiors are usually formed. This work provides a new and simple method for synthesizing novel bimetallic core–shell structure with a hollow interior, which can be applied as high-performance catalysts for the electro-oxidation of formic acid. (paper)

  11. 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)

  12. A comparative study of alumina-supported Ni catalysts prepared by photodeposition and impregnation methods on the catalytic ozonation of 2,4-dichlorophenoxyacetic acid

    International Nuclear Information System (INIS)

    Rodríguez, Julia L.; Valenzuela, Miguel A.; Tiznado, Hugo; Poznyak, Tatiana; Chairez, Isaac; Magallanes, Diana

    2017-01-01

    The heterogeneous catalytic ozonation on unsupported and supported oxides has been successfully tested for the removal of several refractory compounds in aqueous solution. In this work, alumina-supported nickel catalysts prepared by photodeposition and impregnation methods were compared in the catalytic ozonation of 2,4-dichlorophenoxyacetic acid (2,4-D). The catalysts were characterized by high-resolution electron microscopy and X-ray photoelectron spectroscopy. The photochemical decomposition of Ni acetylacetonate to produce Ni(OH) 2 , NiO, and traces of Ni° deposited on alumina was achieved in the presence of benzophenone as a sensitizer. A similar surface composition was found with the impregnated catalyst after its reduction with hydrogen at 500 °C and exposed to ambient air. Results indicated a higher initial activity and maleic acid (byproduct) concentration with the photodeposited catalyst (1 wt% Ni) compared to the impregnated catalyst (3 wt% Ni). These findings suggest the use of the photodeposition method as a simple and reliable procedure for the preparation of supported metal oxide/metal catalysts under mild operating conditions.

  13. A comparative study of alumina-supported Ni catalysts prepared by photodeposition and impregnation methods on the catalytic ozonation of 2,4-dichlorophenoxyacetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Rodríguez, Julia L., E-mail: ozliliana@yahoo.com.mx [Lab. Ing. Química Ambiental. ESIQIE–Instituto Politécnico Nacional (Mexico); Valenzuela, Miguel A. [Lab.Catálisis y Materiales. ESIQIE–Instituto Politécnico Nacional. Zacatenco (Mexico); Tiznado, Hugo [Centro de Nanociencias y Nanotecnología. CNyN Universidad Nacional Autónoma de México (Mexico); Poznyak, Tatiana [Lab. Ing. Química Ambiental. ESIQIE–Instituto Politécnico Nacional (Mexico); Chairez, Isaac [Departamento de Bioprocesos, UPIBI- Instituto Politécnico Nacional (Mexico); Magallanes, Diana [Lab. Ing. Química Ambiental. ESIQIE–Instituto Politécnico Nacional (Mexico)

    2017-02-15

    The heterogeneous catalytic ozonation on unsupported and supported oxides has been successfully tested for the removal of several refractory compounds in aqueous solution. In this work, alumina-supported nickel catalysts prepared by photodeposition and impregnation methods were compared in the catalytic ozonation of 2,4-dichlorophenoxyacetic acid (2,4-D). The catalysts were characterized by high-resolution electron microscopy and X-ray photoelectron spectroscopy. The photochemical decomposition of Ni acetylacetonate to produce Ni(OH){sub 2}, NiO, and traces of Ni° deposited on alumina was achieved in the presence of benzophenone as a sensitizer. A similar surface composition was found with the impregnated catalyst after its reduction with hydrogen at 500 °C and exposed to ambient air. Results indicated a higher initial activity and maleic acid (byproduct) concentration with the photodeposited catalyst (1 wt% Ni) compared to the impregnated catalyst (3 wt% Ni). These findings suggest the use of the photodeposition method as a simple and reliable procedure for the preparation of supported metal oxide/metal catalysts under mild operating conditions.

  14. Pt-Ni and Pt-M-Ni (M = Ru, Sn Anode Catalysts for Low-Temperature Acidic Direct Alcohol Fuel Cells: A Review

    Directory of Open Access Journals (Sweden)

    Ermete Antolini

    2017-01-01

    Full Text Available In view of a possible use as anode materials in acidic direct alcohol fuel cells, the electro-catalytic activity of Pt-Ni and Pt-M-Ni (M = Ru, Sn catalysts for methanol and ethanol oxidation has been widely investigated. An overview of literature data regarding the effect of the addition of Ni to Pt and Pt-M on the methanol and ethanol oxidation activity in acid environment of the resulting binary and ternary Ni-containing Pt-based catalysts is presented, highlighting the effect of alloyed and non-alloyed nickel on the catalytic activity of these materials.

  15. 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.

  16. Two-Stage Conversion of High Free Fatty Acid Jatropha curcas Oil to Biodiesel Using Brønsted Acidic Ionic Liquid and KOH as Catalysts

    Directory of Open Access Journals (Sweden)

    Subrata Das

    2014-01-01

    Full Text Available Biodiesel was produced from high free fatty acid (FFA Jatropha curcas oil (JCO by two-stage process in which esterification was performed by Brønsted acidic ionic liquid 1-(1-butylsulfonic-3-methylimidazolium chloride ([BSMIM]Cl followed by KOH catalyzed transesterification. Maximum FFA conversion of 93.9% was achieved and it reduced from 8.15 wt% to 0.49 wt% under the optimum reaction conditions of methanol oil molar ratio 12 : 1 and 10 wt% of ionic liquid catalyst at 70°C in 6 h. The ionic liquid catalyst was reusable up to four times of consecutive runs under the optimum reaction conditions. At the second stage, the esterified JCO was transesterified by using 1.3 wt% KOH and methanol oil molar ratio of 6 : 1 in 20 min at 64°C. The yield of the final biodiesel was found to be 98.6% as analyzed by NMR spectroscopy. Chemical composition of the final biodiesel was also determined by GC-MS analysis.

  17. Effect of gasoline composition on oxidative desulfurization using a phosphotungstic acid/activated carbon catalyst with hydrogen peroxide

    International Nuclear Information System (INIS)

    Xiao, Jing; Wu, Luoming; Wu, Ying; Liu, Bing; Dai, Lu; Li, Zhong; Xia, Qibin; Xi, Hongxia

    2014-01-01

    Highlights: • Concerned with the question why ODS catalyst is not effective for real gasoline. • Reported the strong inhibiting effect of gasoline composition on ODS for the 1st time. • ODS reactivity is suggested to be determined by partial charge on S atom of thiophene. • Proposed approaches to improve ODS selectivity for real gasoline desulfurization. - Abstract: This work is concerned with the question of why oxidative desulfurization (ODS) catalyst that show good catalytic performance for ODS of model gasoline thiophenic compounds is not effective for real gasoline. For the first time, the effects of gasoline composition on ODS using a phosphotungstic acid/activated carbon (HPW/AC) catalyst with H 2 O 2 were investigated. ODS of thiophene, one of the most difficult thiophenic compounds to be oxidized, was studied in a model fuel system, where a high thiophene conversion rate of 90% could be reached in 2 h at 90 °C. However, when applying the ODS to a real gasoline, the ODS conversion rate decreased to only 32%, suggesting a strong inhibiting effect of gasoline composition on ODS. The ODS studies in different model fuels suggested that the inhibiting effect can be ascribed to the competitive adsorption and oxidation with the presence of the alkenes and alkylated aromatic hydrocarbons in real gasoline. The active pi-electrons in alkenes and alkyl groups in alkylated aromatic hydrocarbons may react with polyoxoperoxo species or peroxo-metallate complexes formed by phosphotungstic acid–H 2 O 2 interaction. Additionally, it was indicated that the ODS selectivity followed the order of benzothiophene > trimethylthiophene > dimethylthiophene ∼ methylthiophene > thiophene, suggesting the partial charge on the electron-rich sulfur atom may play a decisive role for its oxidation reactivity. To mitigate the inhibiting effect of gasoline composition on ODS, we propose (a) implementation of selective separation–oxidation processes; (b) choice of suitable

  18. MoO3/Al2O3 catalyst: Comparison of catalysts prepared by new slurry impregnation with molybdic acid with conventional samples

    International Nuclear Information System (INIS)

    Spojakina, A.; Kostova, N.; Vit, Z.; Zdrazil, M.

    2003-01-01

    Alumina-supported molybdena catalysts were prepared by conventional impregnation with (NH 4 ) 6 Mo 7 O 24 (CIM) and by a new slurry impregnation method (SIM). SIM is the reaction of alumina support with a slurry of MoO 3 in water. Two commercial supports were used and the commercial Mo 3 /Al 2 O 3 catalyst was included for comparison. Maximum amount of MoO 3 deposited by SIM was about 19-20 % MoO 3 with the surface area of the support of 260-280 m 2 g -1 and this corresponded to saturation monolayer of similar density as described in literature for CIM catalysts. At the ratios of MoO 3 to Al 2 O 3 in the impregnation slurry below saturation monolayer, the pH of the slurry was 3.5-6 (depending on loading) and chemical erosion of alumina is negligible. However, using the large excess of MoO 3 (35% MoO 3 ) the pH was 2.4-3.4 and chemical erosion of alumina occurred. Silica contained in alumina supports was partly extracted as soluble silicomolybdic anions during SIM. The catalysts were characterized by BET, IR, DRS (UV-vis and NIR), TPR and catalytic activity in hydrodesulfurization of thiophene. Calcination had no significant effect on the properties of SIM catalysts and this proved that calcination is not needed in that method. All catalysts exhibited features of high monolayer dispersion of molybdena and no significant difference in structure and catalytic properties was observed between SIM and CIM catalysts. This confirmed that SIM is a simple, clean and reliable method of preparation of monolayer type MoO 3 /Al 2 O 3 catalysts. (author)

  19. Nanocarbons as catalyst for selective oxidation of acrolein to acrylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Frank, B.; Blume, R.; Rinaldi, A.; Trunschke, A.; Schloegl, R. [Fritz Haber Institute of the Max Planck Society, Berlin (Germany). Dept. of Inorganic Chemistry

    2011-07-01

    Selective oxidations are key steps of industrial oil and gas processing for the synthesis of high-value chemicals. Mixed metal oxides based on redox active V or Mo are frequently used for oxidative C-H bond activation. However, multiple processes require precious metals or suffer from low product selectivity demanding an ongoing search for cost-effective alternatives. Recently, the nanostructured carbon was reported to catalyze the metal-free selective alkane activation by oxidative dehydrogenation (ODH). Electron-rich surface carbonyls coordinate this reaction and mimic the active oxygen species in metal oxide catalysts. Here we show that the graphitic carbon, beyond ODH, has the potential to selectively mediate the insertion of an oxygen atom into an organic molecule, i.e., acrolein. Multi-step atom rearrangements considerably exceed the mechanistic complexity of hydrogen abstraction and were so far believed to be the exclusive domain of metal (oxide) catalysis. In the carbon catalyzed process, the nucleophilic oxygen atoms terminating the graphite (0001) surface abstract the formyl hydrogen and the activated aldehyde gets oxidized by epoxide-type mobile oxygen, thus the sp{sup 2} carbon acts as a bifunctional catalyst. Substantial similarities between the metal oxide- and carbon-catalyzed reactions could be identified. Our results shed light on a rarely known facet of applications of nanostructured carbon materials being decorated with diverse oxygen functionalities to coordinate complex catalytic processes. We could successfully transfer the results obtained from the graphite model to carbon nanotubes (CNTs) providing a higher surface area, defect density, and intrinsic activity, to substantially increase the reactivity per catalyst volume. Indeed, low dimensional nanostructured carbon is a highly flexible and robust material which can be modified in a multiple manner to optimize its properties with respect to the intended application. The exploration of

  20. Deactivation of vanadia-based commercial SCR catalysts by polyphosphoric acids

    DEFF Research Database (Denmark)

    Castellino, Francesco; Rasmussen, Søren Birk; Jensen, Anker Degn

    2008-01-01

    Commercial vanadia-based SCR monoliths have been exposed to flue gases in a pilot-scale Setup into which phosphoric acid has been added and the deactivation has been followed during the exposure time. Separate measurements by SMPS showed that the phosphoric acid formed polyphosphoric acid aerosols...

  1. Saccharin Sulfonic Acid as an Efficient Catalyst for the Preparation and Deprotection of 1,1-Diacetates

    International Nuclear Information System (INIS)

    Shirini, F.; Mamaghani, M.; Mostashari-Rad, T.; Abedini, M.

    2010-01-01

    Saccharin sulfonic acid can be used as an efficient catalyst for the acylation of aldehydes using acetic anhydride. This is also a suitable catalyst for the regeneration of aldehydes from the related acylals in the presence of wet SiO 2 . The significant advantages of this methodology are mild, solvent-free reaction conditions, relatively short reaction times, high yields of the products, selectivity and easy work-up. The Protection and deprotection of organic functional groups are important procceses during multi-step organic synthesis. The choice of a method which is used for the functional group transformations depends on its simplicity, high yields of the desired products, short reaction times, low cost of the process and ease of the work-up procedure. Between the several methods available for the protection of aldehydes, acylal formation is often preferred due to the ease of preparation and the stability of the produced 1,1-diacetate towards basic and neutral conditions. In addition, 1,1-diacetates serve as valuable precursors for asymmetric allylic alkylation and synthesis of natural products as well as for the synthesis of 1-acetoxydienes and 2,2-dichlorovinylacetates for Diels-Alder reactions. Acylals have also been used as cross-linking agents for cellulose in cotton and as bleaching activators in wine-stained fabrics. Moreover, the acylal functionality can be converted to other functional groups by reaction with appropriate nucleophiles

  2. Carbon-free H2 production from ammonia triggered at room temperature with an acidic RuO2/γ-Al2O3 catalyst.

    Science.gov (United States)

    Nagaoka, Katsutoshi; Eboshi, Takaaki; Takeishi, Yuma; Tasaki, Ryo; Honda, Kyoko; Imamura, Kazuya; Sato, Katsutoshi

    2017-04-01

    Ammonia has been suggested as a carbon-free hydrogen source, but a convenient method for producing hydrogen from ammonia with rapid initiation has not been developed. Ideally, this method would require no external energy input. We demonstrate hydrogen production by exposing ammonia and O 2 at room temperature to an acidic RuO 2 /γ-Al 2 O 3 catalyst. Because adsorption of ammonia onto the catalyst is exothermic, the catalyst bed is rapidly heated to the catalytic ammonia autoignition temperature, and subsequent oxidative decomposition of ammonia produces hydrogen. A differential calorimeter combined with a volumetric gas adsorption analyzer revealed a large quantity of heat evolved both with chemisorption of ammonia onto RuO 2 and acidic sites on the γ-Al 2 O 3 and with physisorption of multiple ammonia molecules.

  3. High-performance oxygen reduction catalysts in both alkaline and acidic fuel cells based on pre-treating carbon material and iron precursor

    Energy Technology Data Exchange (ETDEWEB)

    Song, Ping; Barkholtz, Heather M.; Wang, Ying; Xu, Weilin; Liu, Dijia; Zhuang, Lin

    2017-12-01

    We demonstrate a new and simple method for pre-treating the carbon material and iron precursor to prepare oxygen reduction reaction (ORR) catalysts, which can produce super-high performance and stability in alkaline solution, with high performance in acid solution. This strategy using cheap materials is simply controllable. Moreover, it has achieved smaller uniform nanoparticles to exhibit high stability, and the synergetic effect of Fe and N offered much higher performance in ORR than commercial Pt/C, with high maximum power density in alkaline and acid fuel cell test. So it can make this kind of catalysts be the most promising alternatives of Pt-based catalysts with best performance/price.

  4. Camellia oleifera shell as an alternative feedstock for furfural production using a high surface acidity solid acid catalyst.

    Science.gov (United States)

    Zhang, Luxin; He, Yunfei; Zhu, Yujie; Liu, Yuting; Wang, Xiaochang

    2018-02-01

    This paper focuses on the high-value transformation of camellia oleifera shell, which is an agricultural waste enriched in hemicellulose. An efficient catalytic route employing sulfonated swelling mesoporous polydivinylbenzene (PDVB-SO 3 H) as catalyst in monophasic or biphasic solvents was developed for the conversion of raw camellia oleifera shell into furfural. The reaction parameters were evaluated and optimized for improving the furfural yield. It was found that the solvent greatly influenced the hydrolysis of camellia oleifera shells, and the highest furfural yield of 61.3% was obtained in "γ-butyrolactone + water" system when the feedstock-to-catalyst ratio was 2 for 30 min at 443 K. Camellia oleifera shell exhibited a high potential as feedstock to produce furfural in high yields. The outcome of this study provides an attractive utilization option to camellia oleifera shell, which is currently burned or discarded for producing a bio-based chemical. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. New insights into Cu/SSZ-13 SCR catalyst acidity. Part I: Nature of acidic sites probed by NH 3 titration

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Jinyong; Gao, Feng; Kamasamudram, Krishna; Currier, Neal; Peden, Charles H. F.; Yezerets, Aleksey

    2017-04-01

    In this work we investigated an unusual acidity feature of a Cu/SSZ-13 catalyst used in selective catalytic reduction of NOx with NH3 (NH3-SCR). In particular, this catalyst showed two distinct NH3 desorption peaks in NH3-TPD measurements, in contrast to single, unresolved desorption peaks observed for other Cu-exchanged zeolites conventionally used in the SCR studies, including its isostructural but chemically different analogue Cu/SAPO-34. We further observed that the intensities of the two TPD peaks, which represented the amount of stored NH3, changed in opposite directions in response to progressive mild hydrothermal aging, while the total storage capacity was preserved. We proposed an explanation for this remarkable behavior, by using model reference samples and additional characterization techniques. At least three NH3 storage sites were identified: two distinct populations of Cu sites responsible for low-temperature NH3 storage, and Brønsted acid sites responsible for high-temperature NH3 storage. Contrary to the commonly accepted mechanism that Brønsted acid site loss during hydrothermal aging is driven by dealumination, we concluded that the decline in the number of Brønsted acid sites upon mild hydrothermal aging for Cu/SSZ-13 was not due to dealumination, but rather transformation of Cu sites, i.e., gradual conversion of ZCuOH (Cu2+ singly coordinated with Zeolite) to Z2Cu (Cu2+ doubly coordinated with Zeolite). This transformation was responsible for the increased low-temperature desorption peak in NH3-TPD since each ZCuOH adsorbed ~1 NH3 molecule while each Z2Cu adsorbed ~2 NH3 molecules under the conditions used here. These findings were used in Part II of this series of studies to develop a method for quantifying hydrothermal ageing of industrial Cu/SSZ-13 SCR catalysts. Authors would like to thank Randall Jines for his help with collecting the reactor data, Nancy W. Washton for measuring the NMR data and Tamas Varga for in-situ XRD measurements

  6. Black liquor-derived carbonaceous solid acid catalyst for the hydrolysis of pretreated rice straw in ionic liquid.

    Science.gov (United States)

    Bai, Chenxi; Zhu, Linfeng; Shen, Feng; Qi, Xinhua

    2016-11-01

    Lignin-containing black liquor from pretreatment of rice straw by KOH aqueous solution was applied to prepare a carbonaceous solid acid catalyst, in which KOH played dual roles of extracting lignin from rice straw and developing porosity of the carbon material as an activation agent. The synthesized black liquor-derived carbon material was applied in catalytic hydrolysis of the residue solid from the pretreatment of rice straw, which was mainly composed of cellulose and hemicellulose, and showed excellent activity for the production of total reducing sugars (TRS) in ionic liquid, 1-butyl-3-methyl imidazolium chloride. The highest TRS yield of 63.4% was achieved at 140°C for 120min, which was much higher than that obtained from crude rice straw under the same reaction conditions (36.6% TRS yield). Overall, this study provides a renewable strategy for the utilization of all components of lignocellulosic biomass. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Systematically controlled pore system of ordered mesoporous carbons using phosphoric acid as the in situ generated catalysts for carbonization and activation

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Xing; Lee, Chang Hyun; Kim, Jin Hoe; You, Dae Jong; Shon, Jeong Kuk; Kim, Ji Man [Dept. of Chemistry, Sungkyunkwan University, Suwon (Korea, Republic of); Pak, Chan Ho [Fuel Cell Group, Corporate R and D Center, Samsung SDI Co. Ltd., Yongin (Korea, Republic of)

    2015-08-15

    We report on a facile synthesis of the ordered mesoporous carbon (OMC) materials with systematically controlled microporosity and mesoporosity simultaneously through the nano-replication route using phosphoric acid as the acid catalyst and activation agent. The use of phosphoric acid affects the pore structures of OMC materials, such as the formation of numerous micropores by activation of the carbon framework and the enlargement of mesopores by spontaneous phase separation during the carbonization. The mesopore sizes, surface areas, total pore volumes, and micropore volumes of the OMC materials are highly dependent on the phosphoric acid content and can be systematically controlled in the range 3.7–7.5 nm, 1027–2782 m{sup 2} g{sup -1}, 1.12–3.53 cm{sup 3} g{sup -1} and 0.34–0.95 cm{sup 3} g{sup -1}, respectively. OMC materials with systematically controlled pore structures were successfully synthesized using phosphoric acid as the carbonization catalyst and mesoporous silica materials with cubic Ia3d and 2-D hexagonal mesostructures as the templates. The phosphoric acid in the synthesis of ordered mesoporous carbon materials acts as the chemical activating agent for micropore generation of the carbon framework and pore-expanding agent for controlling of mesopore size, in addition to functioning as the acid catalyst. The present synthesis pathway is very useful for preparing OMC materials with tunable mesopore sizes and well-developed microporosities at the same time.

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

    International Nuclear Information System (INIS)

    Nadejde, C.; Neamtu, M.; Hodoroaba, V.-D.; Schneider, R. J.; Paul, A.; Ababei, G.; Panne, U.

    2015-01-01

    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 3 O 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 2 O 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 2 O 2 , under UV irradiation. The highest mineralization rates were observed for Fe 3 O 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

  9. 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...

  10. The combination of ascorbic acid 6-palmitate and [Fe III 3(µ3-O)]7+ as a catalyst for the oxidation of unsaturated lipids

    NARCIS (Netherlands)

    Micciche, F.; Long, G.J.; Shahin, A.M.; Grandjean, F.; Ming, W.; Haveren, van J.; Linde, van der R.

    2007-01-01

    Recently, iron 2-ethylhexanoate (Fe-eh, 1) in combination with ascorbic acid 6-palmitate (AsA6p) has been reported as a good catalytic system for the oxidation of ethyl linoleate (EL), an unsaturated lipid. In response to the fascinating chemistry of this bio-inspired iron-based catalyst the

  11. Porous nitrogen-enriched carbonaceous material from marine waste: chitosan-derived layered CNX catalyst for aerial oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid

    Science.gov (United States)

    Chitosan derived porous layered nitrogen-enriched carbonaceous CNx catalyst (PLCNx) has been synthesized from marine waste and its use demonstrated in a metal-free heterogeneous selective oxidation of 5-hydroxymethyl-furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) using aeria...

  12. Hydrogenation of Levulinic Acid to gamma-Valerolactone in Water Using Millimeter Sized Supported Ru Catalysts in a Packed Bed Reactor

    NARCIS (Netherlands)

    Piskun, A. S.; de Haan, J. E.; Wilbers, E.; de Bovenkamp, H. H. van; Tang, Z.; Heeres, Hero

    gamma-Valerolactone (GVL) has been identified as a sustainable platform chemical for the production of carbon-based chemicals. We here report an experimental study on the catalytic hydrogenation of levulinic acid (LA) in water to GVL in a packed bed reactor using supported Ru catalysts (carbon,

  13. Highly Efficient Catalytic Synthesis of α-Amino Acids under Phase-Transfer Conditions with a Novel Catalyst/Substrate Pair

    NARCIS (Netherlands)

    Belokon, Yuri N.; Kochetkov, Konstantin A.; Churkina, Tatiana D.; Ikonnikov, Nikolai S.; Larionov, Oleg V.; Harutyunyan, Syuzanna R.; Vyskočil, Štepán; North, Michael; Kagan, Henri B.

    2001-01-01

    A facile and fast enantioselective synthesis of α-amino acids with high ee values was achieved by the asymmetric alkylation of the glycine derivative under phase-transfer conditions with (R)- or (S)-2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN). The ee value of the catalyst can be as little as 40 %

  14. Synthesis of 1,2-Disubstituted Benzimidazoles in the Presence of SBA-Pr-SO3H as a Nano Solid Acid Catalyst

    Directory of Open Access Journals (Sweden)

    G. Mohammadi Ziarani

    2012-06-01

    Full Text Available In this article, simple, convenient synthesis of 2-aryl-1- arylmethyl-1H-1,3-benzimidazole (1,2-disubstituted benzimidazoles via condensation of 1,2-phenylenediamine and aromatic aldehydes using SBA-Pr-SO3H as a nanoporous solid acid catalyst in green protocol was reported.

  15. Synthesis, structure and topological analysis of glycine templated highly stable cadmium sulfate framework: A New Lewis Acid catalyst

    Science.gov (United States)

    Paul, Avijit Kumar

    2018-04-01

    One new open-framework two-dimensional layer, [Cd(NH3CH2COO)(SO4)], I, has been synthesized using amino acid as templating agent. Single crystal structural analysis shows that the compound crystallizes in monoclinic cell with non-centrosymmetric space group P21, a = 4.9513(1) Å, b = 7.9763(2) Å, c = 8.0967(2) Å, β = 105.917(1)° and V = 307.504(12) Å3. The compound has connectivity between the Cd-centers and the sulfate units forming a two-dimensional layer structure. Sulfate unit is coordinated to metal center with η3, μ4 mode possessing a coordination free oxygen atom. The zwitterionic form of glycine molecule is present in the structure bridging with two metal centers through μ2-mode by carboxylate oxygens. The topological analysis reveals that the two-dimensional network is formed with a novel 4- and 6-connected binodal net of (32,42,52)(34,44,54,63) topology. Although one end of the glycine molecule is free from coordination, the structure is highly stable up to 350 °C. Strong N-H⋯ O hydrogen bonding interactions play an important role in the stabilization and formation of three-dimensional supramolecular structure. The cyanosilylation of imines using the present compounds as heterogeneous catalyst indicates good catalytic behavior. The present study illustrates the usefulness of the amino acid for the structure building in less studied sulfate based framework materials as well as designing of new heterogeneous catalysts for the broad application. The compound has also been characterized through elemental analysis, PXRD, IR, SEM and TG-DT studies.

  16. Efficient hydrogenation of biomass-derived furfural and levulinic acid on the facilely synthesized noble-metal-free Cu–Cr catalyst

    International Nuclear Information System (INIS)

    Yan, Kai; Chen, Aicheng

    2013-01-01

    Biomass-derived platform intermediate furfural and levulinic acid were efficiently hydrogenated to the value-added furfuryl alcohol and promising biofuel γ-valerolactone, respectively, using a noble-metal-free Cu–Cr catalyst, which was facilely and successfully synthesized by a modified co-precipitation method using the cheap metal nitrates. In the first hydrogenation of furfural, 95% yield of furfuryl alcohol was highly selectively produced at 99% conversion of furfural under the mild conditions. For the hydrogenation of levulinic acid, 90% yield of γ-valerolactone was highly selectively produced at 97.8% conversion. Besides, the physical properties of the resulting Cu–Cr catalysts were studied by XRD (X-ray diffraction), EDX (Energy-dispersive X-ray), TEM (Transmission electron microscopy) and XPS (X-ray photoelectron spectroscopy) to reveal their influence on the catalytic performance. Subsequently, different reaction parameters were studied and it was found that Cu 2+ /Cr 3+ ratios (0.5, 1 and 2), reaction temperature (120–220 °C) and hydrogen pressure (35–70 bar) presented important influence on the catalytic activities. In the end, the stability of the Cu–Cr catalysts was also studied. - Highlights: • A noble-metal-free Cu–Cr catalyst was successfully synthesized using metal nitrates. • Cu–Cr catalysts were highly selective hydrogenation of biomass-derived furfural to FA. • Cu–Cr catalysts were efficient for hydrogenation of biomass-derived LA to biofuel GVL. • The physical properties of the resulting Cu–Cr catalysts were systematically studied. • Reaction parameters and stability in the hydrogenation of furfural were studied in details

  17. Deoxyribonucleic acid directed metallization of platinum nanoparticles on graphite nanofibers as a durable oxygen reduction catalyst for polymer electrolyte fuel cells

    Science.gov (United States)

    Peera, S. Gouse; Sahu, A. K.; Arunchander, A.; Nath, Krishna; Bhat, S. D.

    2015-11-01

    Effective surface functionalization to the hydrophobic graphite nanofibers (GNF) is performed with the biomolecule, namely deoxy-ribo-nucleic-acid (DNA) via π-π interactions. Pt nanoparticles are impregnated on GNF-DNA composite by ethylene glycol reduction method (Pt/GNF-DNA) and its effect on electro catalytic activity for oxygen reduction reaction (ORR) is systemically studied. Excellent dispersion of Pt nanoparticles over GNF-DNA surfaces with no evidence on particle aggregation is a remarkable achievement in this study. This result in higher electro chemical surface area of the catalyst, enhanced ORR behavior with significant enhancement in mass activity. The catalyst is validated in H2-O2 polymer electrolyte fuel cell (PEFC) and a peak power density of 675 mW cm-2 is achieved at a load current density of 1320 mA cm-2 with a minimal catalyst loading of 0.1 mg cm-2 at a cell temperature of 70 °C and 2 bar absolute pressure. Repeated potential cycling up to 10000 cycles in acidic media is also performed for this catalyst and found excellent stability with only 60 mV drop in the ORR half wave potential. The superior behavior of Pt/GNF-DNA catalyst is credited to the robust fibrous structure of GNF and its effective surface functionalization process via π-π interaction.

  18. Role of the acid-base properties of gallium-antimony oxide catalyst in oxidative ammonolysis of propane to acrylonitrile (AN)

    Energy Technology Data Exchange (ETDEWEB)

    Osipova, Z.G.; Sokolovskii, V.D.

    1979-07-01

    The role of the acid-base properties of gallium-antimony oxide catalyst in oxidative ammonolysis of propane to acrylonitrile (AN) was studied in a differential flow reactor at 550/sup 0/C, with the reaction mixture containing 5 3< by vol propane, 6 3< ammonia, and 18.6Vertical Bar3< oxygen diluted in helium, over ebulliated beds of a 5Vertical Bar3< Ga/Sb or a 1:3:1.5:1 Ga/Sb/Ni/P catalysts, the basicity of which was varied by adding 5 mole Vertical Bar3< of an alkaline earth metal (added as the nitrate and calcined). Both the rate of propane conversion and that of AN formation increased with increasing concentration of the basic sites (determined by back titration with benzoic acid) on both types of the catalysts and linearly correlated with the amount of nitrous oxide desorbed from the catalysts after the reaction. The presence of ammonia in the reaction mixture increased the activity and selectivity of the catalysts and the concentration of the active basic sites. Apparently, the reaction rate is limited by proton abstraction from a propane molecule with the formation of a carbanion stabilized on alkaline-earth metal cations. The rate-determining proton abstraction occurs on nucleophile basic sites, formed by dissociative adsorption of ammonia to form species such as NH, NH/sub 2/, and HNO, which are then oxidized to N/sub 2/ and N/sub 2/O.

  19. A kinetic study of plutonium dioxide dissolution in hydrochloric acid using iron (II) as an electron transfer catalyst

    International Nuclear Information System (INIS)

    Fife, K.W.

    1996-09-01

    Effective dissolution of plutonium dioxide has traditionally been accomplished by contact with strong nitric acid containing a small amount of fluoride at temperatures of ∼ 100 C. In spite of these aggressive conditions, PuO 2 dissolution is sometimes incomplete requiring additional contact with the solvent. This work focused on an alternative to conventional dissolution in nitric acid where an electron transfer catalyst, Fe(II), was used in hydrochloric acid. Cyclic voltammetry was employed as an in-situ analytical technique for monitoring the dissolution reaction rate. The plutonium oxide selected for this study was decomposed plutonium oxalate with > 95% of the material having a particle diameter (< 70 microm) as determined by a scanning laser microscopy technique. Attempts to dry sieve the oxide into narrow size fractions prior to dissolution in the HCl-Fe(II) solvent system failed, apparently due to significant interparticle attractive forces. Although sieve splits were obtained, subsequent scanning laser microscopy analysis of the sieve fractions indicated that particle segregation was not accomplished and the individual sieve fractions retained a particle size distribution very similar to the original powder assemblage. This phenomena was confirmed through subsequent dissolution experiments on the various screen fractions which illustrated no difference in kinetic behavior between the original oxide assemblage and the sieve fractions

  20. Effect of the Pd/MWCNTs anode catalysts preparation methods on their morphology and activity in a direct formic acid fuel cell

    International Nuclear Information System (INIS)

    Lesiak, B.; Mazurkiewicz, M.; Malolepszy, A.; Stobinski, L.; Mierzwa, B.; Mikolajczuk-Zychora, A.; Juchniewicz, K.; Borodzinski, A.; Zemek, J.; Jiricek, P.

    2016-01-01

    Highlights: • Catalysts properties studied by XRD, STEM, XPS methods. • Differences in Pd particle size, content of Pd, functional groups, PdC x. . • Catalytic activity studied in a Direct Formic Acid Fuel Cell. • Highest activity–catalyst prepared using a strong reducing agent (NaBH 4 ). - Abstract: Impact of Pd/MWCNTs catalysts preparation method on the catalysts morphology and activity in a formic acid electrooxidation reaction was investigated. Three reduction methods of Pd precursor involving reduction in a high pressure microwave reactor (Pd1), reduction with NaBH 4 (Pd2) and microwave-assisted polyol method (Pd3) were used in this paper. Crystallites size and morphology were studied using the scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), whereas elemental composition, Pd chemical state and functional groups content by the X-ray photoelectron spectroscopy (XPS). The prepared catalysts were tested in a direct formic acid fuel cell (DFAFC) as an anode material. The catalytic activity was correlated with a mean fraction of the total Pd atoms exposed at the surface (FE). The value of FE was calculated from the crystallites size distribution determined by the STEM measurements. Non-linear dependence of a current density versus FE, approaching the maximum at FE≈0.25 suggests that the catalytic process proceeded at Pd nanocrystallites faces, with inactive edges and corners. Pd2 catalyst exhibited highest activity due to its smallest Pd crystallites (3.2 nm), however the absence of Pd crystallites aggregation and low content of carbon in PdC x phase, i.e. x = 4 at.% may also affect the observed.

  1. Effect of the Pd/MWCNTs anode catalysts preparation methods on their morphology and activity in a direct formic acid fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Lesiak, B., E-mail: blesiak-orlowska@ichf.edu.pl [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa (Poland); Mazurkiewicz, M.; Malolepszy, A. [Faculty of Chemical and Process Engineering, Warsaw University of Technology, Waryńskiego 1, 00-645 Warszawa (Poland); Stobinski, L. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa (Poland); Faculty of Chemical and Process Engineering, Warsaw University of Technology, Waryńskiego 1, 00-645 Warszawa (Poland); Mierzwa, B.; Mikolajczuk-Zychora, A.; Juchniewicz, K.; Borodzinski, A. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa (Poland); Zemek, J.; Jiricek, P. [Institute of Physics, Academy of Sciences of the Czech Republic, 162-53 Prague 6, Cukrovarnicka 10 (Czech Republic)

    2016-11-30

    Highlights: • Catalysts properties studied by XRD, STEM, XPS methods. • Differences in Pd particle size, content of Pd, functional groups, PdC{sub x.}. • Catalytic activity studied in a Direct Formic Acid Fuel Cell. • Highest activity–catalyst prepared using a strong reducing agent (NaBH{sub 4}). - Abstract: Impact of Pd/MWCNTs catalysts preparation method on the catalysts morphology and activity in a formic acid electrooxidation reaction was investigated. Three reduction methods of Pd precursor involving reduction in a high pressure microwave reactor (Pd1), reduction with NaBH{sub 4} (Pd2) and microwave-assisted polyol method (Pd3) were used in this paper. Crystallites size and morphology were studied using the scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), whereas elemental composition, Pd chemical state and functional groups content by the X-ray photoelectron spectroscopy (XPS). The prepared catalysts were tested in a direct formic acid fuel cell (DFAFC) as an anode material. The catalytic activity was correlated with a mean fraction of the total Pd atoms exposed at the surface (FE). The value of FE was calculated from the crystallites size distribution determined by the STEM measurements. Non-linear dependence of a current density versus FE, approaching the maximum at FE≈0.25 suggests that the catalytic process proceeded at Pd nanocrystallites faces, with inactive edges and corners. Pd2 catalyst exhibited highest activity due to its smallest Pd crystallites (3.2 nm), however the absence of Pd crystallites aggregation and low content of carbon in PdC{sub x} phase, i.e. x = 4 at.% may also affect the observed.

  2. H3PO4/Al2O3 catalysts: characterization and catalytic evaluation of oleic acid conversion to biofuels and biolubricant

    Directory of Open Access Journals (Sweden)

    Lucia Regina Raddi de Araujo

    2006-06-01

    Full Text Available Al2O3 and H3PO4/Al2O3 catalysts were investigated in the conversion of oleic acid to biofuels and biolubricant at 1 atm and at 623 K. The catalytic tests were performed in a fixed bed and continuous flow reactor, using an oleic acid-catalyst ratio of 4 and N2 as the carrier gas. The reaction products were analyzed by gas chromatography and acidity measurements. N2 adsorption-desorption, X ray diffraction, 31P nuclear magnetic resonance and FT-IR spectroscopy were also employed to evaluate the textural, structural and acidic properties of the catalysts. The results showed that phosphoric acid impregnation improved the alumina decarboxylation activities, generating hydrocarbons in the range of gasoline, diesel oil and lubricant oil. The best catalytic performance was achieved with the highest surface area alumina impregnated with H3PO4, which was the solid that allied high total acidity with a large quantity of mesopores.

  3. Gas chromatography and silver-ion high-performance liquid chromatography analysis of conjugated linoleic acid isomers in free fatty acid form using sulphuric acid in methanol as catalyst.

    Science.gov (United States)

    Luna, Pilar; Juárez, Manuela; de la Fuente, Miguel Angel

    2008-09-12

    This study used GC and silver-ion HPLC to examine the effects of temperature and time on methylation of individual and mixtures of conjugated linoleic acid (CLA) isomers in free fatty acid form using sulphuric acid as catalyst. In the conditions tested (temperatures between 20 and 50 degrees C and times between 10 and 60 min) methylation was complete while avoiding isomerization of conjugated dienes and the formation of artefacts that could interfere with chromatographic determinations. An analytical method using solvent extraction of the lipids followed by selective elution of the free fatty acids from aminopropyl bonded phase columns and methylation with H(2)SO(4) in mild conditions was then applied to determine the CLA isomers in free fatty acid form in rumen fluid, and the results were evaluated.

  4. Tannic Acid an Efficient Catalyst for the Synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one Derivatives

    Directory of Open Access Journals (Sweden)

    Deepak S. Kawade

    2015-06-01

    Full Text Available Tannic acid explore a highly efficient catalytic activity for the synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one derivatives in excellent yields via cyclocondensation of aromatic aldehyde, β-naphthol and dimedone. Catalyst having advantages such as it is cheap and biodegradable and the protocol avoids the use of expensive catalyst and toxic solvent. We believe that this methodology is an efficient, simple, highly yielding, time saving and environmentally friendly. DOI: http://dx.doi.org/10.17807/orbital.v7i2.683

  5. Formic acid decomposition on Pt1/Cu (111) single platinum atom catalyst: Insights from DFT calculations and energetic span model analysis

    Science.gov (United States)

    Wang, Ying-Fan; Li, Kun; Wang, Gui-Chang

    2018-04-01

    Inspired by the recent surface experimental results that the monatomic Pt catalysts has more excellent hydrogen production that Cu(111) surface, the mechanism of decomposition of formic acid on Cu(111) and single atom Pt1/Cu(111) surface was studied by periodic density functional theory calculations in the present work. The results show that the formic acid tends to undergo dehydrogenation on both surfaces to obtain the hydrogen product of the target product, and the selectivity and catalytic activity of Pt1/Cu (111) surface for formic acid dehydrogenation are better. The reason is that the single atom Pt1/Cu(111) catalyst reduces the reaction energy barrier (i.e., HCOO → CO2 + H) of the critical step of the dehydrogenation reaction due to the fact that the single atom Pt1/Cu(111) catalyst binds formate weakly compared to that of Cu (111) one. Moreover, it was found that the Pt1/Cu (111) binds CO more strongly than that of Cu (111) one and thus leading to the difficult for the formation of CO. These two factors would make the single Pt atom catalyst had the high selectivity for the H2 production. It is hoped that the present work may help people to design the efficient H2 production from HCOOH decomposition by reduce the surface binding strength of HCOO species, for example, using the low coordination number active site like single atom or other related catalytic system.

  6. MoO3/Al2O3 Catalyst: Comparison of Catalysts Prepared by New Slurry Impregnation with Molybdic Acid with Conventional Samples

    Czech Academy of Sciences Publication Activity Database

    Spojakina, A. A.; Kostova, N. G.; Vít, Zdeněk; Zdražil, Miroslav

    2003-01-01

    Roč. 77, - (2003), s. 767-778 ISSN 0137- 5083 R&D Projects: GA AV ČR IAA4072802 Institutional research plan: CEZ:AV0Z4072921 Keywords : hydrodesulfurization * molybdenum sulphide catalyst * alumina supported molybdenum oxide Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.515, year: 2003

  7. 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.

  8. The Effect of Acidic and Redox Properties of V2O5/CeO2-ZrO2 Catalysts in Selective Catalytic Reduction of NO by NH3

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Riisager, Anders; Fehrmann, Rasmus

    2009-01-01

    V2O5 supported ZrO2 and CeO2–ZrO2 catalysts were prepared and characterized by N2 physisorption, XRPD, TPR, and NH3-TPD methods. The influence of calcination temperature from 400 to 600 °C on crystallinity, acidic and redox properties were studied and compared with the catalytic activity...... in the selective catalytic reduction (SCR) of NO with ammonia. The surface area of the catalysts decreased gradually with increasing calcination temperature. The SCR activity of V2O5/ZrO2 catalysts was found to be related with the support crystallinity, whereas V2O5/CeO2–ZrO2 catalysts were also dependent...... on acidic and redox properties of the catalyst. The V2O5/CeO2–ZrO2 catalysts showed high activity and selectivity for reduction of NO with NH3....

  9. Synthesis and characterization of 12-phosphotungstic acid supported on BEA zeolite

    Energy Technology Data Exchange (ETDEWEB)

    Jović, A.; Bajuk-Bogdanović, D.; Nedić Vasiljević, B. [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11000 Belgrade (Serbia); Milojević-Rakić, M., E-mail: maja@ffh.bg.ac.rs [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11000 Belgrade (Serbia); Krajišnik, D. [Department of Pharmaceutical Technology and Cosmetology, University of Belgrade-Faculty of Pharmacy, Vojvode Stepe 450, 11000 Belgrade (Serbia); Dondur, V. [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11000 Belgrade (Serbia); Popa, A. [Institute of Chemistry Timisoara, Bl. Mihai Viteazul 24, 300223 Timisoara (Romania); Uskoković-Marković, S. [Department of Analytical Chemistry, University of Belgrade-Faculty of Pharmacy, Vojvode Stepe 450, 11000 Belgrade (Serbia); Holclajtner-Antunović, I. [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11000 Belgrade (Serbia)

    2017-01-15

    An optimized synthetic route for obtaining heteropoly acid (HPA) species supported on BEA zeolite was applied, and different samples, comprising 20 to 50 wt% of 12-phosphotungstic acid (HPW) were prepared. The as-synthesized supported HPW were subjected to different post-synthesis routes, which involved calcination and ultrasound treatment. Characterization of these materials was performed by means of Scanning Electron Microscopy, zeta potential measurements, Infrared Spectroscopy and X-ray Powder Diffraction analysis. Results suggest strong interaction of HPW with the support and revealed that ultrasound treatment resulted in better dispersion of active phase and thus homogeneous morphology of the samples. The zeta potential was found to be dependent on the preparation procedure and HPW content in these materials, while higher HPW loadings induced its agglomeration. Catalytic activity of the synthesized materials was investigated in an ethanol dehydration reaction, where lower HPW loadings induced higher ethanol conversion. Acid sites distribution and accessibility for ethanol molecules were found to be more essential for catalytic activity than HPW loadings, i.e., amount of active sites present in these hybrid materials. - Highlights: • An optimized route for supporting heteropoly acid on beta zeolite is applied. • Ultrasound treatment of the composites gives dispersed morphology. • Lower heteropoly acid amount induces higher conversion in ethanol dehydration. • Acid sites distribution and accessibility for ethanol are essential for catalytic activity.

  10. Synthesis and characterization of 12-phosphotungstic acid supported on BEA zeolite

    International Nuclear Information System (INIS)

    Jović, A.; Bajuk-Bogdanović, D.; Nedić Vasiljević, B.; Milojević-Rakić, M.; Krajišnik, D.; Dondur, V.; Popa, A.; Uskoković-Marković, S.; Holclajtner-Antunović, I.

    2017-01-01

    An optimized synthetic route for obtaining heteropoly acid (HPA) species supported on BEA zeolite was applied, and different samples, comprising 20 to 50 wt% of 12-phosphotungstic acid (HPW) were prepared. The as-synthesized supported HPW were subjected to different post-synthesis routes, which involved calcination and ultrasound treatment. Characterization of these materials was performed by means of Scanning Electron Microscopy, zeta potential measurements, Infrared Spectroscopy and X-ray Powder Diffraction analysis. Results suggest strong interaction of HPW with the support and revealed that ultrasound treatment resulted in better dispersion of active phase and thus homogeneous morphology of the samples. The zeta potential was found to be dependent on the preparation procedure and HPW content in these materials, while higher HPW loadings induced its agglomeration. Catalytic activity of the synthesized materials was investigated in an ethanol dehydration reaction, where lower HPW loadings induced higher ethanol conversion. Acid sites distribution and accessibility for ethanol molecules were found to be more essential for catalytic activity than HPW loadings, i.e., amount of active sites present in these hybrid materials. - Highlights: • An optimized route for supporting heteropoly acid on beta zeolite is applied. • Ultrasound treatment of the composites gives dispersed morphology. • Lower heteropoly acid amount induces higher conversion in ethanol dehydration. • Acid sites distribution and accessibility for ethanol are essential for catalytic activity.

  11. An additional role for the Brønsted acid-base catalysts of mandelate racemase in transition state stabilization.

    Science.gov (United States)

    Nagar, Mitesh; Bearne, Stephen L

    2015-11-10

    Mandelate racemase (MR) catalyzes the interconversion of the enantiomers of mandelate and serves as a paradigm for understanding the enzyme-catalyzed abstraction of an α-proton from a carbon acid substrate with a high pKa. The enzyme utilizes a two-base mechanism with Lys 166 and His 297 acting as Brønsted acid and base catalysts, respectively, in the R → S reaction direction. In the S → R reaction direction, their roles are reversed. Using isothermal titration calorimetry (ITC), MR is shown to bind the intermediate/transition state (TS) analogue inhibitor benzohydroxamate (BzH) in an entropy-driven process with a value of ΔCp equal to -358 ± 3 cal mol(-1) K(-1), consistent with an increased number of hydrophobic interactions. However, MR binds BzH with an affinity that is ∼2 orders of magnitude greater than that predicted solely on the basis of hydrophobic interactions [St. Maurice, M., and Bearne, S. L. (2004) Biochemistry 43, 2524], suggesting that additional specific interactions contribute to binding. To test the hypothesis that cation-π/NH-π interactions between the side chains of Lys 166 and His 297 and the aromatic ring and/or the hydroxamate/hydroximate moiety of BzH contribute to the binding of BzH, site-directed mutagenesis was used to generate the MR variants K166M, K166C, H297N, and K166M/H297N and their binding affinity for various ligands determined using ITC. Comparison of the binding affinities of these MR variants with the intermediate/TS analogues BzH and cyclohexanecarbohydroxamate revealed that cation-π/NH-π interactions between His 297 and the hydroxamate/hydroximate moiety and the phenyl ring of BzH contribute approximately 0.26 and 0.91 kcal/mol to binding, respectively, while interactions with Lys 166 contribute approximately 1.74 and 1.74 kcal/mol, respectively. Similarly, comparison of the binding affinities of these mutants with substrate analogues revealed that Lys 166 contributes >2.93 kcal/mol to the binding of (R

  12. Preparation and characterization of alumina supported nickel-oxalate catalyst for the hydrodeoxygenation of oleic acid into normal and iso-octadecane biofuel

    International Nuclear Information System (INIS)

    Ayodele, O.B.; Togunwa, Olayinka S.; Abbas, Hazzim F.; Daud, Wan Mohd Ashri Wan

    2014-01-01

    Highlights: • Preparation of nickel oxalate complex as catalyst precursor. • Incorporation of nickel oxalate complex into alumina support. • Characterization of the alumina supported nickel oxalate catalyst. • Hydrodeoxygenation of oleic acid with nickel oxalate catalyst. • Nickel oxalate catalyst reusability studies. - Abstract: In this study, nickel II oxalate complex (NiOx) was prepared by functionalization of nickel with oxalic acid (OxA) and incorporated into Al 2 O 3 to synthesize alumina supported nickel oxalate (NiOx/Al 2 O 3 ) catalyst for the hydrodeoxygenation (HDO) of oleic acid (OA) into biofuel. The synthesized NiOx/Al 2 O 3 was characterized and the X-ray fluorescence and elemental dispersive X-ray results showed that NiOx was successfully incorporated into the structure of Al 2 O 3 . The X-ray diffraction and Raman spectroscopy results confirmed that highly dispersed Ni species are present in the NiOx/Al 2 O 3 due to the functionalization with OxA. The catalytic activity of the NiOx/Al 2 O 3 on the HDO of OA produced a mixture of 21% iso-C18 and 72% n-C18 at a 360 °C, 20 bar, 30 mg NiOx/Al 2 O 3 loading pressure and gas flow rate of 100 mL/min. The presence of i-C 18 was ascribed to the OxA functionalization which increased the acidity of NiOx/Al 2 O 3 . The NiOx/Al 2 O 3 reusability study showed consistent HDO ability after 5 runs. These results are promising for further research into biofuel production for commercialization

  13. Structural and electrochemical characterization of carbon supported Pt-Pr catalysts for direct ethanol fuel cells prepared using a modified formic acid method in a CO atmosphere.

    Science.gov (United States)

    Corradini, Patricia Gon; Antolini, Ermete; Perez, Joelma

    2013-07-28

    Pt-Pr/C electrocatalysts were prepared using a modified formic acid method, and their activity for carbon monoxide and ethanol oxidation was compared to Pt/C. No appreciable alloy formation was detected by XRD analysis. By TEM measurements it was found that Pt particle size increases with an increasing Pr content in the catalysts and with decreasing metal precursor addition time. XPS measurements indicated Pt segregation on the catalyst surface and the presence of Pr2O3 and PrO2 oxides. The addition of Pr increased the electro-catalytic activity of Pt for both CO and CH3CH2OH oxidation. The enhanced activity of Pt-Pr/C catalysts was ascribed to both an electronic effect, caused by the presence of Pr2O3, and the bi-functional mechanism, caused by the presence of PrO2.

  14. Silica sulfuric acid: a reusable solid catalyst for one pot synthesis of densely substituted pyrrole-fused isocoumarins under solvent-free conditions

    Directory of Open Access Journals (Sweden)

    Sudipta Pathak

    2013-11-01

    Full Text Available A convenient and efficient methodology for the synthesis of densely substituted pyrrole-fused isocoumarins, which employs solid-supported silica sulfuric acid (SSA as catalyst, has been developed. When the mixture of ninhydrin adducts of acetylacetone/ethyl acetoacetate and primary amines was heated on the solid surface of SSA under solvent-free conditions, the pyrrole-fused isocoumarins were formed in good yields. This synthetic method has several advantages such as the employment of solvent-free reaction conditions without the use of any toxic reagents and metal catalysts, the ease of product isolation, the use of a recyclable catalyst, the low cost, the easy availability of the starting materials, and the excellent yields of products.

  15. A recyclable Au(I) catalyst for selective homocoupling of arylboronic acids: significant enhancement of nano-surface binding for stability and catalytic activity.

    Science.gov (United States)

    Zhang, Xin; Zhao, Haitao; Wang, Jianhui

    2010-08-01

    Au nanoparticles stabilized by polystyrene-co-polymethacrylic acid microspheres (PS-co-PMAA) were prepared and characterized via X-ray diffraction (XRD), and transmission electron microscope (TEM). The Au nanoparticles supported on the microspheres showed highly selective catalytic activity for homo-coupling reactions of arylboronic acids in a system of aryl-halides and arylboronic acids. X-ray photoelectron spectroscopy (XPS) spectra of the catalyst shows large amounts of Au(I) complexes band to the surface of the Au nanoparticles, which contributes to the selective homocoupling of the arylboronic acids. More importantly, this supported Au complex is a highly recyclable catalyst. The supported Au catalyst can be recycled and reused at least 6 times for a phenylboronic acid reactant, whereas the parent complex shows very low catalytic activity for this compound. The high catalytic activity of this material is attributed to: (1) the high surface to volume ratio which leads to more active sites being exposed to reactants; (2) the strong surface binding of the Au nanoparticle to the Au(I) complexes, which enhances both the stability and the catalytic activity of these complexes.

  16. Oxygen exchange between C18O2 and ''acidic'' oxide and zeolite catalysts

    International Nuclear Information System (INIS)

    Peri, J.B.

    1975-01-01

    The exchange of oxygen between C 18 O 2 and several high-area oxides, including silica, γ-alumina, silica--alumina, and zeolite catalysts, was studied. Infrared spectra of adsorbed CO 2 and of surface ''carbonates'' were used to follow the rate of oxygen exchange and investigate the nature of unusually exchangeable surface oxide ions, present at low concentrations. Interaction of CO 2 with the surface typically produced initial exchange of one oxygen atom, as expected from interaction with a single oxide ion (CO 2 + O 2- reversible CO 3 2- ), and the number of exchangeable ions increased with increasing temperature. The rate of oxygen exchange did not correlate with chemisorption to form stable surface carbonates or with the extent of strong physical adsorption of CO 2 . With dry silica, exchange was insignificant below 600 0 ; with catalytically active zeolites and dry γ-alumina, it was detectable at 200 0 and fairly rapid at 300--400 0 . Silica--alumina required 100--150 0 higher temperature for exchange than did an active zeolite. Activity for cracking and other hydrocarbon reactions may be related to the ease of exchange of some surface oxide ions with CO 2 . Active zeolites have reactive oxide sites resembling those on dry γ-alumina, but such sites on zeolites are probably less-readily eliminated by chemisorption of H 2 O or other compounds. (U.S.)

  17. Design of an effective bifunctional catalyst organotriphosphonic acid-functionalized ferric alginate (ATMP-FA) and optimization by Box-Behnken model for biodiesel esterification synthesis of oleic acid over ATMP-FA.

    Science.gov (United States)

    Liu, Wei; Yin, Ping; Liu, Xiguang; Qu, Rongjun

    2014-12-01

    Biodiesel production has become an intense research area because of rapidly depleting energy reserves and increasing petroleum prices together with environmental concerns. This paper focused on the optimization of the catalytic performance in the esterification reaction of oleic acid for biodiesel production over the bifunctional catalyst organotriphosphonic acid-functionalized ferric alginate ATMP-FA. The reaction parameters including catalyst amount, ethanol to oleic acid molar ratio and reaction temperature have been optimized by response surface methodology (RSM) using the Box-Behnken model. It was found that the reaction temperature was the most significant factor, and the best conversion ratio of oleic acid could reach 93.17% under the reaction conditions with 9.53% of catalyst amount and 8.62:1 of ethanol to oleic acid molar ratio at 91.0 °C. The research results show that two catalytic species could work cooperatively to promote the esterification reaction, and the bifunctional ATMP-FA is a potential catalyst for biodiesel production. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. The Deoxygenation Pathways of Palmitic Acid into Hydrocarbons on Silica-Supported Ni12P5 and Ni2P Catalysts

    Directory of Open Access Journals (Sweden)

    Wenjun Zhou

    2018-04-01

    Full Text Available Pure Ni12P5/SiO2 and pure Ni2P/SiO2 catalysts were obtained by adjusting the Ni and P molar ratios, while Ni/SiO2 catalyst was prepared as a reference against which the deoxygenation pathways of palmitic acid were investigated. The catalysts were characterized by N2 adsorption, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission election microscopy (TEM, infrared spectroscopy of pyridine adsorption (Py-IR, H2-adsorption and temperature-programmed desorption of hydrogen (H2-TPD. The crystallographic planes of Ni(111, Ni12P5(400, Ni2P(111 were found mainly exposed on the above three catalysts, respectively. It was found that the deoxygenation pathway of palmitic acid mainly proceeded via direct decarboxylation (DCO2 to form C15 on Ni/SiO2. In contrast, on the Ni12P5/SiO2 catalyst, there were two main competitive pathways producing C15 and C16, one of which mainly proceeded via the decarbonylation (DCO to form C15 accompanying water formation, and the other pathway produced C16 via the dehydration of hexadecanol intermediate, and the yield of C15 was approximately twofold that of C16. Over the Ni2P/SiO2 catalyst, two main deoxygenation pathways formed C15, one of which was mainly the DCO pathway and the other was dehydration accompanying the hexadecanal intermediate and then direct decarbonylation without water formation. The turn over frequency (TOF followed the order: Ni12P5/SiO2 > Ni/SiO2 > Ni2P/SiO2.

  19. Graphene-Based Nanomaterials as Heterogeneous Acid Catalysts: A Comprehensive Perspective

    Directory of Open Access Journals (Sweden)

    Bhaskar Garg

    2014-09-01

    Full Text Available Acid catalysis is quite prevalent and probably one of the most routine operations in both industrial processes and research laboratories worldwide. Recently, “graphene”, a two dimensional single-layer carbon sheet with hexagonal packed lattice structure, imitative of nanomaterials, has shown great potential as alternative and eco-friendly solid carbocatalyst for a variety of acid-catalyzed reactions. Owing to their exceptional physical, chemical, and mechanical properties, graphene-based nanomaterials (G-NMs offer highly stable Brønsted acidic sites, high mass transfer, relatively large surface areas, water tolerant character, and convenient recoverability as well as recyclability, whilst retaining high activity in acid-catalyzed chemical reactions. This comprehensive review focuses on the chemistry of G-NMs, including their synthesis, characterization, properties, functionalization, and up-to-date applications in heterogeneous acid catalysis. In line with this, in certain instances readers may find herein some criticisms that should be taken as constructive and would be of value in understanding the scope and limitations of current approaches utilizing graphene and its derivatives for the same.

  20. CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

    Science.gov (United States)

    Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

    2014-07-01

    An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system.

  1. Synthesis of waste cooking oil based biodiesel via ferric-manganese promoted molybdenum oxide / zirconia nanoparticle solid acid catalyst: influence of ferric and manganese dopants.

    Science.gov (United States)

    Alhassan, Fatah H; Rashid, Umer; Taufiq-Yap, Yun Hin

    2015-01-01

    The utilization of ferric-manganese promoted molybdenum oxide/zirconia (Fe-Mn- MoO3/ZrO2) (FMMZ) solid acid catalyst for production of biodiesel was demonstrated. FMMZ is produced through impregnation reaction followed by calcination at 600°C for 3 h. The characterization of FMMZ had been done using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), temperature programmed desorption of NH3 (TPD-NH3), transmission electron microscopy(TEM) and Brunner-Emmett-Teller (BET) surface area measurement. The effect of waste cooking oil methyl esters (WCOME's) yield on the reactions variables such as reaction temperature, catalyst loading, molar ratio of methanol/oil and reusability were also assessed. The catalyst was used to convert the waste cooking oil into corresponding methyl esters (95.6%±0.15) within 5 h at 200℃ reaction temperature, 600 rpm stirring speed, 1:25 molar ratio of oil to alcohol and 4% w/w catalyst loading. The reported catalyst was successfully recycled in six connective experiments without loss in activity. Moreover, the fuel properties of WCOME's were also reported using ASTM D 6751 methods.

  2. Biodiesel from Hydrolyzed Waste Cooking Oil Using a S-ZrO2/SBA-15 Super Acid Catalyst under Sub-Critical Conditions

    Directory of Open Access Journals (Sweden)

    Muhammad Nobi Hossain

    2018-01-01

    Full Text Available Due to rapid changes in food habits, a substantial amount of waste fat and used oils are generated each year. Due to strong policies, the disposal of this material into nearby sewers causes ecological and environmental problems in many parts of the world. For efficient management, waste cooking oil, a less expensive, alternative and promising feedstock, can be used as a raw material for producing biofuel. In the present study, we produced a biodiesel from hydrolyzed waste cooking oil with a subcritical methanol process using a synthesized solid super acid catalyst, a sulfated zirconium oxide supported on Santa Barbara Amorphous silica (S-ZrO2/SBA-15. The characterization of the synthesized catalyst was carried out using scanning electron microscopy (SEM, X-ray diffraction (XRD, and the Brunauer-Emmett-Teller (BET method. The catalytic effect on biodiesel production was examined by varying the parameters: temperatures of 120 to 200 °C, 5–20 min times, oil-to-methanol mole ratios between 1:5 to 1:20, and catalyst loadings of 1–2.5%. The maximum biodiesel yield was 96.383%, obtained under optimum reaction conditions of 140 °C, 10 min, and a 1:10 oil-to-methanol molar ratio with a 2.0% catalyst loading. We successfully reused the catalyst five times without regeneration with a 90% efficiency. The fuel properties were found to be within the limits set by the biodiesel standard.

  3. Catalyst evaluation for oxygen reduction reaction in concentrated phosphoric acid at elevated temperatures

    DEFF Research Database (Denmark)

    Hu, Yang; Jiang, Yiliang; Jensen, Jens Oluf

    2018-01-01

    Phosphoric acid is the common electrolyte for high-temperature polymer electrolyte fuel cells (HT-PEMFCs) that have advantages such as enhanced CO tolerance and simplified heat and water management. The currently used rotating disk electrode technique is limited to tests in dilute solutions at lo...

  4. Sulfuric acid as a catalyst for ring-opening of biobased bis-epoxides

    Science.gov (United States)

    Vegetable oils can be relatively and easily transformed into bio-based epoxides. Because of this, the acid-catalyzed epoxide ring-opening has been explored for the preparation of bio-based lubricants and polymers. Detailed model studies are carried out only with mono-epoxide made from methyl oleate,...

  5. Silica Sulphuric Acid as an Efficient Catalyst for the Catalytic and ...

    African Journals Online (AJOL)

    NJD

    presence of a catalytic amount of silica sulphuric acid under micellar media in moderate to good yields. KEYWORDS. Sodium ... Production of aromatic nitro compounds is an important industrial process and involves the unsolved problems of ... V7 and Re9) and titanium and chromium silicates.10 Some of the procedures ...

  6. Catalytic Hydrogenation of Levulinic Acid in Water into g-Valerolactone over Bulk Structure of Inexpensive Intermetallic Ni-Sn Alloy Catalysts

    Directory of Open Access Journals (Sweden)

    Rodiansono Rodiansono

    2015-07-01

    Full Text Available A bulk structure of inexpensive intermetallic nickel-tin (Ni-Sn alloys catalysts demonstrated highly selective in the hydrogenation of levulinic acid in water into g-valerolactone. The intermetallic Ni-Sn catalysts were synthesized via a very simple thermochemical method from non-organometallic precursor at low temperature followed by hydrogen treatment at 673 K for 90 min. The molar ratio of nickel salt and tin salt was varied to obtain the corresponding Ni/Sn ratio of 4.0, 3.0, 2.0, 1.5, and 0.75. The formation of Ni-Sn alloy species was mainly depended on the composition and temperature of H2 treatment. Intermetallics Ni-Sn that contain Ni3Sn, Ni3Sn2, and Ni3Sn4 alloy phases are known to be effective heterogeneous catalysts for levulinic acid hydrogenation giving very excellence g-valerolactone yield of >99% at 433 K, initial H2 pressure of 4.0 MPa within 6 h. The effective hydrogenation was obtained in H2O without the formation of by-product. Intermetallic Ni-Sn(1.5 that contains Ni3Sn2 alloy species demonstrated very stable and reusable catalyst without any significant loss of its selectivity. © 2015 BCREC UNDIP. All rights reserved. Received: 26th February 2015; Revised: 16th April 2015; Accepted: 22nd April 2015  How to Cite: Rodiansono, R., Astuti, M.D., Ghofur, A., Sembiring, K.C. (2015. Catalytic Hydrogenation of Levulinic Acid in Water into g-Valerolactone over Bulk Structure of Inexpensive Intermetallic Ni-Sn Alloy Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (2: 192-200. (doi:10.9767/bcrec.10.2.8284.192-200Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.8284.192-200  

  7. The enhancement of the hydrolysis of bamboo biomass in ionic liquid with chitosan-based solid acid catalysts immobilized with metal ions.

    Science.gov (United States)

    Cheng, Jie; Wang, Nan; Zhao, Dezhou; Qin, Dandan; Si, Wenqing; Tan, Yunfei; Wei, Shun'an; Wang, Dan

    2016-11-01

    Three kinds of sulfonated cross-linked chitosan (SCCR) immobilized with metal ions of Cu(2+), Fe(3+) and Zn(2+) individually were synthesized and firstly used as solid acid catalysts in the hydrolysis of bamboo biomass. FTIR spectra showed that metal ions had been introduced into SCCR and the N-metal ions coordinate bound was formed. The particle sizes of these catalysts were about 500-1000μm with a pore size of 50-160μm. All of the three kinds of catalysts performed well for bamboo hydrolysis with 1-butyl-3-methyl-imidazolium chloride used as solvent. The most effective one was sulfonated cross-linked chitosan immobilized with Fe(3+) (Fe(3+)-SCCR). TRS yields were up to 73.42% for hydrolysis of bamboo powder in [C4mim]Cl with Fe(3+)-SCCR at 120°C and 20RPM after 24h. These novel chitosan-based metal ions immobilized solid acid catalysts with ionic liquids as the solvent might be promising to facilitate cost-efficient conversion of biomass into biofuels and bioproducts. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Facile and Low-Cost Preparation of Nb/Al Oxide Catalyst with High Performance for the Conversion of Kiwifruit Waste Residue to Levulinic Acid

    Directory of Open Access Journals (Sweden)

    Rui Wang

    2015-09-01

    Full Text Available The kiwifruit industry is booming worldwide. As a result, a great deal of kiwifruit waste residue (KWR containing monosaccharides is produced and discarded. This material shows great potential for the production of platform chemicals. In this study, a series of Nb/Al oxide catalysts were synthesized via a facile and low-cost coprecipitation method, and their structures were characterized using: thermal gravimetric analysis (TGA, XRD, FESEM, TEM, X-ray photoelectron spectroscopy (XPS, NH3-TPD, N2 adsorption-desorption, and FTIR-Pyridine adsorption. Experimental results of sugar-to-levulinic acid (LA conversion revealed that the 20%Nb/Al oxide catalyst provided the highest catalytic performance and durability in terms of LA yield from fructose (74.2% at 463 K after 10 min and from glucose (47.5% at 473 K after 15 min. Notably, the 20% Nb/Al oxide catalyst with a 10% dosage is capable of converting kiwifruit waste residue to LA at 473 K after 10 min. In conclusion, the enhanced catalytic performance was obtained due to the high acidity, and large surface areaof Nb/Al oxide catalyst.

  9. Physical-chemical properties of the surface of B2O3-P2O5-MeOx/SiO2 catalysts and its effect on the parameters of the process of aldol condensation of propionic acid with formaldehyde

    International Nuclear Information System (INIS)

    Yivasyiv, V.V.; Pyikh, Z.G.; Zhiznevs'kij, V.M.; Nebesnij, R.V.

    2011-01-01

    Effect of catalyst B 2 O 3 -P 2 O 5 -MeO x /SiO 2 composition on its physical-chemical properties has been investigated. Relations between physical-chemical and catalytic properties of catalysts in the gas-phase reaction of propionic acid with formaldehyde to methacrylic acid have been found. Effect of the specific surface area and the specific surface acidity on the propionic acid conversion has been determined. Effect of the acidic active site's strength on the selectivity of reaction products has been determined. It has been pointed that methacrylic acid is formed on the moderate strength acidic active sites, whereas the by-product (diethyl ketone) - on the strong acidic active sites of the catalyst.

  10. Niobium, catalyst repair kit

    International Nuclear Information System (INIS)

    Tanabe, K.

    1991-01-01

    This paper reports that niobium oxides, when small amounts are added to known catalysts, enhance catalytic activity and selectivity and prolong catalyst life. Moreover, niobium oxides exhibit a pronounced effect as supports of metal or metal oxide catalysts. Recently we found that the surface acidity of hydrated niobium pentoxide, niobic acid (Nb 2 O 5 · nH 2 O), corresponds to the acidity of 70% sulfuric acid and exhibits high catalytic activity, selectivity, and stability for acid-catalyzed reactions in which water molecules participate. Although there are few differences in electronegativity and ionic radius between niobium and its neighbors in the periodic table, it is interesting that the promoter effect, support effect, and acidic nature of niobium compounds are quite different from those of compounds of the surrounding elements. Here we review what's known of niobium compounds from the viewpoint of their pronounced catalytic behavior

  11. High efficient conversion of furfural to 2-methylfuran over Ni-Cu/Al2O3 catalyst with formic acid as a hydrogen donor

    DEFF Research Database (Denmark)

    Fu, Zhaolin; Wang, Ze; Lin, Weigang

    2017-01-01

    Conversion of furfural to 2-methylfuran over Cu/Al2O3, Ni/Al2O3 and Ni-Cu/Al2O3 catalysts were investigated with formic acid as a hydrogen donor. Ni/Al2O3 showed a high catalytic activity but a moderate selectivity to 2-methylfuran. Contrarily, Cu/Al2O3 showed a low catalytic activity but a high...... selectivity for carbonyl reduction. Over the bimetallic catalysts Ni-10%Cu/Al2O3, by increasing Ni content, more furfural was converted with the reduction of carbonyl primarily. The effect of reaction solvent and the fraction of formic acid were also studied. The result showed that isopropanol solvent could...

  12. 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)

  13. Use of Pyrolyzed Iron Ethylenediaminetetraacetic Acid Modified Activated Carbon as Air–Cathode Catalyst in Microbial Fuel Cells

    KAUST Repository

    Xia, Xue

    2013-08-28

    Activated carbon (AC) is a cost-effective catalyst for the oxygen reduction reaction (ORR) in air-cathode microbial fuel cells (MFCs). To enhance the catalytic activity of AC cathodes, AC powders were pyrolyzed with iron ethylenediaminetetraacetic acid (FeEDTA) at a weight ratio of FeEDTA:AC = 0.2:1. MFCs with FeEDTA modified AC cathodes and a stainless steel mesh current collector produced a maximum power density of 1580 ± 80 mW/m2, which was 10% higher than that of plain AC cathodes (1440 ± 60 mW/m 2) and comparable to Pt cathodes (1550 ± 10 mW/m2). Further increases in the ratio of FeEDTA:AC resulted in a decrease in performance. The durability of AC-based cathodes was much better than Pt-catalyzed cathodes. After 4.5 months of operation, the maximum power density of Pt cathode MFCs was 50% lower than MFCs with the AC cathodes. Pyridinic nitrogen, quaternary nitrogen and iron species likely contributed to the increased activity of FeEDTA modified AC. These results show that pyrolyzing AC with FeEDTA is a cost-effective and durable way to increase the catalytic activity of AC. © 2013 American Chemical Society.

  14. 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.

  15. Bio-inspired CO2 reduction by a rhenium tricarbonyl bipyridine-based catalyst appended to amino acids and peptidic platforms: incorporating proton relays and hydrogen-bonding functional groups.

    Science.gov (United States)

    Chabolla, S A; Machan, C W; Yin, J; Dellamary, E A; Sahu, S; Gianneschi, N C; Gilson, M K; Tezcan, F A; Kubiak, C P

    2017-06-02

    Herein, we report a new approach to bio-inspired catalyst design. The molecular catalyst employed in these studies is based on the robust and selective Re(bpy)(CO) 3 Cl-type (bpy = 2,2'-bipyridine) homogeneous catalysts, which have been extensively studied for their ability to reduce CO 2 electrochemically or photochemically in the presence of a photosensitizer. These catalysts can be highly active photocatalysts in their own right. In this work, the bipyridine ligand was modified with amino acids and synthetic peptides. These results build on earlier findings wherein the bipyridine ligand was functionalized with amide groups to promote dimer formation and CO 2 reduction by an alternate bimolecular mechanism at lower overpotential (ca. 250 mV) than the more commonly observed unimolecular process. The bio-inspired catalysts were designed to allow for the incorporation of proton relays to support reduction of CO 2 to CO and H 2 O. The coupling of amino acids tyrosine and phenylalanine led to the formation of two structurally similar Re catalyst/peptide catalysts for comparison of proton transport during catalysis. This article reports the synthesis and characterization of novel catalyst/peptide hybrids by molecular dynamics (MD simulations of structural dynamics), NMR studies of solution phase structures, and electrochemical studies to measure the activities of new bio-inspired catalysts in the reduction of CO 2.

  16. Gadolinium heteropoly complex K 17[Gd(P 2W 17O 61) 2] as a potential MRI contrast agent

    Science.gov (United States)

    Sun, Guoying; Feng, Jianghua; Wu, Huifeng; Pei, Fengkui; Fang, Ke; Lei, Hao

    2004-10-01

    Gadolinium heteropoly complex K17[Gd(P2W17O61)2] has been evaluated by in vitro and in vivo experiments as a potential contrast agent for magnetic resonance imaging (MRI). The thermal analysis and conductivity study indicate that this complex has good thermal stability and wide pH stability range. The T1 relaxivity is 7.59 mM-1 s-1 in aqueous solution and 7.97 mM-1 s-1 in 0.725 mmol l-1 bovine serum albumin (BSA) solution at 25 °C and 9.39 T, respectively. MR imaging of three male Sprague-Dawley rats showed remarkable enhancement in rat liver after intravenous injection, which persisted longer than with Gd-DTPA. The signal intensity increased by 57.1±16.9% during the whole imaging period at 0.082 mmol kg-1dose. Our preliminary in vitro and in vivo studies indicate that K17[Gd(P2W17O61)2] is a potential liver-specific MRI contrast agent.

  17. Novel Ion-Exchange Catalysts for Reactions Involving Lipophilic Reagents: Perspectives in the Reaction of Esterifications of Fatty Acids with Methanol

    Czech Academy of Sciences Publication Activity Database

    Centomo, P.; Bonato, I.; Hanková, Libuše; Holub, Ladislav; Jeřábek, Karel; Zecca, M.

    2013-01-01

    Roč. 56, 9-10 (2013), s. 611-617 ISSN 1022-5528. [Nordic Symposium on Catalysis /15./. Mariehamn, Åland, 10.06.2012-12.06.2012] Grant - others:IMUR(IT) 2008SXASBC_004 Institutional support: RVO:67985858 Keywords : sulfonated resin s * acylation * lipophilic acid catalysts Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.220, year: 2013

  18. Effect of the structural characteristics of binary Pt-Ru and ternary Pt-Ru-M fuel cell catalysts on the activity of ethanol electrooxidation in acid medium.

    Science.gov (United States)

    Antolini, Ermete

    2013-06-01

    In view of their possible use as anode materials in acid direct ethanol fuel cells, the electrocatalytic activity of Pt-Ru and Pt-Ru-M catalysts for ethanol oxidation has been investigated. This minireview examines the effects of the structural characteristics of Pt-Ru, such as the degree of alloying and Ru oxidation state, on the electrocatalytic activity for ethanol oxidation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. TUNGSTOPHOSPHORIC ACID HETEROGENIZED ONTO NH4ZSM5 AS AN EFFICIENT AND RECYCLABLE CATALYST FOR THE PHOTOCATALYTIC DEGRADATION OF DYES

    Directory of Open Access Journals (Sweden)

    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.

  20. Fluidized bed catalytic pyrolysis of eucalyptus over hzsm-5: effect of acid density and gallium modification on catalyst deactivation

    Science.gov (United States)

    Catalytic fast pyrolysis of eucalyptus wood was performed on a continuous laboratory scale fluidized bed fast pyrolysis system. Catalytic activity was monitored from use of fresh catalyst up to a cumulative biomass to catalyst ratio (B/C) of 4/1 over extruded pellets of three different ZSM-5 catalys...

  1. Performance and selectivity of PtxSn/C electro-catalysts for ethanol oxidation prepared by reduction with different formic acid concentrations

    International Nuclear Information System (INIS)

    Zignani, Sabrina C.; Baglio, Vincenzo; Linares, José J.; Monforte, Giuseppe; Gonzalez, Ernesto R.; Aricò, Antonino S.

    2012-01-01

    Carbon supported Pt–Sn catalysts were prepared by reduction of Pt and Sn precursors with formic acid and characterized in terms of structure, morphology and surface properties. The electrocatalytic activity for ethanol oxidation was studied in a direct ethanol fuel cell (DEFC) at 70 °C and 90 °C. Electrochemical and physico-chemical data indicated that a proper balance of Pt and Sn species in the near surface region was necessary to maximize the reaction rate. The best atomic surface composition, in terms of electrochemical performance, was Pt:Sn 65:35 corresponding to a bulk composition 75:25 namely Pt 3 Sn 1 /C. The reaction products of ethanol electro-oxidation in single cell and their distribution as a function of the nature of catalyst were determined. Essentially, acetaldehyde and acetic acid were detected as the main reaction products; whereas, a lower content of CO 2 was formed. The selectivity toward acetic acid vs. acetaldehyde increased with the increase of the Sn content and decreased by decreasing the concentration of the reducing agent used in the catalyst preparation. According to the recent literature, these results have been interpreted on the basis of ethanol adsorption characteristics and ligand effects occurring for Sn-rich electrocatalysts.

  2. Synthesis of fatty acid methyl ester from the transesterification of high- and low-acid-content crude palm oil (Elaeis guineensis) and karanj oil (Pongamia pinnata) over a calcium-lanthanum-aluminum mixed-oxides catalyst.

    Science.gov (United States)

    Syamsuddin, Y; Murat, M N; Hameed, B H

    2016-08-01

    The synthesis of fatty acid methyl ester (FAME) from the high- and low-acid-content feedstock of crude palm oil (CPO) and karanj oil (KO) was conducted over CaO-La2O3-Al2O3 mixed-oxide catalyst. Various reaction parameters were investigated using a batch reactor to identify the best reaction condition that results in the highest FAME yield for each type of oil. The transesterification of CPO resulted in a 97.81% FAME yield with the process conditions of 170°C reaction temperature, 15:1 DMC-to-CPO molar ratio, 180min reaction time, and 10wt.% catalyst loading. The transesterification of KO resulted in a 96.77% FAME yield with the conditions of 150°C reaction temperature, 9:1 DMC-to-KO molar ratio, 180min reaction time, and 5wt.% catalyst loading. The properties of both products met the ASTM D6751 and EN 14214 standard requirements. The above results showed that the CaO-La2O3-Al2O3 mixed-oxide catalyst was suitable for high- and low-acid-content vegetable oil. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Catalyst in Basic Oleochemicals

    Directory of Open Access Journals (Sweden)

    Eva Suyenty

    2007-10-01

    Full Text Available Currently Indonesia is the world largest palm oil producer with production volume reaching 16 million tones per annum. The high crude oil and ethylene prices in the last 3 – 4 years contribute to the healthy demand growth for basic oleochemicals: fatty acids and fatty alcohols. Oleochemicals are starting to replace crude oil derived products in various applications. As widely practiced in petrochemical industry, catalyst plays a very important role in the production of basic oleochemicals. Catalytic reactions are abound in the production of oleochemicals: Nickel based catalysts are used in the hydrogenation of unsaturated fatty acids; sodium methylate catalyst in the transesterification of triglycerides; sulfonic based polystyrene resin catalyst in esterification of fatty acids; and copper chromite/copper zinc catalyst in the high pressure hydrogenation of methyl esters or fatty acids to produce fatty alcohols. To maintain long catalyst life, it is crucial to ensure the absence of catalyst poisons and inhibitors in the feed. The preparation methods of nickel and copper chromite catalysts are as follows: precipitation, filtration, drying, and calcinations. Sodium methylate is derived from direct reaction of sodium metal and methanol under inert gas. The sulfonic based polystyrene resin is derived from sulfonation of polystyrene crosslinked with di-vinyl-benzene. © 2007 BCREC UNDIP. All rights reserved.[Presented at Symposium and Congress of MKICS 2007, 18-19 April 2007, Semarang, Indonesia][How to Cite: E. Suyenty, H. Sentosa, M. Agustine, S. Anwar, A. Lie, E. Sutanto. (2007. Catalyst in Basic Oleochemicals. Bulletin of Chemical Reaction Engineering and Catalysis, 2 (2-3: 22-31.  doi:10.9767/bcrec.2.2-3.6.22-31][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.2.2-3.6.22-31 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/6

  4. Melamine Trisulfonic Acid as a New, Efficient and Reusable Catalyst for the Chemoselective Oxathioacetalyzation of Aldehydes

    International Nuclear Information System (INIS)

    Shirini, F.; Albadi, J.

    2010-01-01

    We developed an efficient and high yielding method for the chemoselective oxathioacetalyzation of aldehydes. Relatively short reaction times, high efficiency, heterogeneous reaction conditions, availability and recyclability of the reagent and easy work-up are among the other advantages of this method, which make this procedure a useful and attractive addition to the available methods. We are exploring further applications of MTSA for the other types of functional group transformations in our laboratory. 1,3-Oxathiolanes are synthetically important protecting groups for aldehydes due to their considerable stability under a variety of reaction conditions, ease of formation and removal, equality to acyl carbanions in C-C bond forming reactions, and use in enantioselective synthesis of tertiary α-hydroxy acids and glycols

  5. Optimization of Acid Orange 7 Degradation in Heterogeneous Fenton-like Reaction Using Fe3-xCoxO4 Catalyst

    Science.gov (United States)

    Ibrahim, M. Z.; Alrozi, R.; Zubir, N. A.; Bashah, N. A.; Ali, S. A. Md; Ibrahim, N.

    2018-05-01

    The oxidation process such as heterogeneous Fenton and/or Fenton-like reactions is considered as an effective and efficient method for treatment of dye degradation. In this study, the degradation of Acid Orange 7 (AO7) was investigated by using Fe3-xCoxO4 as a heterogeneous Fenton-like catalyst. Response surface methodology (RSM) was used to optimize the operational parameters condition and the interaction of two or more parameters. The parameter studies were catalyst dosage (X1 ), pH (X2 ) and H2O2 concentration (X3 ) towards AO7 degradation. Based on analysis of variance (ANOVA), the derived quadratic polynomial model was significant whereby the predicted values matched the experimental values with regression coefficient of R2 = 0.9399. The optimum condition for AO7 degradation was obtained at catalyst dosage of 0.84 g/L, pH of 3 and H2O2 concentration of 46.70 mM which resulted in 86.30% removal of AO7 dye. These findings present new insights into the influence of operational parameters in the heterogeneous Fenton-like oxidation of AO7 using Fe3-xCoxO4 catalyst.

  6. 3-[(3-(Trimethoxysilylpropylthio]propane-1-oxy-sulfonic acid: An efficient recyclable heterogeneous catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H-ones/thiones

    Directory of Open Access Journals (Sweden)

    Srinivasa Rao Jetti

    2017-05-01

    Full Text Available An efficient method for the synthesis of 3,4-dihydropyrimidin-2(1H-ones and thiones through one-pot three-component reaction of ethyl acetoacetate, aryl aldehyde and urea or thiourea in ethanol using 3-[(3-(trimethoxysilylpropylthio]propane-1-oxy-sulfonic acid as catalyst is described. The use of 3-[(3-(trimethoxysilylpropylthio]propane-1-oxy-sulfonic acid as a catalyst offers several advantages such as high yields, short reaction times, mild reaction condition and a recyclable catalyst with a very easy work up.

  7. Effect of metal ratio and calcination temperature of chromium based mixed oxides catalyst on FAME density from palm fatty acid distillate

    Science.gov (United States)

    Wan, Z.; Fatimah, S.; Shahar, S.; Noor, A. C.

    2017-09-01

    Mixed oxides chromium based catalysts were synthesized via sol-gel method for the esterification of palm fatty acid distillate (PFAD) to produce fatty acid methyl ester (FAME). The reactions were conducted in a batch reactor at reaction temperature of 160 °C for 4 h and methanol to PFAD molar ratio of 3:1. The effects of catalyst preparation conditions which are the mixed metal ratio and calcination temperature were studied. The various metal ratio of Cr:Mn (1:0, 0:1, 1:1, 1:2 and 2:1) and Cr:Ti (0:1, 1:1, 1:2 and 2:1) resulted in FAME density ranges from 1.041 g/cm3 to 0.853 g/cm3 and 1.107 g/cm3 to 0.836 g/cm3, respectively. The best condition catalyst was found to be Cr:Ti metal ratio of 1:2 and Cr:Mn metal ratio of 1:1. The calcination temperature of the mixed oxides between 300 °C to 700°C shows effect on the FAME density obtained in the reaction. The calcination at 500°C gave the lowest FAME density of 0.836 g/cm3 and 0.853 g/cm3 for Cr:Ti and Cr:Mn mixed oxides, respectively. The density of FAME is within the value range of the biodiesel fuel property. Thus, mixed oxides of Cr-Ti and Cr-Mn have good potentials as heterogeneous catalyst for FAME synthesis from high acid value oils such as PFAD.

  8. Catalysts and methods of using the same

    Energy Technology Data Exchange (ETDEWEB)

    Slowing, Igor Ivan; Kandel, Kapil

    2017-02-14

    The present invention provides a catalyst including a mesoporous silica nanoparticle and a catalytic material comprising iron. In various embodiments, the present invention provides methods of using and making the catalyst. In some examples, the catalyst can be used to hydrotreat fatty acids or to selectively remove fatty acids from feedstocks.

  9. Optimization of catalyst-free production of biodiesel from Ceiba pentandra (kapok) oil with high free fatty acid contents

    International Nuclear Information System (INIS)

    Ong, Lu Ki; Effendi, Chintya; Kurniawan, Alfin; Lin, Chun Xiang; Zhao, Xiu Song; Ismadji, Suryadi

    2013-01-01

    Catalyst-free biodiesel production from non-edible Ceiba pentandra (kapok) oil via supercritical methanol transesterification was demonstrated in this work. The supercritical transesterification experiments were performed in a batch reactor at temperatures of 250–350 °C, pressures of 10–18 MPa, reaction times of 120–600 s, and methanol to oil molar ratios of 15:1–35:1. Response surface methodology (RSM) and four-way analysis of variance (ANOVA) were applied for the design and optimization of the experiments with respect to temperature, pressure, reaction time, and molar ratio of methanol to oil simultaneously. The response (i.e., FAME yield) was fitted by a quadratic polynomial regression model using least square analysis in a five-level-four-factor central composite design (CCD). The optimum conditions were found as follows: methanol to oil molar ratio of 30:1, temperature of 322 °C, pressure of 16.7 MPa, and reaction time of 476 s with FAME (fatty acid methyl ester) yield of 95.5%. The significance of the reaction parameters toward FAME yield was in the order of methanol to oil molar ratio > reaction time > pressure > temperature. - Highlights: • Transesterification of non-edible kapok oil into biodiesel via a non-catalytic route. • Methanol to oil molar ratio, temperature, pressure, and reaction time were optimized. • Experimental design in a five-level-four-factor central composite design. • Application of quadratic polynomial model for fitting the response (FAME yield)

  10. Highly active carbon supported ternary PdSnPtx (x=0.1-0.7) catalysts for ethanol electro-oxidation in alkaline and acid media.

    Science.gov (United States)

    Wang, Xiaoguang; Zhu, Fuchun; He, Yongwei; Wang, Mei; Zhang, Zhonghua; Ma, Zizai; Li, Ruixue

    2016-04-15

    A series of trimetallic PdSnPtx (x=0.1-0.7)/C catalysts with varied Pt content have been synthesized by co-reduction method using NaBH4 as a reducing agent. These catalysts were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and chronoamperometry (CA). The electrochemical results show that, after adding a minor amount of Pt dopant, the resultant PdSnPtx/C demonstrated more superior catalytic performance toward ethanol oxidation as compared with that of mono-/bi-metallic Pd/C or PdSn/C in alkaline solution and the PdSnPt0.2/C with optimal molar ratio reached the best. In acid solution, the PdSnPt0.2/C also depicted a superior catalytic activity relative to the commercial Pt/C catalyst. The possible enhanced synergistic effect between Pd, Sn/Sn(O) and Pt in an alloyed state should be responsible for the as-revealed superior ethanol electro-oxidation performance based upon the beneficial electronic effect and bi-functional mechanism. It implies the trimetallic PdSnPt0.2/C with a low Pt content has a promising prospect as anodic electrocatalyst in fields of alkali- and acid-type direct ethanol fuel cells. Copyright © 2016 Elsevier Inc. All rights reserved.

  11. Transesterification of palm oil to biodiesel using Br(φ)nsted acidic ionic liquid as high-efficient and eco-friendly catalyst

    Institute of Scientific and Technical Information of China (English)

    Yaoyao Feng; Ting Qiu; Jinbei Yang; Ling Li; Xiaoda Wang; Hongxing Wang

    2017-01-01

    The transesterification of palm oil and methanol catalyzed by Br(φ)nsted acidic ionic liquids was investigated.Four eco-friendly Br(φ)nsted acidic ionic liquids were prepared and their structures were characterized by NMR,FT-IR and TG-DTG.The results demonstrated that [CyN1,1PrSO3H][p-TSA] was more efficient than the other ionic liquids and chosen as catalyst for further research.The influences of various reaction parameters on the conversion of palm oil to biodiesel were performed,and the orthogonal test was investigated to seek the optimum reaction conditions,which were illustrated as follows:methanol to oil mole ratio of 24∶1,catalyst dosage of 3.0 wt% of oil,reaction temperature of 120 ℃,reaction time of 150 min,and the biodiesel yield achieved 98.4%.In addition,kinetic study was established for the conversion process,with activation energy and preexponential factor of 122.93 kJ·mol-1 and 1.83 × 1015,respectively.Meanwhile,seven-time recycling runs of ionic liquid were completed with ignorable loss of its catalyst activity.The refined biodiesel met the biodiesel standard EN 14214.

  12. Synthesis of fatty acid methyl ester from crude jatropha (Jatropha curcas Linnaeus) oil using aluminium oxide modified Mg-Zn heterogeneous catalyst.

    Science.gov (United States)

    Olutoye, M A; Hameed, B H

    2011-06-01

    The synthesis of fatty acid methyl esters (FAME) as a substitute to petroleum diesel was investigated in this study from crude jatropha oil (CJO), a non-edible, low-cost alternative feedstock, using aluminium modified heterogeneous basic oxide (Mg-Zn) catalyst. The transesterification reaction with methanol to methyl esters yielded 94% in 6h with methanol-oil ratio of 11:1, catalyst loading of 8.68 wt.% at 182°C and the properties of CJO fuel produced were determine and found to be comparable to the standards according to ASTM. In the range of experimental parameters investigated, it showed that the catalyst is selective to production of methyl esters from oil with high free fatty acid (FFA) and water content of 7.23% and 3.28%, respectively in a single stage process. Thus, jatropha oil is a promising feedstock for methyl ester production and large scale cultivation will help to reduce the product cost. Copyright © 2011 Elsevier Ltd. All rights reserved.

  13. Study on the effective utilization of palm oil (Part 1). Survey of catalysts for oxidative cleavage of palm stearin into mono and dibasic acids with middle carbon chains

    Energy Technology Data Exchange (ETDEWEB)

    Kubota, Yasuhiko; Shiina, Hisako; Mamuro, Hideo; Nakasato, Satoshi; Ooi, T L; S H, Ong A

    1987-05-01

    Production of palm oil in Malaysia increases annually and it is estimated that the production will reach 6 million tons in 1990. Palm stearin which constitutes 20% or more of palm oil is not suitable for the food production, but if it is successfully converted into mono and dibasic acids with middle carbon chains, a big potential demand as excellent lubricating oil is expected. Chemical Engineering Institute, Agency of Industrial Science and Technology studied this matter jointly with Malaysian Institute of Palm Oil. Various metal (II) ion-exchanged zeolites which were considered to be effective catalysts for the above conversion were screened and from the analytical results utilizing signal strength of carboxyl proton, it was found that several catalysts were effective for the formation of carboxylic acids. Furthermore, it was revealed that Mn (II) ion-exchanged zeolite 5A and Co(II)-Cu(II) ion-exchanged zeolite Y were the catalysts suitable for the objective of this study, but a study for finding out the conditions to obtain high conversion ratio is required. (4 tabs, 28 refs)

  14. Activity of ruthenium, rhodium, iridium-ruthenium and iridium-rhodium adsorbed catalysts in dehydrogenation of formic acid

    Energy Technology Data Exchange (ETDEWEB)

    Mikhailov, V A; Zubovich, I A [Yaroslavskij Politekhnicheskij Inst. (USSR)

    1977-04-01

    The activity of Ru-, Rh- (Ir+nRu)- and (Ir+nRn) catalysts on sugar carbon and silicon dioxide in decomposition of HCOOH was studied. The catalyst activity increases in the series Ircatalysts on silicon dioxide. The results obtained point to activity of single centres (Ru)/sub 1/ and (Rh)/sub 1/ in the reaction of dehydration of HCOOH. It is shown that in the course of preparation of (Ir+nRh)- and (Ir+nRu)-catalysts the Ir atoms interact with Ru(Rh), and variable-composition structures are formed.

  15. Effect of W on activity of Pt-Ru/C catalyst for methanol electrooxidation in acidic medium

    International Nuclear Information System (INIS)

    Wang Zhenbo; Zuo Pengjian; Yin Geping

    2009-01-01

    The effect of W on the activity of Pt-Ru/C catalyst was investigated. The Pt-Ru-W/C and Pt-Ru/C-TR catalysts were prepared by thermal reduction method. Comparison was made to a homemade Pt-Ru/C-CR catalyst prepared by chemical reduction. Their performances were tested by using a glassy carbon thin film electrode through cyclic voltammetric and chronoamperometric curves. The particle size, structure, composition, and surface state of homemade catalyst were determined by means of X-ray diffraction (XRD), energy dispersive analysis of X-ray (EDAX), transmission electron microscopy (TEM), and X-ray photoelectron spectrometry (XPS). The result of XRD analysis shows that the homemade ternary catalyst exhibits face-centered cubic structure and has smaller lattice parameter than Pt-alone and homemade Pt-Ru/C catalysts. The particle size of Pt-Ru-W/C catalyst is relatively large of 6.5 nm. Its electrochemically active specific area is 20 m 2 g -1 less than that of Pt-Ru/C-CR, and much twice as big as that of Pt-Ru/C-TR. But, XPS analysis shows that the addition of W changes the surface state of Pt components in the alloy and can clean Pt surface active sites which are adsorbed by hydrogen. The electrocatalytic activity and tolerance performance to CO ads of Pt-Ru-W/C catalyst for methanol electrooxidation is the best due to the promoting function of W in comparison with homemade Pt-Ru/C ones.

  16. Production of Bio-Hydrogenated Diesel by Hydrotreatment of High-Acid-Value Waste Cooking Oil over Ruthenium Catalyst Supported on Al-Polyoxocation-Pillared Montmorillonite

    Directory of Open Access Journals (Sweden)

    Kinya Sakanishi

    2012-02-01

    Full Text Available Waste cooking oil with a high-acid-value (28.7 mg-KOH/g-oil was converted to bio-hydrogenated diesel by a hydrotreatment process over supported Ru catalysts. The standard reaction temperature, H2 pressure, liquid hourly space velocity (LHSV, and H2/oil ratio were 350 °C, 2 MPa, 15.2 h–1, and 400 mL/mL, respectively. Both the free fatty acids and the triglycerides in the waste cooking oil were deoxygenated at the same time to form hydrocarbons in the hydrotreatment process. The predominant liquid hydrocarbon products (98.9 wt% were n-C18H38, n-C17H36, n-C16H34, and n-C15H32 when a Ru/SiO2 catalyst was used. These long chain normal hydrocarbons had high melting points and gave the liquid hydrocarbon product over Ru/SiO2 a high pour point of 20 °C. Ru/H-Y was not suitable for producing diesel from waste cooking oil because it formed a large amount of C5–C10 gasoline-ranged paraffins on the strong acid sites of HY. When Al-polyoxocation-pillared montmorillonite (Al13-Mont was used as a support for the Ru catalyst, the pour point of the liquid hydrocarbon product decreased to −15 °C with the conversion of a significant amount of C15–C18 n-paraffins to iso-paraffins and light paraffins on the weak acid sites of Al13-Mont. The liquid product over Ru/Al13-Mont can be expected to give a green diesel for current diesel engines because its chemical composition and physical properties are similar to those of commercial petro-diesel. A relatively large amount of H2 was consumed in the hydrogenation of unsaturated C=C bonds and the deoxygenation of C=O bonds in the hydrotreatment process. A sulfided Ni-Mo/Al13-Mont catalyst also produced bio-hydrogenated diesel by the hydrotreatment process but it showed slow deactivation during the reaction due to loss of sulfur. In contrast, Ru/Al13-Mont did not show catalyst deactivation in the hydrotreatment of waste cooking oil after 72 h on-stream because the waste cooking oil was not found to contain sulfur

  17. ALKALI RESISTANT CATALYST

    DEFF Research Database (Denmark)

    2008-01-01

    The present invention concerns the selective removal of nitrogen oxides (NOx) from gasses. In particular, the invention concerns a process, a catalyst and the use of a catalyst for the selective removal of nitrogen oxides in the presence of ammonia from gases containing a significant amount...... of alkali metal and/or alkali-earth compounds which process comprises using a catalyst combined of (i) a formed porous superacidic support, said superacidic support having an Hammett acidity stronger than Ho=-12, and (ii) a metal oxide catalytic component deposited on said superacidic support selected from...

  18. Paraffin Alkylation Using Zeolite Catalysts in a slurry reactor: Chemical Engineering Principles to Extend Catalyst Lifetime

    NARCIS (Netherlands)

    Jong, K.P. de; Mesters, C.M.A.M.; Peferoen, D.G.R.; Brugge, P.T.M. van; Groot, C. de

    1996-01-01

    The alkylation of isobutane with 2-butene is carried out using a zeolitic catalyst in a well stirred slurry reactor. Whereas application of fixed bed technology using a solid acid alkylation catalyst has in the led to catalysts lifetimes in the range of minutes, in this work we report catalyst

  19. Production of furfural from xylose, water-insoluble hemicelluloses and water-soluble fraction of corncob via a tin-loaded montmorillonite solid acid catalyst.

    Science.gov (United States)

    Li, Huiling; Ren, Junli; Zhong, Linjie; Sun, Runcang; Liang, Lei

    2015-01-01

    The conversion of xylose, water-insoluble hemicelluloses (WIH) and water-soluble fraction (WSF) of corncob to furfural was performed using montmorillonite with tin ions (Sn-MMT) containing double acid sites as a solid acid catalyst. The co-existence of Lewis acids and Brønsted acids in Sn-MMT was shown to improve the furfural yield and selectivity. 76.79% furfural yield and 82.45% furfural selectivity were obtained from xylose using Sn-MMT as a catalyst in a biphasic system with 2-s-butylphenol (SBP) as the organic extracting layer and dimethyl sulfoxide (DMSO) as the co-solvent in contact with an aqueous phase saturated with NaCl (SBP/NaCl-DMSO) at 180°C for 30min. Furthermore, Sn-MMT also demonstrated the excellent catalytic performance in the conversion of pentose-rich materials of corncob and 39.56% and 54.15% furfural yields can be directly obtained from WIH and WSF in the SBP/NaCl-DMSO system, respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. Reuse of Hydrotreating Spent Catalyst

    International Nuclear Information System (INIS)

    Habib, A.M.; Menoufy, M.F.; Amhed, S.H.

    2004-01-01

    All hydro treating catalysts used in petroleum refining processes gradually lose activity through coking, poisoning by metal, sulfur or halides or lose surface area from sintering at high process temperatures. Waste hydrotreating catalyst, which have been used in re-refining of waste lube oil at Alexandria Petroleum Company (after 5 years lifetime) compared with the same fresh catalyst were used in the present work. Studies are conducted on partial extraction of the active metals of spent catalyst (Mo and Ni) using three leaching solvents,4% oxidized oxalic acid, 10% aqueous sodium hydroxide and 10% citric acid. The leaching experiments are conducting on the de coked extrude [un crushed] spent catalyst samples. These steps are carried out in order to rejuvenate the spent catalyst to be reused in other reactions. The results indicated that 4% oxidized oxalic acid leaching solution gave total metal removal 45.6 for de coked catalyst samples while NaOH gave 35% and citric acid gave 31.9 % The oxidized leaching agent was the most efficient leaching solvent to facilitate the metal removal, and the rejuvenated catalyst was characterized by the unchanged crystalline phase The rejuvenated catalyst was applied for hydrodesulfurization (HDS) of vacuum gas oil as a feedstock, under different hydrogen pressure 20-80 bar in order to compare its HDS activity

  1. Preparation, characterization and first application of aerosil silica supported acidic ionic liquid as a reusable heterogeneous catalyst for the synthesis of 2,3-dihydroquinazoline-4(1H)-ones

    Energy Technology Data Exchange (ETDEWEB)

    Yassaghi, Ghazaleh; Davodnia, Abolghasem; Allameh, Sadegh; Zarebidaki, Atefeh; Tavakolihoseini, Niloofar [Islamic Azad Univ., Mashhad (Iran, Islamic Republic of)

    2012-04-15

    A new heterogeneous acidic catalyst was successfully prepared by impregnation of silica (Aerosil 300) by an acidic ionic liquid, named 1-(4-sulfonic acid)butyl pyridinium hydrogen sulfate [PYC{sub 4}SO{sub 3}H][HSO{sub 4}], and characterized using FT-IR spectroscopy, the N{sub 2} adsorption/desorption analysis (BET), thermal analysis (TG/DTG), and X-ray diffraction (XRD) techniques. The amount of loaded acidic ionic liquid on Aerosil 300 support was determined by acid-base titration. This new solid acidic supported heterogeneous catalyst exhibits excellent activity in the synthesis of 2-aryl-2,3-dihydroquinazoline-4(1H)-ones by cyclo condensation reaction of 2-aminobenzamide with aromatic aldehydes under solvent-free conditions and the desired products were obtained in very short reaction times with high yields. This catalyst has the advantages of an easy catalyst separation from the reaction medium and lower problems of corrosion. Recycling of the catalyst and avoidance of using harmful organic solvent are other advantages of this simple procedure.

  2. Reuse of sewage sludge as a catalyst in ozonation – Efficiency for the removal of oxalic acid and the control of bromate formation

    International Nuclear Information System (INIS)

    Wen, Gang; Pan, Zhi-Hui; Ma, Jun; Liu, Zheng-Qian; Zhao, Lei; Li, Jun-Jing

    2012-01-01

    Highlights: ► Sewage sludge was converted into catalyst (SBC) and characterized. ► SBC can enhance oxalic acid degradation in ozonation. ► Surface reaction mechanism is responsible for enhancement of ozonation by SBC. ► SBC can control the formation of bromate in ozonation. ► Several combined reasons for the control of bromate formation are proposed. - Abstract: Sewage derived sludge is produced with an annual amount increase of 2% all over the world and it is an urgent issue to be addressed by human being. In the present study, sludge was converted into sludge-based catalyst (SBC) with ZnCl 2 as activation agent and characterized by several methods (e.g., scanning electron microscope, X-ray photoelectron spectroscope and Fourier transform infrared spectroscope). Then it was used as a catalyst to enhance the removal of refractory organic matter, oxalic acid, and to control the formation of bromate (BrO 3 − ) in bench semi-continuous ozonation experiments. The effects of various operating parameters on the control of BrO 3 − formation were investigated. Furthermore, the mechanism for the enhancement of organic matter removal and the control of BrO 3 − formation was discussed as well. Results indicate that the combination of SBC with ozone shows a strong synergistic effect, resulting in a notable improvement on oxalic acid removal. A crucial surface reaction mechanism for the enhancement of organic matter removal is proposed on the basis of negative effect of higher pH and no inhibition effect of tert-butanol. The control for BrO 3 − formation was demonstrated and the reason for its control in the process of O 3 /SBC is the combined effect of SBC reductive properties, ozone exposure decrease and hydrogen peroxide concentration increase.

  3. Ultrasound-assisted oxidative desulfurization process of liquid fuel by phosphotungstic acid encapsulated in a interpenetrating amine-functionalized Zn(II)-based MOF as catalyst.

    Science.gov (United States)

    Afzalinia, Ahmad; Mirzaie, Abbas; Nikseresht, Ahmad; Musabeygi, Tahereh

    2017-01-01

    In this work, ultrasound-assisted oxidative desulfurization (UAOD) of liquid fuels performed with a novel heterogeneous highly dispersed Keggin-type phosphotungstic acid (H 3 PW 12 O 40 , PTA) catalyst that encapsulated into an amino-functionalized MOF (TMU-17-NH 2 ). The prepared composite exhibits high catalytic activity and reusability in oxidative desulfurization of model fuel. Ultrasound-assisted oxidative desulfurization (UAOD) is a new way to performed oxidation reaction of sulfur-contain compounds rapidly, economically, environment-friendly and safely, under mild conditions. Ultrasound waves can be apply as an efficient tool to decrease the reaction time and improves oxidative desulfurization system performance. PTA@TMU-17-NH 2 could be completely performed desulfurization of the model oil by 20mg of catalyst, O/S molar ratio of 1:1 in presence of MeCN as extraction solvent. The obtained results indicated that the conversions of DBT to DBTO 2 achieve 98% after 15min in ambient temperature. In this work, we prepared TMU-17-NH 2 and PTA/TMU-17-NH 2 composite by ultrasound irradiation for first time and employed in UAOD process. Prepared catalyst exhibit an excellent reusability without PTA leaching and loss of activity. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

  4. Modified montmorillonite as a heterogeneous catalyst in (m)ethyl esterification reaction of lauric acid; Montmorilonita modificada como catalisador heterogeneo em reacoes de esterificacao (M)etilica de acido laurico

    Energy Technology Data Exchange (ETDEWEB)

    Zatta, Leandro; Nepel, Angelita; Barison, Andersson; Wypych, Fernando, E-mail: wypych@ufpr.br [Departamento de Quimica, Universidade Federal do Parana (UFPR), Curitiba , PR (Brazil)

    2012-07-01

    Montmorillonite was modified with zirconium polyoxycations in the presence of ammonium sulphate. The material was characterized and used as a catalyst in the esterification of lauric acid, the reactions being accompanied by 2{sup 3} factorial design. Conversions of up to 95.33 and 83.35% were observed for the methyl and ethyl esterification reactions respectively, proving superior to results obtained by thermal conversion. The material was submitted to three reaction cycles and similar conversions were observed, indicating the catalyst is not significantly deactivated after reuse. The catalyst was also tested under reflux conditions, yielding a maximum conversion of 36.86%. (author)

  5. ACETAL OBTAINED FROM ETHANOL AND ACID-ACTIVATED BENTONITE AS A CATALYST: AN ALTERNATIVE FOR THE SUGAR-ALCOHOL AGROINDUSTRY

    Directory of Open Access Journals (Sweden)

    Oscar Yecid Buitrago Suescún

    2010-05-01

    Full Text Available This study discusses the results of characterizing and activating a bentonite from the Valle del Cauca region. The betonite is used as a catalyst in the reaction to obtain 1,1-Diethoxyethane from ethanol, which can be extracted from sugar cane. Important factors are analyzed such as: the activation of the bentonite; the percentage of bentonite; the reaction temperature; and the ethanol/acetaldehyde feed ratio. In addition, comparison tests are performed against the CaCl2 catalyst which is commonly used in previous literature. Physical and spectrometric constants are measured for the obtained product confirming that it is 1,1-Diethoxyethane.

  6. Effective Liquid-phase Nitration of Benzene Catalyzed by a Stable Solid Acid Catalyst: Silica Supported Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40}

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Shu-wen; Liu, Li-jun; Zhang, Qian; Wang, Liang-yin [Liaocheng University, Liaocheng (China)

    2012-04-15

    Silica supported Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40} catalyst was prepared through sol-gel method with ethyl silicate-40 as silicon resource and characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, nitrogen adsorption-desorption and potentiometric titration methods. The Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40} particles with Keggin-type structure well dispersed on the surface of silica, and the catalyst exhibited high surface area and acidity. The catalytic performance of the catalysts for benzene liquid-phase nitration was examined with 65% nitric acid as nitrating agent, and the effects of various parameters were tested, which including temperature, time and amount of catalyst, reactants ratio, especially the recycle of catalyst was emphasized. Benzene was effectively nitrated to mononitro-benzene with high conversion (95%) in optimized conditions. Most importantly, the supported catalyst was proved has excellent stability in the nitration progress, and there were no any other organic solvent and sulfuric acid were used in the reaction system, so the liquid-phase nitration of benzene that we developed was an eco-friendly and attractive alternative for the commercial technology

  7. pKa modulation of the acid/base catalyst within GH32 and GH68: a role in substrate/inhibitor specificity?

    Directory of Open Access Journals (Sweden)

    Shuguang Yuan

    Full Text Available Glycoside hydrolases of families 32 (GH32 and 68 (GH68 belong to clan GH-J, containing hydrolytic enzymes (sucrose/fructans as donor substrates and fructosyltransferases (sucrose/fructans as donor and acceptor substrates. In GH32 members, some of the sugar substrates can also function as inhibitors, this regulatory aspect further adding to the complexity in enzyme functionalities within this family. Although 3D structural information becomes increasingly available within this clan and huge progress has been made on structure-function relationships, it is not clear why some sugars bind as inhibitors without being catalyzed. Conserved aspartate and glutamate residues are well known to act as nucleophile and acid/bases within this clan. Based on the available 3D structures of enzymes and enzyme-ligand complexes as well as docking simulations, we calculated the pKa of the acid-base before and after substrate binding. The obtained results strongly suggest that most GH-J members show an acid-base catalyst that is not sufficiently protonated before ligand entrance, while the acid-base can be fully protonated when a substrate, but not an inhibitor, enters the catalytic pocket. This provides a new mechanistic insight aiming at understanding the complex substrate and inhibitor specificities observed within the GH-J clan. Moreover, besides the effect of substrate entrance on its own, we strongly suggest that a highly conserved arginine residue (in the RDP motif rather than the previously proposed Tyr motif (not conserved provides the proton to increase the pKa of the acid-base catalyst.

  8. Hydrothermal synthesis of highly crystalline RuS2 nanoparticles as cathodic catalysts in the methanol fuel cell and hydrochloric acid electrolysis

    International Nuclear Information System (INIS)

    Li, Yanjuan; Li, Nan; Yanagisawa, Kazumichi; Li, Xiaotian; Yan, Xiao

    2015-01-01

    Highlights: • Highly crystalline RuS 2 nanoparticles have been first synthesized by a “one-step” hydrothermal method. • The product presents a pure cubic phase of stoichiometric ratio RuS 2 with average particle size of 14.8 nm. • RuS 2 nanoparticles were used as cathodic catalysts in methanol fuel cell and hydrochloric acid electrolysis. • The catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl − . - Abstract: Highly crystalline ruthenium sulfide (RuS 2 ) nanoparticles have been first synthesized by a “one-step” hydrothermal method at 400 °C, using ruthenium chloride and thiourea as reactants. The products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy/energy disperse spectroscopy (SEM/EDS), thermo gravimetric-differential thermal analyze (TG-DTA), transmission electron microscopy equipped with selected area electron diffraction (TEM/SAED). Fourier transform infrared spectra (IR), and X-ray photoelectron spectroscopy (XPS). XRD result illustrates that the highly crystalline product presents a pure cubic phase of stoichiometric ratio RuS 2 and the average particle size is 14.8 nm. SEM and TEM images display the products have irregular shape of 6–25 nm. XPS analyst indicates that the sulfur exists in the form of S 2 2− . Cyclic voltammetry (CV), rotating disk electrode (RDE), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) measurements are conducted to evaluate the electrocatalytic activity and stability of the highly crystalline RuS 2 nanoparticles in oxygen reduction reaction (ORR) for methanol fuel cell and hydrochloric acid electrolysis. The results illustrate that RuS 2 is active towards oxygen reduction reaction. Although the activity of RuS 2 is lower than that of Pt/C, the RuS 2 catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl −

  9. Effects of Lewis acidity of metal oxide promoters on the activity and selectivity of Co-based Fischer–Tropsch synthesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Gregory R.; Bell, Alexis T. (LBNL); (UCB)

    2016-06-17

    Metal oxides of Ce, Gd, La, Mn, and Zr were investigated as promoters for improving the activity and selectivity of Co-based FTS catalysts. The extent to which these promoters decrease the selectivity toward CH4 and increase the selectivity toward C5+ hydrocarbons was found to depend on both the loading and the composition of the oxide promoter. Elemental mapping by STEM–EDS revealed that the propensity for a given metal oxide to associate with Co affects the sensitivity of the product distribution to changes in promoter loading. For all promoters, a sufficiently high loading resulted in the product distributions becoming insensitive to further increases in promoter loading, very likely due to the formation of a half monolayer of promoter oxide over the Co surface. Simulations suggest that the fraction of Co active sites that are adjacent to the promoter moieties approaches unity at this degree of coverage. The oxidation state of the promoter metal cation under reaction conditions, determined by in situ XANES measurements, was used to calculate relative Lewis acidity of the promoter metal cation. A strong positive correlation was found between the C5+ product selectivity and the Lewis acidity of the promoter metal cations, suggesting that the promotional effects are a consequence of Lewis acid–base interactions between the reaction intermediates and the promoter metal cations. Rate data obtained at different pressures were used to estimate the apparent rate coefficient and the CO adsorption constant appearing in the Langmuir–Hinshelwood expression that describes the CO consumption kinetics for both unpromoted and the metal oxide-promoted catalysts. Both parameters exhibited positive correlations with the promoter Lewis acidity. In conclusion, these results are consistent with the hypothesis that the metal cations of the promoter act as Lewis acids that interact with the O atom of adsorbed CO to facilitate CO adsorption and

  10. Pore structure modification of diatomite as sulfuric acid catalyst support by high energy electron beam irradiation and hydrothermal treatment

    Science.gov (United States)

    Li, Chong; Zhang, Guilong; Wang, Min; Chen, Jianfeng; Cai, Dongqing; Wu, Zhengyan

    2014-08-01

    High energy electron beam (HEEB) irradiation and hydrothermal treatment (HT), were applied in order to remove the impurities and enlarge the pore size of diatomite, making diatomite more suitable to be a catalyst support. The results demonstrated that, through thermal, charge, impact and etching effects, HEEB irradiation could make the impurities in the pores of diatomite loose and remove some of them. Then HT could remove rest of them from the pores and contribute significantly to the modification of the pore size distribution of diatomite due to thermal expansion, water swelling and thermolysis effects. Moreover, the pore structure modification improved the properties (BET (Brunauer-Emmett-Teller) specific surface area, bulk density and pore volume) of diatomite and the catalytic efficiency of the catalyst prepared from the treated diatomite.

  11. The n-butyl amine TPD measurement of Brönsted acidity for solid catalysts by simultaneous TG/DTG-DTA

    Science.gov (United States)

    Sasca, V.; Avram, Livia; Verdes, Orsina; Popa, A.

    2010-06-01

    The method for Brönsted acidity measurement based on TPD of alkyl amines desorption by gas-chromatography or thermogravimetry was adapted for simultaneous TG/DTG-DTA analysis. The acidity measurements were focused on the 12-tungstophosphoric acid (H 3PW 12O 40) and its salts, especially with Cesium since these posses the highest Brönsted acidity and they are among the most interesting catalysts. The n-butyl amine (NBA) desorption takes place in three steps for Cs xH 3- xPW 12O 40, x = 0-2, and four steps for the Cs 2.5H 0.5PW 12O 40. The steps of desorption correspond to the release of NBA molecules in stages, as NBA or butene molecules resulted from the Hofmann elimination reaction and NH 3 + H 2O formed by decomposition of ammonium salt. The quantities of desorption products, C 4H 8 and NH 3 + H 2O, corresponding to the stages with the maximum desorption rates at 400-420 °C, respectively 560-600 °C, are in the stoichiometric ratio with the Brönsted acidity.

  12. 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)

  13. Pore structure modification of diatomite as sulfuric acid catalyst support by high energy electron beam irradiation and hydrothermal treatment

    International Nuclear Information System (INIS)

    Li, Chong; Zhang, Guilong; Wang, Min; Chen, Jianfeng; Cai, Dongqing; Wu, Zhengyan

    2014-01-01

    Highlights: • High energy electron beam (HEEB) irradiation and hydrothermal treatment were used. • HEEB irradiation could make the impurities in the pores of diatomite loose. • Hydrothermal treatment (HT) could remove these impurities from the pores. • They could effectively improve pore size distribution and decrease the bulk density. • Catalytic performance of the corresponding catalyst was significantly improved. - Abstract: High energy electron beam (HEEB) irradiation and hydrothermal treatment (HT), were applied in order to remove the impurities and enlarge the pore size of diatomite, making diatomite more suitable to be a catalyst support. The results demonstrated that, through thermal, charge, impact and etching effects, HEEB irradiation could make the impurities in the pores of diatomite loose and remove some of them. Then HT could remove rest of them from the pores and contribute significantly to the modification of the pore size distribution of diatomite due to thermal expansion, water swelling and thermolysis effects. Moreover, the pore structure modification improved the properties (BET (Brunauer–Emmett–Teller) specific surface area, bulk density and pore volume) of diatomite and the catalytic efficiency of the catalyst prepared from the treated diatomite

  14. Pore structure modification of diatomite as sulfuric acid catalyst support by high energy electron beam irradiation and hydrothermal treatment

    Energy Technology Data Exchange (ETDEWEB)

    Li, Chong [Research Center of the Ministry of Education for High Gravity Engineering and Technology, Beijing University of Chemical Technology, Beijing 100029 (China); Zhang, Guilong; Wang, Min [Key Laboratory of Ion Beam Bioengineering, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031 (China); Chen, Jianfeng [Research Center of the Ministry of Education for High Gravity Engineering and Technology, Beijing University of Chemical Technology, Beijing 100029 (China); Cai, Dongqing, E-mail: dqcai@ipp.ac.cn [Key Laboratory of Ion Beam Bioengineering, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031 (China); Wu, Zhengyan, E-mail: zywu@ipp.ac.cn [Key Laboratory of Ion Beam Bioengineering, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031 (China)

    2014-08-15

    Highlights: • High energy electron beam (HEEB) irradiation and hydrothermal treatment were used. • HEEB irradiation could make the impurities in the pores of diatomite loose. • Hydrothermal treatment (HT) could remove these impurities from the pores. • They could effectively improve pore size distribution and decrease the bulk density. • Catalytic performance of the corresponding catalyst was significantly improved. - Abstract: High energy electron beam (HEEB) irradiation and hydrothermal treatment (HT), were applied in order to remove the impurities and enlarge the pore size of diatomite, making diatomite more suitable to be a catalyst support. The results demonstrated that, through thermal, charge, impact and etching effects, HEEB irradiation could make the impurities in the pores of diatomite loose and remove some of them. Then HT could remove rest of them from the pores and contribute significantly to the modification of the pore size distribution of diatomite due to thermal expansion, water swelling and thermolysis effects. Moreover, the pore structure modification improved the properties (BET (Brunauer–Emmett–Teller) specific surface area, bulk density and pore volume) of diatomite and the catalytic efficiency of the catalyst prepared from the treated diatomite.

  15. Catalytic Upgrading of 5-Hydroxymethylfurfural to Drop-in Biofuels by Solid Base and Bifunctional Metal-Acid Catalysts.

    Science.gov (United States)

    Bohre, Ashish; Saha, Basudeb; Abu-Omar, Mahdi M

    2015-12-07

    Design and synthesis of effective heterogeneous catalysts for the conversion of biomass intermediates into long chain hydrocarbon precursors and their subsequent deoxygenation to hydrocarbons is a viable strategy for upgrading lignocellulose into distillate range drop-in biofuels. Herein, we report a two-step process for upgrading 5-hydroxymethylfurfural (HMF) to C9 and C11 fuels with high yield and selectivity. The first step involves aldol condensation of HMF and acetone with a water tolerant solid base catalyst, zirconium carbonate (Zr(CO3 )x ), which gave 92 % C9 -aldol product with high selectivity at nearly 100 % HMF conversion. The as-synthesised Zr(CO3 )x was analysed by several analytical methods for elucidating its structural properties. Recyclability studies of Zr(CO3 )x revealed a negligible loss of its activity after five consecutive cycles over 120 h of operation. Isolated aldol product from the first step was hydrodeoxygenated with a bifunctional Pd/Zeolite-β catalyst in ethanol, which showed quantitative conversion of the aldol product to n-nonane and 1-ethoxynonane with 40 and 56 % selectivity, respectively. 1-Ethoxynonane, a low oxygenate diesel range fuel, which we report for the first time in this paper, is believed to form through etherification of the hydroxymethyl group of the aldol product with ethanol followed by opening of the furan ring and hydrodeoxygenation of the ether intermediate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Communicating catalysts

    Science.gov (United States)

    Weckhuysen, Bert M.

    2018-06-01

    The beauty and activity of enzymes inspire chemists to tailor new and better non-biological catalysts. Now, a study reveals that the active sites within heterogeneous catalysts actively cooperate in a fashion phenomenologically similar to, but mechanistically distinct, from enzymes.

  17. Investigation of the behaviour of solid acid catalysts for acylations and cyanisations of aromatics. Final report; Untersuchungen zur Wirkungsweise von festen sauren Katalysatoren bei Acylierungen und Cyanierungen von Aromaten. Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Kemnitz, E.

    2002-01-01

    The present state of the art in the field of FRIEDEL-CRAFTS-ACYLATIONS is characterized by the application of homogenous catalysts (at least stochiometric amounts) like AlCl{sub 3} or FeCl{sub 3}. Problems arising from this application are corrosions, difficult product separations from the catalyst and the origin of acid waste water. Hence, the aim of this project was the development of suitable solid catalysts which overcome the problems ascribed above. Sulfated zirconia (SZ) was found to be an excellent solid Br.o/nsted-acid to be used especially in their aerogel or cryogel form. Thus with this catalyst system, in the benzoylation of anisol nearly 100% conversion may be achieved. In this way it could be proved, that with SZ a solid Br.o/nsted-acid might be available which gives reasonable hope to substitute in a near future, at least for some reactions, the classical homogeneous catalysts and to overcome their problems in use. (orig.)

  18. Comparative study of kinetic reaction of 4,4′-Methylenebis (2-m ethel cyclo hexyl amine) with dimeric fatty acid c36 by use of a catalyst of phosphoric acid and dioxide manganese

    International Nuclear Information System (INIS)

    Al-Mohanna, N.; Al-Mohammad, H.

    2015-01-01

    Kinetic study was carried out on the reaction between 4,4′-Methylenebis (2-methylcyclohexylamine and dimeric fatty acid C 3 6 in molten state by use a catalyst of phosphoric acid and dioxide manganese the reaction was performed at 150 o C, and followed by determining the acid value of the product the polyamidation reaction was found to be of overall a second order until equilibrium state moreover the reaction was faster in the presence of the dioxide manganese polyamidation reaction was automatic where the value of free energy was negative the kinetics of thermal degradation was studied by use of thermogravimetric analysis (TGA) and was found to be of overall a second order and was followed by determining the thermodynamic constants of the thermal degradation reaction melting points and transitional glass in the presence of the catalyst were determined by use of differential calorimetry scanning (DSC) and was found to be close the degree of polymerization number average molecular weight and weight average molecular weight have been calculated during different times we noticed that the relationship between degree of polymerization and number average molecular weight, weight average molecular weight with time is linear until equilibrium state the prepared polyamide involve crystallization and amorphous area this was shown by XRD spectra. (author)

  19. Preparation of the Pt/CNTs Catalyst and Its Application to the Fabrication of Hydrogenated Soybean Oil Containing a Low Content of Trans Fatty Acids Using the Solid Polymer Electrolyte Reactor.

    Science.gov (United States)

    Zheng, Huanyu; Ding, Yangyue; Xu, Hui; Zhang, Lin; Cui, Yueting; Han, Jianchun; Zhu, Xiuqing; Yu, Dianyu; Jiang, Lianzhou; Liu, Lilai

    2018-08-01

    Pt/CNTs were synthesized with an ethylene glycol reduction method, and the effects of carboxyl functionalization, ultrasonic power and the concentration of chloroplatinic acid on the catalytic activity of Pt/CNTs were investigated. The optimal performance of the Pt/CNTs catalyst was obtained when the ultrasonic power was 300 W and the concentration of chloroplatinic acid was 40 mg/mL. The durability and stability of the Pt/CNTs catalyst were considerably better compared to Pt/C, as shown by cyclic voltammetry measurement results. The trans fatty acids content of the obtained hydrogenated soybean oil (IV: 108.4 gl2/100 g oil) using Pt/CNTs as the cathode catalyst in a solid polymer electrolyte reactor was only 1.49%. The IV of hydrogenated soybean oil obtained using CNTs as carrier with Pt loading 0.1 mg/cm2 (IV: 108.4 gl2/100 g oil) was lower than carbon with a Pt loading of 0.8 mg/cm2 (IV: 109.9 gl2/100 g oil). Thus, to achive the same IV, the usage of Pt was much less when carbon nanotubes were selected as catalyst carrier compared to traditional carbon carrier. The changes of fatty acid components and the hydrogenated selectivity of octadecenoic acid were also discussed.

  20. A convenient catalyst system for microwave accelerated cross-coupling of a range of aryl boronic acids with aryl chlorides

    Directory of Open Access Journals (Sweden)

    Milton Edward J

    2007-05-01

    Full Text Available Abstract A convenient microwave accelerated cross-coupling procedure between aryl chlorides with a range of boronic acids has been developed. An explanation for the low reactivity of highly fluorinated boronic acids in Suzuki coupling is provided.

  1. Metal chloride hydrates as Lewis acid catalysts in multicomponent synthesis of 2,4,5-triarylimidazoles or 2,4,5-triaryloxazoles

    Energy Technology Data Exchange (ETDEWEB)

    Marques, Marcelo V. [Departamento de Engenharia de Processos, Fundacao de Ciencia e Tecnologia, Cachoeirinha, RS (Brazil); Russowsky, Dennis, E-mail: dennis@iq.ufrgs.br [Laboratorio de Sinteses Organicas, Instituto de Quimica, Universidade Federal do Rio Grande do Sul, Porto Alegre-RS (Brazil); Ruthner, Marcelo M.; Fontoura, Luiz A.M. [Curso de Quimica, Universidade Luterana do Brasil, Canoas, RS (Brazil)

    2012-07-01

    A series of nine metal chloride hydrates (ZnCl{sub 2}.2H{sub 2}O, SnCl{sub 2}.2H{sub 2}O, CdCl{sub 2}.2H{sub 2}O, MnCl{sub 2}.4H{sub 2}O, CoCl{sub 2}.6H{sub 2}O, SrCl{sub 2}.6H{sub 2}O, NiCl{sub 2}.6H{sub 2}O, CrCl{sub 3}.6H{sub 2}O and CeCl{sub 3}.7H{sub 2}O) was investigated as mild and inexpensive Lewis acid catalysts to promote the multicomponent synthesis of triarylimidazoles. Reactions starting from benzil showed the best results when SnCl{sub 2}.2H{sub 2}O was used, while for benzoin as the starting material, CeCl{sub 3}.7H{sub 2}O was more efficient. All reactions were performed in EtOH as solvent. These catalysts were also successfully employed in the synthesis of triaryloxazoles. (author)

  2. Laser-induced removal of a dye C.I. Acid Red 87 using n-type WO{sub 3} semiconductor catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Qamar, M. [Center of Excellence in Nanotechnology, King Fahd University of Petroleum and Minerals, KFUPM Box 741, Dhahran 31261 (Saudi Arabia); Gondal, M.A., E-mail: magondal@kfupm.edu.sa [Center of Excellence in Nanotechnology, King Fahd University of Petroleum and Minerals, KFUPM Box 741, Dhahran 31261 (Saudi Arabia); Laser Research Laboratory, Physics Department, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Hayat, K. [Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Yamani, Z.H. [Center of Excellence in Nanotechnology, King Fahd University of Petroleum and Minerals, KFUPM Box 741, Dhahran 31261 (Saudi Arabia); Laser Research Laboratory, Physics Department, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Al-Hooshani, K. [Center of Excellence in Nanotechnology, King Fahd University of Petroleum and Minerals, KFUPM Box 741, Dhahran 31261 (Saudi Arabia); Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia)

    2009-10-30

    Water contamination by organic substances such as dyes is of great concern worldwide due to their utilization in many industrial processes and environmental concerns. To cater the needs for waste water treatment polluted with organic dyes, laser-induced photocatalytic process was investigated for removal of a dye derivative namely Acid Red 87 using n-type WO{sub 3} semiconductor catalyst. The degradation was investigated in aqueous suspensions of tungsten oxide under different experimental conditions using laser instead of conventional UV lamp as an irradiation source. The degradation process was monitored by measuring the change in dye concentration as a function of laser irradiation time by employing UV spectroscopic analysis. The degradation of dye was studied by varying different parameters such as laser energy, reaction pH, substrate concentration, catalyst concentration, and in the presence of electron acceptors such as hydrogen peroxide (H{sub 2}O{sub 2}), and potassium bromate (KBrO{sub 3}). The degradation rates were found to be strongly dependent on all the above-mentioned parameters. Our experimental results revealed that the dye degradation process was very fast (within few minutes) under laser irradiation as compared to conventional setups using broad spectral lamps (hours or days) and this laser-induced photocatalytic degradation method could be an effective means to eliminate the pollutants present in liquid phase. The experience gained through this study could be beneficial for treatment of waste water contaminated with organic dyes and other organic pollutants.

  3. Polyphosphoric acid supported on Ni0.5Zn0.5Fe2O4 nanoparticles as a magnetically-recoverable green catalyst for the synthesis of pyranopyrazoles

    Directory of Open Access Journals (Sweden)

    Farid Moeinpour

    2017-05-01

    Full Text Available Polyphosphoric acid supported on silica coated Ni0.5Zn0.5Fe2O4 nanoparticles was found to be magnetically separable, highly efficient, eco-friendly, green and recyclable heterogeneous catalyst. This new catalyst at first was fully characterized by TEM, SEM, FTIR and XRD techniques and then catalytic activity of this catalyst was investigated in the synthesis of 5-cyano-1,4-dihydropyrano[2,3-c]pyrazoles. Also the Ni0.5Zn0.5Fe2O4 magnetic nanoparticle-supported polyphosphoric acid could be reused at least six times without significant loss of activity. It could be recovered easily by applying an external magnet.

  4. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    Science.gov (United States)

    Ginosar, Daniel M.; Petkovic, Lucia M.

    2010-12-28

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  5. Catalytic Transformation of Ethylbenzene over Y-Zeolite-based Catalysts

    KAUST Repository

    Al-Khattaf, Sulaiman

    2008-11-19

    Catalytic transformation of ethylbenzene (EB) has been investigated over ultrastable Y (USY)-zeolite-based catalysts in a novel riser simulator at different operating conditions. The effect of reaction conditions on EB conversion is reported. The USY catalyst (FCC-Y) was modified by steaming to form a significantly lower acidity catalyst (FCC-SY). The current study shows that the FCC-SY catalyst favors EB disproportionation more than cracking. A comparison has been made between the results of EB conversion over the lowly acidic catalyst (FCC-SY) and the highly acidic catalyst (FCC-Y) under identical conditions. It was observed that increase in catalyst acidity favored cracking of EB at the expense of disproportionation. Kinetic parameters for EB disappearance during disproportionation reaction over the FCC-SY catalyst were calculated using the catalyst activity decay function based on time on stream (TOS). © 2008 American Chemical Society.

  6. THE EFFECT OF WATER CAPACITY ON THE ACTIVITY OF PD(II-CU(II CATALYST ANCHORED TO ACID-MODIFIED CLINOPTILOLITE IN THE REACTION OF LOW-TEMPERATURE CARBON MONOXIDE OXIDATION

    Directory of Open Access Journals (Sweden)

    T. L. Rakitskaya

    2015-02-01

    Full Text Available The maximum activity of Pd(II-Cu(II catalyst anchored to acid modified clinoptilolite in the reaction of low-temperature carbon monoxide oxidation with air oxygen has been found at the water content in the range from 3.3 to 4.2 mmol/g.

  7. Boosting the performance of Pt electro-catalysts toward formic acid electro-oxidation by depositing sub-monolayer Au clusters

    International Nuclear Information System (INIS)

    Bi Xuanxuan; Wang Rongyue; Ding Yi

    2011-01-01

    Highlights: → Au decoration on Pt nanoparticles simultaneously increases the activity and stability. → Sub-monolayer Au decoration changes the reaction path and results in the activity improvement. → Increasing the Au coverage will increase the specific activity. → Proper Au coverage results in a maximum mass specific activity. - Abstract: CO poisoning is the main obstacle to the application of Pt nanoparticles as anode catalysts in direct formic acid fuel cells (DFAFCs). Significant types of Pt alloys have been investigated, which often demonstrate evidently improved catalytic performance governed by difference mechanisms. By using a well-known electrochemical technique of under potential deposition and in situ redox replacement, sub-monolayer Au clusters are deposited onto Pt nanoparticle surfaces in a highly controlled manner, generating a unique surface alloy structure. Under optimum conditions, the modified Pt nanoparticles can exhibit greatly enhanced specific activity (up to 23-fold increase) at potential of -0.2 V vs. MSE toward formic acid electro-oxidation (FAEO). Interestingly, the mass specific activity can also be improved by a factor of 2.3 at potential of -0.35 V vs. MSE although significant amount of surface Pt atoms are covered by the overlayer Au clusters. The much enhanced catalytic activity can be ascribed to a Pt surface ensemble effect, which induces change of the reaction path. Moreover, the sub-monolayer Au coating on the surface also contributes to the enhanced catalyst durability by inhibiting the Pt oxidation. These results show great potential to rationally design more active and stable nanocatalysts by modifying the Pt surface with otherwise inactive materials.

  8. Hydrothermal synthesis of highly crystalline RuS{sub 2} nanoparticles as cathodic catalysts in the methanol fuel cell and hydrochloric acid electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yanjuan [Key Laboratory of Marine Chemistry Theory and Technology, Minisry of Education Ocean University of China, Qingdao, 266100 (China); College of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Li, Nan, E-mail: lin@jlu.edu.cn [College of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Yanagisawa, Kazumichi [Research Laboratory of Hydrothermal Chemistry, Kochi University, Kochi 780-8520 (Japan); Li, Xiaotian [College of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Yan, Xiao [Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), College of Physics, Jilin University, Changchun 130012 (China)

    2015-05-15

    Highlights: • Highly crystalline RuS{sub 2} nanoparticles have been first synthesized by a “one-step” hydrothermal method. • The product presents a pure cubic phase of stoichiometric ratio RuS{sub 2} with average particle size of 14.8 nm. • RuS{sub 2} nanoparticles were used as cathodic catalysts in methanol fuel cell and hydrochloric acid electrolysis. • The catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl{sup −}. - Abstract: Highly crystalline ruthenium sulfide (RuS{sub 2}) nanoparticles have been first synthesized by a “one-step” hydrothermal method at 400 °C, using ruthenium chloride and thiourea as reactants. The products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy/energy disperse spectroscopy (SEM/EDS), thermo gravimetric-differential thermal analyze (TG-DTA), transmission electron microscopy equipped with selected area electron diffraction (TEM/SAED). Fourier transform infrared spectra (IR), and X-ray photoelectron spectroscopy (XPS). XRD result illustrates that the highly crystalline product presents a pure cubic phase of stoichiometric ratio RuS{sub 2} and the average particle size is 14.8 nm. SEM and TEM images display the products have irregular shape of 6–25 nm. XPS analyst indicates that the sulfur exists in the form of S{sub 2}{sup 2−}. Cyclic voltammetry (CV), rotating disk electrode (RDE), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) measurements are conducted to evaluate the electrocatalytic activity and stability of the highly crystalline RuS{sub 2} nanoparticles in oxygen reduction reaction (ORR) for methanol fuel cell and hydrochloric acid electrolysis. The results illustrate that RuS{sub 2} is active towards oxygen reduction reaction. Although the activity of RuS{sub 2} is lower than that of Pt/C, the RuS{sub 2} catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl{sup −}.

  9. Aerobic Oxidation of 5-(Hydroxymethyl)furfural Cyclic Acetal Enables Selective Furan-2,5-dicarboxylic Acid Formation with CeO2 -Supported Gold Catalyst.

    Science.gov (United States)

    Kim, Minjune; Su, Yaqiong; Fukuoka, Atsushi; Hensen, Emiel J M; Nakajima, Kiyotaka

    2018-05-14

    The utilization of 5-(hydroxymethyl)furfural (HMF) for the large-scale production of essential chemicals has been largely limited by the formation of solid humin as a byproduct, which prevents the operation of stepwise batch-type and continuous flow-type processes. The reaction of HMF with 1,3-propanediol produces an HMF acetal derivative that exhibits excellent thermal stability. Aerobic oxidation of the HMF acetal with a CeO 2 -supported Au catalyst and Na 2 CO 3 in water gives a 90-95 % yield of furan 2,5-dicarboxylic acid, an increasingly important commodity chemical for the biorenewables industry, from concentrated solutions (10-20 wt %) without humin formation. The six-membered acetal ring suppresses thermal decomposition and self-polymerization of HMF in concentrated solutions. Kinetic studies supported by DFT calculations identify two crucial steps in the reaction mechanism, that is, the partial hydrolysis of the acetal into 5-formyl-2-furan carboxylic acid involving OH - and Lewis acid sites on CeO 2 , and subsequent oxidative dehydrogenation of the in situ generated hemiacetal involving Au nanoparticles. These results represent a significant advance over the current state of the art, overcoming an inherent limitation of the oxidation of HMF to an important monomer for biopolymer production. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Lunar CATALYST

    Data.gov (United States)

    National Aeronautics and Space Administration — Lunar Cargo Transportation and Landing by Soft Touchdown (Lunar CATALYST) is a NASA initiative to encourage the development of U.S. private-sector robotic lunar...

  11. Method of performing sugar dehydration and catalyst treatment

    Science.gov (United States)

    Hu, Jianli [Kennewick, WA; Holladay, Johnathan E [Kennewick, WA; Zhang, Xinjie [Burlington, MA; Wang, Yong [Richland, WA

    2010-06-01

    The invention includes a method of treating a solid acid catalyst. After exposing the catalyst to a mixture containing a sugar alcohol, the catalyst is washed with an organic solvent and is then exposed to a second reaction mixture. The invention includes a process for production of anhydrosugar alcohol. A solid acid catalyst is provided to convert sugar alcohol in a first sample to an anhydrosugar alcohol. The catalyst is then washed with an organic solvent and is subsequently utilized to expose a second sample. The invention includes a method for selective production of an anhydrosugar. A solid acid catalyst is provided within a reactor and anhydrosugar alcohol is formed by flowing a starting sugar alcohol into the reactor. The acid catalyst is then exposed to an organic solvent which allows a greater amount of additional anhydrosugar to be produced than would occur without exposing the acid catalyst to the organic solvent.

  12. Effect of acid catalysts and accelerated aging on the reaction of methanol with hydroxy-acetaldehyde in bio-oil

    Directory of Open Access Journals (Sweden)

    Bhattacharya, P.

    2010-05-01

    Full Text Available Bio-oil is a promising alternative source of energy produced from fast pyrolysis of biomass. Increasing the viscosity of bio-oil during storage is a major problem that can be controlled by the addition of methanol or other alcohols. This paper reports the results of our investigation of the reactions of short chain alcohols with aldehydes and acids in bio-oil. The reaction of methanol with hydroxyacetaldehyde (HA to form the acetal was catalyzed by the addition of 7 x 10-4 M strong acids such as sulfuric, hydrochloric, p-toluene sulfonic acid, and methanesulfonic acid. HA formed 2,2-dimethoxyethanol (DME, and at 60 oC the equilibrium was reached in less than one hour. Smaller amounts of DME were formed in the absence of strong acid. HA, acetaldehyde, and propanal formed their corresponding acetals when reacted with methanol, ethanol, 1-propanol or 1-butanol. Esters of acetic acid and hydroxyacetic acid were observed from reactions with these same four alcohols. Other acetals and esters were observed by GC/MS analysis of the reaction products. The results from accelerated aging experiments at 90 oC suggest that the presence of methanol slows polymerization by formation of acetals and esters from low molecular weight aldehydes and organic acids.

  13. Sulfonic acid-functionalized golf nanoparticles: A colloid-bound catalyst for soft lithographic application on self-assembled monolayers

    NARCIS (Netherlands)

    Li, X.; Paraschiv, V.; Huskens, Jurriaan; Reinhoudt, David

    2003-01-01

    In this report, we present a new lithographic approach to prepare patterned surfaces. Self-assembled monolayers (SAMs) of the acid-labile trimethylsilyl ether (TMS-OC11H22S)2 (TMS adsorbate) was formed on gold. 5-Mercapto-2-benzimidazole sulfonic acid sodium salt (MBS-Na+) was used as a ligand for

  14. Large Ferrierite Crystals as Models for Catalyst Deactivation during Skeletal Isomerisation of Oleic Acid : Evidence for Pore Mouth Catalysis

    NARCIS (Netherlands)

    Wiedemann, Sophie C. C.; Ristanovic, Zoran; Whiting, Gareth T.; Marthala, V. R. Reddy; Kaerger, Joerg; Weitkamp, Jens; Wels, Bas; Bruijnincx, Pieter C. A.; Weckhuysen, Bert M.

    2016-01-01

    Large zeolite crystals of ferrierite have been used to study the deactivation, at the single particle level, of the alkyl isomerisation catalysis of oleic acid and elaidic acid by a combination of visible micro-spectroscopy and fluorescence microscopy (both polarised wide-field and confocal modes).

  15. Combined use of titration calorimetry and spectrofluorimetry for the screening of the acidity of solid catalysts in different liquids

    International Nuclear Information System (INIS)

    Gervasini, Antonella; Auroux, Aline

    2013-01-01

    Graphical abstract: Measurements of acidity of oxides of catalytic importance in various liquids open the possibility to know their effective acidity, which is related with their activity in liquid-heterogeneous catalysis. Titration-calorimetry alone or in connection with spectrofluorimetry is efficient for this scope. - Highlights: • Measurements of acidity of oxides of catalytic importance in various liquids. • Titration-calorimetry alone or in connection with spectrofluorimetry is efficient for this scope. • Effective acidities are expressed by given sample in various liquids. • Nb-containing samples are able to maintain acidity in protic liquids. - Abstract: The effective acid and base surface properties of selected acidic and basic samples of catalytic interest (alumina, titania, zirconia, silica–alumina, niobium oxide, niobium phosphate, boron nitride, and hydrotalcite) were measured by titration with basic and acidic molecular probes (aniline, 2-phenylethylamine, and phenol) in various liquids (cyclohexane, 1,4-dioxane, isopropanol, n-decane, and toluene) with different polar and protic characteristics. The combined use of a reaction calorimeter and a spectrofluorimeter has been performed. The set-up of the coupled technique and the most interesting results are shown here. The study confirmed that the acid–base properties of solids are deeply affected by the nature and properties of the liquid surrounding the samples. Few oxides are able to maintain their surface acidity in highly polar and protic solvents, in particular whose containing niobium. In general, the solvating and coordinative ability of the most polar and protic liquids caused remarkable loss of acidity/basicity of the oxide surfaces

  16. Combined use of titration calorimetry and spectrofluorimetry for the screening of the acidity of solid catalysts in different liquids

    Energy Technology Data Exchange (ETDEWEB)

    Gervasini, Antonella, E-mail: antonella.gervasini@unimi.it [Dipartimento di Chimica, Università degli Studi di Milano, via Camillo Golgi, 19, 20133 Milano (Italy); Auroux, Aline, E-mail: aline.auroux@ircelyon.univ-lyon1.fr [Université Lyon 1, CNRS, UMR 5256, Institut de Recherches sur la Catalyse et l‘Environnement de Lyon (IRCELYON), 2 Avenue A. Einstein, 69626 Villeurbanne (France)

    2013-09-10

    Graphical abstract: Measurements of acidity of oxides of catalytic importance in various liquids open the possibility to know their effective acidity, which is related with their activity in liquid-heterogeneous catalysis. Titration-calorimetry alone or in connection with spectrofluorimetry is efficient for this scope. - Highlights: • Measurements of acidity of oxides of catalytic importance in various liquids. • Titration-calorimetry alone or in connection with spectrofluorimetry is efficient for this scope. • Effective acidities are expressed by given sample in various liquids. • Nb-containing samples are able to maintain acidity in protic liquids. - Abstract: The effective acid and base surface properties of selected acidic and basic samples of catalytic interest (alumina, titania, zirconia, silica–alumina, niobium oxide, niobium phosphate, boron nitride, and hydrotalcite) were measured by titration with basic and acidic molecular probes (aniline, 2-phenylethylamine, and phenol) in various liquids (cyclohexane, 1,4-dioxane, isopropanol, n-decane, and toluene) with different polar and protic characteristics. The combined use of a reaction calorimeter and a spectrofluorimeter has been performed. The set-up of the coupled technique and the most interesting results are shown here. The study confirmed that the acid–base properties of solids are deeply affected by the nature and properties of the liquid surrounding the samples. Few oxides are able to maintain their surface acidity in highly polar and protic solvents, in particular whose containing niobium. In general, the solvating and coordinative ability of the most polar and protic liquids caused remarkable loss of acidity/basicity of the oxide surfaces.

  17. A new sol-gel synthesis of 45S5 bioactive glass using an organic acid as catalyst.

    Science.gov (United States)

    Faure, J; Drevet, R; Lemelle, A; Ben Jaber, N; Tara, A; El Btaouri, H; Benhayoune, H

    2015-02-01

    In this paper a new sol-gel approach was explored for the synthesis of the 45S5 bioactive glass. We demonstrate that citric acid can be used instead of the usual nitric acid to catalyze the sol-gel reactions. The substitution of nitric acid by citric acid allows to reduce strongly the concentration of the acid solution necessary to catalyze the hydrolysis of silicon and phosphorus alkoxides. Two sol-gel powders with chemical compositions very close to that of the 45S5 were obtained by using either a 2M nitric acid solution or either a 5mM citric acid solution. These powders were characterized and compared to the commercial Bioglass®. The surface properties of the two bioglass powders were assessed by scanning electron microscopy (SEM) and by Brunauer-Emmett-Teller method (BET). The Fourier transformed infrared spectroscopy (FTIR) and the X-ray diffraction (XRD) revealed a partial crystallization associated to the formation of crystalline phases on the two sol-gel powders. The in vitro bioactivity was then studied at the key times during the first hours of immersion into acellular Simulated Body Fluid (SBF). After 4h immersion into SBF we clearly demonstrate that the bioactivity level of the two sol-gel powders is similar and much higher than that of the commercial Bioglass®. This bioactivity improvement is associated to the increase of the porosity and the specific surface area of the powders synthesized by the sol-gel process. Moreover, the nitric acid is efficiently substituted by the citric acid to catalyze the sol-gel reactions without alteration of the bioactivity of the 45S5 bioactive glass. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Fatty acid methyl ester synthesis catalyzed by solid superacid catalyst SO{sub 4}{sup 2-}/ZrO{sub 2}-TiO{sub 2}/La{sup 3+}

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yan; Zhang, Xiao-Dong; Sun, Li; Zhang, Jie; Xu, Hai-Peng [Energy Research Institute of Shandong Academy of Sciences, Jinan 250014 (China)

    2010-01-15

    A new type of solid superacid catalyst with the composition of SO{sub 4}{sup 2-}/ZrO{sub 2}-TiO{sub 2} loaded with lanthanum was prepared by precipitation and impregnation. The catalytic performance for the synthesis of fatty acid methyl ester from fatty acid and methanol was investigated. The influences of preparation conditions on catalyst performance were studied, the optimum results of which showed that amount of La(NO{sub 3}){sub 3} was 0.1 wt.%, the concentration of H{sub 2}SO{sub 4} for impregnation was 0.5 mol l{sup -1} and calcination temperature was 550 C. In addition, the effects of reaction parameters on esterification efficiency were also studied. With the catalyst amount of 5 wt.%, methanol amount of 1 ml/g fatty acid (FA) and reaction duration of 5 h at 60 C, the conversion ratio could reach above 95%. The catalyst recycled without any treatments could exhibit high activity with the conversion efficiency of above 90% after being reused five times. (author)

  19. Support acidity influence in NiMoS (Nickel and Molybdenum) catalyst for Marlim diesel; Influencia da acidez do suport de catalisadores NiMoS (Niquel e Molibidenio) no hidrotratamento de diesel Marlim

    Energy Technology Data Exchange (ETDEWEB)

    Ferraz, Sheila Guimaraes de Almeida; Zotin, Jose Luiz; Jesus, Anderson Gomes de; Santos, Bruno Martins; Medeiros, Marcus Vinicius Costa [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil). Centro de Pesquisas (CENPES)

    2008-07-01

    The specification of diesel points to the reduction of the sulfur content, of the final boiling point, of the density range and increase of the cetane number. These two last properties are directly related with the ability of the hydrotreating catalytic system in promoting the hydrogenation of aromatic structures and ring opening of the naphthenic compounds, which are both associated to low cetane number. In such way, more acidic catalysts, able to promote the cracking of naphthenic structures, should be evaluated for the diesel HDT. Three bifunctional NiMo catalysts with the same metal content, different acidity and similar active phase dispersion were prepared using alumina, silica-alumina and alumina-Y zeolite as supports. These catalysts were evaluated in a micro-reactor unit for diesel HDT aiming to correlate their activity with the support acidity. The alumina and alumina-zeolite supported catalysts presented better performance than the one supported on silica-alumina. NiMo/alumina-zeolite showed higher cetane and density improvement, associated with a slight decrease in the initial boiling point. (author)

  20. Attrition resistant Fischer-Tropsch catalyst and support

    Science.gov (United States)

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    2004-05-25

    A catalyst support having improved attrition resistance and a catalyst produced therefrom. The catalyst support is produced by a method comprising the step of treating calcined .gamma.-alumina having no catalytic material added thereto with an acidic aqueous solution having an acidity level effective for increasing the attrition resistance of the calcined .gamma.-alumina.

  1. Process and catalysts for the gasification of methanol. [German Patent

    Energy Technology Data Exchange (ETDEWEB)

    Harris, N.; Dennis, A.J.; Shevels, T.F.

    1975-02-13

    The invention concerns catalysts and catalytic processes for the gasification of methanol which is used to manufacture methane from methanol. Mixtures of iron and chromium oxide, phosphate, phosphoric acid, tungstate, tungstic acid, aluminium phosphate, aluminium oxide are suitable as dehydrating catalysts. Gasification takes place together with steam and dehydrogenating catalysts at high temperature. The molar ratios steam: methanol are described.

  2. Mordenite - Type Zeolite SCR Catalysts with Iron or Copper

    DEFF Research Database (Denmark)

    2012-01-01

    Cu/mordenite catalysts were found to be highly active for the SCR of NO with NH3 and exhibited high resistance to alkali poisoning. Redox and acidic properties of Cu/mordenite were well preserved after poisoning with potassium unlike that of vanadium catalysts. Fe-mordenite catalysts also reveale...... to be essential requirements for the high alkali resistance. Mordenite-type zeolite based catalysts could therefore be attractive alternatives to conventional SCR catalysts for biomass fired power plant flue gas treatment....

  3. Large Ferrierite Crystals as Models for Catalyst Deactivation during Skeletal Isomerisation of Oleic Acid : Evidence for Pore Mouth Catalysis

    OpenAIRE

    Wiedemann, Sophie C. C.; Ristanovic, Zoran; Whiting, Gareth T.; Marthala, V. R. Reddy; Kaerger, Joerg; Weitkamp, Jens; Wels, Bas; Bruijnincx, Pieter C. A.; Weckhuysen, Bert M.

    2016-01-01

    Large zeolite crystals of ferrierite have been used to study the deactivation, at the single particle level, of the alkyl isomerisation catalysis of oleic acid and elaidic acid by a combination of visible micro-spectroscopy and fluorescence microscopy (both polarised wide-field and confocal modes). The large crystals did show the desired activity, albeit only traces of the isomerisation product were obtained and low conversions were achieved compared to commercial ferrierite powders. This lim...

  4. Reduction of FFA in jatropha curcas oil via sequential direct-ultrasonic irradiation and dosage of methanol/sulfuric acid catalyst mixture on esterification process

    International Nuclear Information System (INIS)

    Andrade-Tacca, Cesar Augusto; Chang, Chia-Chi; Chen, Yi-Hung; Ji, Dar-Ren; Wang, Yi-Yu; Yen, Yue-Quen; Chang, Ching-Yuan

    2014-01-01

    Highlights: • Ultrasonic irradiation (UI) can auto-induce temperature rise. • Esterification at higher temperature (T) by UI offers greater reduction of acid value. • Sequential UI and catalyst dosing enhance esterification conversion efficiency (η). • UR of jatropha oil at higher T results in less water content on ester as product. • A 99.35% of η is achievable via sequential UI and dosing of 5 mL per dose. - Abstract: Production of jatropha-ester (JO-ester) from jatropha oil (JO) under sequential direct-ultrasonic irradiation (UI) with auto-induced temperature rise followed by adding a mixture of methanol/sulfuric-acid catalyst (M/C) dose between high temperature intervals was studied. Comparisons with various doses of 5, 10, 16.6 and 25 mL at different temperature intervals of 108.9–120 °C, 100–120 °C, 85–120 °C and 75–120 °C respectively were performed. System parameters examined include: esterification times (t E ) for UI, settling time (t S ) after esterification and temperature (T). Properties of acid value (AV), iodine value (IV), kinematic viscosity (kV), density (ρ LO ) and water content (m w ) of JO and JO-ester product were measured. The esterification conversion efficiencies (η) were determined and assessed. An η of 99.35% was obtained at temperature interval of 108.9–120 °C with 5 mL per dose for 20 doses and t E of 167.39 min (denoted as Process U 120-5 ), which is slightly higher than η of 98.87% at temperature interval of 75–120 °C with 25 mL per dose for 4 doses and t E of 108.79 min (noted as Process U 120-25 ). The JO-ester obtained via sequential UI with adding doses of 5 mL possess AV of 0.24 mg KOH/g, IV of 124.77 g I 2 /100 g, kV of 9.89 mm 2 /s, ρ LO of 901.73 kg/m 3 and m w of 0.3 wt.% showing that sequential UI and dose at higher temperature interval can give higher reduction of AV compared with 36.56 mg KOH/g of original oil. The effects of t S and t E on AV are of minor and moderate importance

  5. Selective oxidation of i-butene and i-butene to methacrolein and methacrylic acid over Keggin-type polyoxometalate and MoVTeNbOx catalysts. A comparative catalytic and in situ-spectroscopic study

    Energy Technology Data Exchange (ETDEWEB)

    Bentrup, U.; Brueckner, A.; Kant, M.; Kolf, S.; Dingerdissen, U. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V. (Germany); Jansen, S.; Maschmeyer, D.; Sieger, H.; Zanthoff, H.W. [Degussa AG, Marl (Germany)

    2005-07-01

    An alternative to overcome the drawbacks connected with POM catalysts may be the development of suitable mixed metal oxide catalysts. MoVTeNbO{sub x} materials could be promising candidates since they revaled remarkable performance in the selective oxidation of propane to acrylic acid. However, up to now their behaviour in the selective oxidation of i-butane has rarely been studied. The investigations presented in this paper are focused on the interaction of feed components (i-butane / i-butene, O{sub 2}, H{sub 2}O) with Keggin-type polyoxometalate and MoVTeNbO{sub x} catalysts. FTIR spectroscopy was used to identify adsorbed intermediates and products while the novel simultaneous operando-EPR/UV-vis/Raman/GC technique revealed to be an excellent tool to follow the behaviour of V and Mo sites. In relation to the results of catalytic tests, structure-reactivity relationships are derived. (orig.)

  6. A new sol–gel synthesis of 45S5 bioactive glass using an organic acid as catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Faure, J., E-mail: joel.faure@univ-reims.fr [Université de Reims Champagne-Ardenne, Laboratoire Ingénierie et Sciences des Matériaux, LISM EA 4695, 21 rue Clément ADER, 51685 REIMS Cedex 2 (France); Drevet, R., E-mail: richard.drevet@univ-reims.fr [Université de Reims Champagne-Ardenne, Laboratoire Ingénierie et Sciences des Matériaux, LISM EA 4695, 21 rue Clément ADER, 51685 REIMS Cedex 2 (France); Lemelle, A.; Ben Jaber, N.; Tara, A. [Université de Reims Champagne-Ardenne, Laboratoire Ingénierie et Sciences des Matériaux, LISM EA 4695, 21 rue Clément ADER, 51685 REIMS Cedex 2 (France); El Btaouri, H. [Université de Reims Champagne-Ardenne UMR CNRS MEDyC, EA 7369, Campus Moulin de la Housse, 51687 REIMS Cedex 2 (France); Benhayoune, H. [Université de Reims Champagne-Ardenne, Laboratoire Ingénierie et Sciences des Matériaux, LISM EA 4695, 21 rue Clément ADER, 51685 REIMS Cedex 2 (France)

    2015-02-01

    In this paper a new sol–gel approach was explored for the synthesis of the 45S5 bioactive glass. We demonstrate that citric acid can be used instead of the usual nitric acid to catalyze the sol–gel reactions. The substitution of nitric acid by citric acid allows to reduce strongly the concentration of the acid solution necessary to catalyze the hydrolysis of silicon and phosphorus alkoxides. Two sol–gel powders with chemical compositions very close to that of the 45S5 were obtained by using either a 2 M nitric acid solution or either a 5 mM citric acid solution. These powders were characterized and compared to the commercial Bioglass®. The surface properties of the two bioglass powders were assessed by scanning electron microscopy (SEM) and by Brunauer–Emmett–Teller method (BET). The Fourier transformed infrared spectroscopy (FTIR) and the X-ray diffraction (XRD) revealed a partial crystallization associated to the formation of crystalline phases on the two sol–gel powders. The in vitro bioactivity was then studied at the key times during the first hours of immersion into acellular Simulated Body Fluid (SBF). After 4 h immersion into SBF we clearly demonstrate that the bioactivity level of the two sol–gel powders is similar and much higher than that of the commercial Bioglass®. This bioactivity improvement is associated to the increase of the porosity and the specific surface area of the powders synthesized by the sol–gel process. Moreover, the nitric acid is efficiently substituted by the citric acid to catalyze the sol–gel reactions without alteration of the bioactivity of the 45S5 bioactive glass. - Highlights: • Citric acid is employed as a catalyzer of the sol–gel process. • This catalyzer is used at a very low concentration for the hydrolysis reaction. • The chemical composition of the bioglass synthesized by the sol–gel process is optimized. • The properties of two sol–gel bioglasses are compared with those of the commercial

  7. A new sol–gel synthesis of 45S5 bioactive glass using an organic acid as catalyst

    International Nuclear Information System (INIS)

    Faure, J.; Drevet, R.; Lemelle, A.; Ben Jaber, N.; Tara, A.; El Btaouri, H.; Benhayoune, H.

    2015-01-01

    In this paper a new sol–gel approach was explored for the synthesis of the 45S5 bioactive glass. We demonstrate that citric acid can be used instead of the usual nitric acid to catalyze the sol–gel reactions. The substitution of nitric acid by citric acid allows to reduce strongly the concentration of the acid solution necessary to catalyze the hydrolysis of silicon and phosphorus alkoxides. Two sol–gel powders with chemical compositions very close to that of the 45S5 were obtained by using either a 2 M nitric acid solution or either a 5 mM citric acid solution. These powders were characterized and compared to the commercial Bioglass®. The surface properties of the two bioglass powders were assessed by scanning electron microscopy (SEM) and by Brunauer–Emmett–Teller method (BET). The Fourier transformed infrared spectroscopy (FTIR) and the X-ray diffraction (XRD) revealed a partial crystallization associated to the formation of crystalline phases on the two sol–gel powders. The in vitro bioactivity was then studied at the key times during the first hours of immersion into acellular Simulated Body Fluid (SBF). After 4 h immersion into SBF we clearly demonstrate that the bioactivity level of the two sol–gel powders is similar and much higher than that of the commercial Bioglass®. This bioactivity improvement is associated to the increase of the porosity and the specific surface area of the powders synthesized by the sol–gel process. Moreover, the nitric acid is efficiently substituted by the citric acid to catalyze the sol–gel reactions without alteration of the bioactivity of the 45S5 bioactive glass. - Highlights: • Citric acid is employed as a catalyzer of the sol–gel process. • This catalyzer is used at a very low concentration for the hydrolysis reaction. • The chemical composition of the bioglass synthesized by the sol–gel process is optimized. • The properties of two sol–gel bioglasses are compared with those of the commercial

  8. TiO2 and Al2O3 promoted Pt/C nanocomposites as low temperature fuel cell catalysts for electro oxidation of methanol in acidic media

    International Nuclear Information System (INIS)

    Naeem, Rabia; Ahmed, Riaz; Ansari, Muhammad Shahid

    2014-01-01

    Carbon corrosion and platinum dissolution are the two major catalyst layer degradation problems in polymer electrolyte membrane fuel cells (PEMFC). Ceramic addition can reduce the corrosion of carbon and increase the stability of catalysts. Pt/TiO 2 , Pt/TiO 2 -C, Pt/Al 2 O 3 and Pt/Al 2 O 3 -C catalysts were synthesized and characterized. Electrochemical surface area of Pt/TiO 2 -C and Pt/Al 2 O 3 -C nanocomposite catalysts was much higher than the Pt/TiO 2 and Pt/Al 2 O 3 catalysts. Peak current, specific activity and mass activity of the catalysts was also determined by cyclic voltammetry and were much higher for the carbon nanocomposites. Exchange current densities were determined from Tafel plots. Heterogeneous rates of reaction of electro oxidation of methanol were determined for all the catalysts and were substantially higher for titania catalysts as compared to alumina added catalysts. Mass activity of Pt/TiO 2 -C was much higher than mass activity of Pt/Al 2 O 3 -C. Stability studies showed that addition of ceramics have increased the catalytic activity and durability of the catalysts considerably

  9. Highly dispersed metal catalyst

    Science.gov (United States)

    Xiao, Xin; West, William L.; Rhodes, William D.

    2016-11-08

    A supported catalyst having an atomic level single atom structure is provided such that substantially all the catalyst is available for catalytic function. A process of forming a single atom catalyst unto a porous catalyst support is also provided.

  10. Ru decorated carbon nanotubes - a promising catalyst for reforming bio-based acetic acid in the aqueous phase

    NARCIS (Netherlands)

    de Vlieger, Dennis; Lefferts, Leonardus; Seshan, Kulathuiyer

    2014-01-01

    Catalytic reforming of biomass derived waste streams in the aqueous phase is a promising process for the production of sustainable hydrogen. Acetic acid will be a major component (up to 20 wt%) in many anticipated gasification feed streams (e.g. the aqueous fraction of pyrolysis oil). Conventional

  11. Toward understanding of the role of Lewis acidity in aldol condensation of acetone and furfural using MOF and zeolite catalysts

    Czech Academy of Sciences Publication Activity Database

    Kikhtyanin, O.; Kubička, D.; Čejka, Jiří

    2015-01-01

    Roč. 243, APR 2015 (2015), s. 158-162 ISSN 0920-5861 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : metal organic framework * aldol condensation * acidic catalysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.312, year: 2015

  12. Kinetic modeling of levulinic acid hydrogenation to gamma-valerolactone in water using a carbon supported Ru catalyst

    NARCIS (Netherlands)

    Piskun, A.S.; van de Bovenkamp, H.H.; Rasrendra, C.B.; Winkelman, J.G.M.; Heeres, H.J.

    2016-01-01

    gamma-Valerolactone (GVL) is considered a very interesting green, bio-based platform chemical with highapplication potential for the production of both biofuels and biobased chemicals. In this contribution, wereport a kinetic study on the hydrogenation of levulinic acid (LA) to 4-hydroxypentanoic

  13. ZrOCl2·8H2O: An Efficient, Cheap and Reusable Catalyst for the Esterification of Acrylic Acid and Other Carboxylic Acids with Equimolar Amounts of Alcohols

    Directory of Open Access Journals (Sweden)

    Yingwu Yin

    2006-04-01

    Full Text Available Esterifications of carboxylic acids with equimolar amount of alcohols could beefficiently catalyzed by ZrOCl2·8H2O. Acrylate esters were obtained in good yields undersolvent-free conditions at ambient temperature. The esterification of other carboxylicacids with alcohols also proceeded at ambient temperature or at 50 oC to afford esters inhigh yields. If the esterification was performed in toluene under azeotropic refluxconditions to remove water, both the catalytic activity of ZrOCl2·8H2O and the rate ofesterification could be increased greatly. Furthermore, in the present catalytic system, theesters could be easily separated from the reaction mixtures and the catalyst could beeasily recovered and reused.

  14. Effects of particulates, heavy metals and acid gas on the removals of NO and PAHs by V2O5-WO3 catalysts in waste incineration system

    International Nuclear Information System (INIS)

    Chang, Feng-Yim; Chen, Jyh-Cherng; Wey, Ming-Yen; Tsai, Shih-An

    2009-01-01

    This study investigated the activities of prepared and commercial V 2 O 5 -WO 3 catalysts for simultaneous removals of NO and polycyclic aromatic hydrocarbons (PAHs) and the influences of particulates, heavy metals, SO 2 , and HCl on the performances of catalysts. The experiments were carried out in a laboratory-scale waste incineration system equipped with a catalyst reactor. The DREs of PAHs by prepared and commercial V 2 O 5 -WO 3 catalysts were 64% and 72%, respectively. Increasing the particulate concentrations in flue gas suppressed the DRE of PAHs, but increasing the carbon content on surface of catalysts promotes the NO conversions. The DRE of PAHs by the catalysts was significantly decreased by the increased concentrations of heavy metal Cd, but was promoted by high concentration of Pb. The influence level of SO 2 was higher than HCl on the performances of V 2 O 5 -WO 3 catalysts for PAHs removal, but was lower than HCl for NO removal. Prepared and commercial V 2 O 5 -WO 3 catalysts have similar trends on the effects of particulates, heavy metals, SO 2 , and HCl. The results of ESCA analysis reveal that the presences of these pollutants on the surface of catalysts did not change the chemical state of V and W.

  15. Synthesis of nanolayers hydroxo-(SnxOyHz) and heteropoly-(HxPWyOz) compounds of hybrid-type on silica surfaces by successive ionic layer deposition method

    International Nuclear Information System (INIS)

    Tolstoy, V.P.; Gulina, L.B.; Korotchenkov, G.S.; Brynsari, V.I.

    2004-01-01

    We determined the synthesis conditions for successive ionic layer deposition of the Sn 16 (OH) x PW 19 O y ·nH 2 O nanolayers on silica surfaces. The synthesized layers were characterized using UV-Vis and FTIR absorption spectroscopies, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). On heating the as-synthesized layers to 200-500 deg. C in air, incorporated water evaporate, while M-OH groups are condensed and concentration of the W-O-W and W-O-Sn bonds increase. The layers have amorphous agglomerate-like structure. The agglomerate size is from 20 to 100 nm. Upon heating to 600 deg. C, the size insignificantly increases, the agglomerate form being practically unchanged. The data obtained allow conclusion that the layers present a hybrid compound consisting of fragments of isopoly-(Sn x O y H z ) and heteropoly-(H x PW y O z ) compounds

  16. Optimization of furfural production from D-xylose with formic acid as catalyst in a reactive extraction system.

    Science.gov (United States)

    Yang, Wandian; Li, Pingli; Bo, Dechen; Chang, Heying; Wang, Xiaowei; Zhu, Tao

    2013-04-01

    Furfural is one of the most promising platform chemicals derived from biomass. In this study, response surface methodology (RSM) was utilized to determine four important parameters including reaction temperature (170-210°C), formic acid concentration (5-25 g/L), o-nitrotoluene volume percentage (20-80 vt.%), and residence time (40-200 min). The maximum furfural yield of 74% and selectivity of 86% were achieved at 190°C for 20 g/L formic acid concentration and 75 vt.% o-nitrotoluene by 75 min. The high boiling solvent, o-nitrotoluene, was recommended as extraction solvent in a reactive extraction system to obtain high furfural yield and reduce furfural-solvent separation costs. Although the addition of halides to the xylose solutions enhanced the furfural yield and selectivity, the concentration of halides was not an important factor on the furfural yield and selectivity. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. omega-Amino acid:pyruvate transaminase from Alcaligenes denitrificans Y2k-2: a new catalyst for kinetic resolution of beta-amino acids and amines.

    Science.gov (United States)

    Yun, Hyungdon; Lim, Seongyop; Cho, Byung-Kwan; Kim, Byung-Gee

    2004-04-01

    Alcaligenes denitrificans Y2k-2 was obtained by selective enrichment followed by screening from soil samples, which showed omega-amino acid:pyruvate transaminase activity, to kinetically resolve aliphatic beta-amino acid, and the corresponding structural gene (aptA) was cloned. The gene was functionally expressed in Escherichia coli BL21 by using an isopropyl-beta-D-thiogalactopyranoside (IPTG)-inducible pET expression system (9.6 U/mg), and the recombinant AptA was purified to show a specific activity of 77.2 U/mg for L-beta-amino-n-butyric acid (L-beta-ABA). The enzyme converts various beta-amino acids and amines to the corresponding beta-keto acids and ketones by using pyruvate as an amine acceptor. The apparent K(m) and V(max) for L-beta-ABA were 56 mM and 500 U/mg, respectively, in the presence of 10 mM pyruvate. In the presence of 10 mM L-beta-ABA, the apparent K(m) and V(max) for pyruvate were 11 mM and 370 U/mg, respectively. The enzyme exhibits high stereoselectivity (E > 80) in the kinetic resolution of 50 mM D,L-beta-ABA, producing optically pure D-beta-ABA (99% enantiomeric excess) with 53% conversion.

  18. ω-Amino Acid:Pyruvate Transaminase from Alcaligenes denitrificans Y2k-2: a New Catalyst for Kinetic Resolution of β-Amino Acids and Amines

    Science.gov (United States)

    Yun, Hyungdon; Lim, Seongyop; Cho, Byung-Kwan; Kim, Byung-Gee

    2004-01-01

    Alcaligenes denitrificans Y2k-2 was obtained by selective enrichment followed by screening from soil samples, which showed ω-amino acid:pyruvate transaminase activity, to kinetically resolve aliphatic β-amino acid, and the corresponding structural gene (aptA) was cloned. The gene was functionally expressed in Escherichia coli BL21 by using an isopropyl-β-d-thiogalactopyranoside (IPTG)-inducible pET expression system (9.6 U/mg), and the recombinant AptA was purified to show a specific activity of 77.2 U/mg for l-β-amino-n-butyric acid (l-β-ABA). The enzyme converts various β-amino acids and amines to the corresponding β-keto acids and ketones by using pyruvate as an amine acceptor. The apparent Km and Vmax for l-β-ABA were 56 mM and 500 U/mg, respectively, in the presence of 10 mM pyruvate. In the presence of 10 mM l-β-ABA, the apparent Km and Vmax for pyruvate were 11 mM and 370 U/mg, respectively. The enzyme exhibits high stereoselectivity (E > 80) in the kinetic resolution of 50 mM d,l-β-ABA, producing optically pure d-β-ABA (99% enantiomeric excess) with 53% conversion. PMID:15066855

  19. Sugar and ethanol production from woody biomass via supercritical water hydrolysis in a continuous pilot-scale system using acid catalyst.

    Science.gov (United States)

    Jeong, Hanseob; Park, Yong-Cheol; Seong, Yeong-Je; Lee, Soo Min

    2017-12-01

    The aim of this study were to efficiently produce fermentable sugars by continuous type supercritical water hydrolysis (SCWH) of Quercus mongolica at the pilot scale with varying acid catalyst loading and to use the obtained sugars for ethanol production. The SCWH of biomass was achieved in under one second (380°C, 230bar) using 0.01-0.1% H 2 SO 4 . With 0.05% H 2 SO 4 , 49.8% of sugars, including glucose (16.5% based on biomass) and xylose monomers (10.8%), were liberated from biomass. The hydrolysates were fermented with S. cerevisiae DXSP and D452-2 to estimate ethanol production. To prepare the fermentation medium, the hydrolysates were detoxified using activated charcoal and then concentrated. The ethanol yield of fermentation with S. cerevisiae DXSP was 14.1% (based on biomass). The proposed system has potential for improvement in yield through process optimization. After further development, it is expected to be a competitive alternative to traditional systems for ethanol production from woody biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Ultrasound assisted production of fatty acid methyl esters from transesterification of triglycerides with methanol in the presence of KOH catalyst: optimization, mechanism and kinetics.

    Science.gov (United States)

    Thanh, Le Tu; Okitsu, Kenji; Maeda, Yasuaki; Bandow, Hiroshi

    2014-03-01

    Ultrasound assisted transesterification of triglycerides (TG) with methanol in the presence of KOH catalyst was investigated, where the changes in the reactants and products (diglycerides (DG), monoglycerides (MG), fatty acid methyl esters (FAME) and glycerin (GL)) concentrations were discussed to understand the reaction mechanism and kinetics under ultrasound irradiation. The optimum reaction condition for the FAME production was the concentration of KOH 1.0 wt.%, molar ratio of TG to methanol of 1:6, and irradiation time of 25 min. The rate constants during the TG transesterification with methanol into GL and FAME were estimated by a curve fitting method with simulated curves to the obtained experimental results. The rate constants of [Formula: see text] were estimated to be 0.21, 0.008, 0.23, 0.005, 0.14 and 0.001 L mol(-1)min(-1), respectively. The rate determining step for the TG transesterification with methanol into GL and FAME was the reaction of MG with methanol into GL and FAME. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. Materiales basados en heteropoliácidos tipo Keggin y su aplicación en reacciones de esterificación para la valorización de derivados de biomasa

    OpenAIRE

    Escobar Caicedo, Angélica María

    2017-01-01

    Objetivos: - Sintetizar y caracterizar catalizadores basados en heteropoliácidos con estructura tipo Keggin inmovilizados sobre óxido de zirconio (ZrO2), óxido de titanio (TiO2) y materiales magnéticos (Fe3O4) encapsulados en óxido de silicio (SiO2), y evaluarlos en reacciones de esterificación de los ácidos 2-furoico y levulínico (los cuales pueden obtenerse a partir de biomasa vegetal) con diferentes alcoholes, para la obtención de compuestos de alto valor agregado. - Desarrollo de u...

  2. Humic acid coated Fe3O4 magnetic nanoparticles as highly efficient Fenton-like catalyst for complete mineralization of sulfathiazole

    International Nuclear Information System (INIS)

    Niu Hongyun; Zhang Di; Zhang Shengxiao; Zhang Xiaole; Meng Zhaofu; Cai Yaqi

    2011-01-01

    Humic acid coated Fe 3 O 4 magnetic nanoparticles (Fe 3 O 4 /HA) were prepared for the removal of sulfathiazole from aqueous media. Fe 3 O 4 /HA exhibited high activity to produce hydroxyl (·OH) radicals through catalytic decomposition of H 2 O 2 . The degradation of sulfathiazole was strongly temperature-dependent and favored in acidic solution. The catalytic rate was increased with Fe 3 O 4 /HA dosage and H 2 O 2 concentration. When 3 g L -1 of Fe 3 O 4 /HA and 0.39 M of H 2 O 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 4 2- , CO 2 , and N 2 ). The corresponding degradation rate (k) of sulfathiazole and TOC was 0.034 and 0.0048 min -1 , respectively. However, when 3 g L -1 of bare Fe 3 O 4 were used as catalyst, only 54% of TOC was eliminated, and SO 4 2- was not detected within 6 h. The corresponding degradation rate for sulfathiazole and TOC was 0.01 and 0.0016 min -1 , respectively. The high catalytic ability of Fe 3 O 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 ·OH radicals.

  3. Copolymers Based on Indole-6-Carboxylic Acid and 3,4-Ethylenedioxythiophene as Platinum Catalyst Support for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Tzi-Yi Wu

    2015-10-01

    Full Text Available Indole-6-carboxylic acid (ICA and 3,4-ethylenedioxythiophene (EDOT are copolymerized electrochemically on a stainless steel (SS electrode to obtain poly(indole-6-carboxylic acid-co-3,4-ethylenedioxythiophenes (P(ICA-co-EDOTs. The morphology of P(ICA-co-EDOTs is checked using scanning electron microscopy (SEM, and the SEM images reveal that these films are composed of highly porous fibers when the feed molar ratio of ICA/EDOT is greater than 3/2. Platinum particles can be electrochemically deposited into the P(ICA-co-EDOTs and PICA films to obtain P(ICA-co-EDOTs-Pt and PICA-Pt composite electrodes, respectively. These composite electrodes are further characterized using X-ray photoelectron spectroscopy (XPS, SEM, X-ray diffraction analysis (XRD, and cyclic voltammetry (CV. The SEM result indicates that Pt particles disperse more uniformly into the highly porous P(ICA3-co-EDOT2 fibers (feed molar ratio of ICA/EDOT = 3/2. The P(ICA3-co-EDOT2-Pt nanocomposite electrode exhibited excellent catalytic activity for the electrooxidation of methanol in these electrodes, which reveals that P(ICA3-co-EDOT2-Pt nanocomposite electrodes are more promising for application in an electrocatalyst as a support material.

  4. Sputtered catalysts

    International Nuclear Information System (INIS)

    Tyerman, W.J.R.

    1978-01-01

    A method is described for preparing a supported catalyst by a sputtering process. A material that is catalytic, or which is a component of a catalytic system, is sputtered on to the surface of refractory oxide particles that are compatible with the sputtered material and the sputtered particles are consolidated into aggregate form. The oxide particles before sputtering should have a diameter in the range 1000A to 50μ and a porosity less than 0.4 ml/g, and may comprise MgO, Al 2 O 3 or SiO 2 or mixtures of these oxides, including hydraulic cement. The particles may possess catalytic activity by themselves or in combination with the catalytic material deposited on them. Sputtering may be effected epitaxially and consolidation may be effected by compaction pelleting, extrusion or spray drying of a slurry. Examples of the use of such catalysts are given. (U.K.)

  5. Hollow Ag@Pd core-shell nanotubes as highly active catalysts for the electro-oxidation of formic acid

    DEFF Research Database (Denmark)

    Jiang, Yuanyuan; Lu, Yizhong; Han, Dongxue

    2012-01-01

    by detailed characterizations. The Ag@Pd can significantly improve the electrocatalytic activity towards the electro-oxidation of formic acid and enhance the stability of the Pd component. It is proposed that the enhanced electrochemically active surface area and modulated electron structure of Pd by Ag......Ag nanowires are prepared as templates by a polyol reduction process. Then Ag nanotubes coated with a thin layer of Pd are synthesized through sequential reduction accompanied with the galvanic displacement reaction. The products show a hollow core-shell nanotubular structure, as demonstrated...... are responsible for the improvement of electrocatalytic activity and durability. The results obtained in this work are different from those previous reports, in which alloy walls with hollow interiors are usually formed. This work provides a new and simple method for synthesizing novel bimetallic core...

  6. Morphological features of electrodeposited Pt nanoparticles and its application as anode catalysts in polymer electrolyte formic acid fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, Hongrae; Joo, Jiyong; Kwon, Youngkook [Electrochemical Reaction and Technology Laboratory (ERTL), Department of Environmental Science and Engineering, GIST, Gwangju 500-712 (Korea); Uhm, Sunghyun [Ertl Center for Electrochemistry and Catalysis, GIST, Gwangju 500-712 (Korea); Lee, Jaeyoung [Electrochemical Reaction and Technology Laboratory (ERTL), Department of Environmental Science and Engineering, GIST, Gwangju 500-712 (Korea); Ertl Center for Electrochemistry and Catalysis, GIST, Gwangju 500-712 (Korea)

    2010-09-15

    Electrodeposited Pt nanoparticles on carbon substrate show various morphologies depending on the applied potentials. Dendritic, pyramidal, cauliflower-like, and hemi-spherical morphologies of Pt are formed at potential ranges between -0.2 and 0.3 V (vs. Ag/AgCl) and its particle sizes are distributed from 8 to 26 nm. Dendritic bulky particles over 20 nm are formed at an applied potential of -0.2 V, while low deposition potential of 0.2 V causes dense hemi-spherical structure of Pt less than 10 nm. The influence of different Pt shapes on an electrocatalytic oxidation of formic acid is represented. Consequently, homogeneous distribution of Pt nanoparticles with average particle of ca. 14 nm on carbon paper results in a high surface to volume ratio and the better power performance in a fuel cell application. (author)

  7. Potential risk of coupling products between tetrahalobisphenol A and humic acid prepared via oxidation with a biomimetic catalyst.

    Science.gov (United States)

    Kodama, Ritsu; Sazawa, Kazuto; Miyamoto, Takafumi; Zhu, Qianqian; Igarashi, Mami; Oda, Kohki; Kuramitz, Hideki; Fukushima, Masami

    2018-04-04

    Tetrahalobisphenol A (TXPBAs, X = Br or Cl), TBBPA and TCBPA, which are widely used as flame retardants, ultimately disposed of in landfills. In landfills, enzymatically oxidized TXBPAs can be covalently incorporated into humic acids (HAs) to form coupling products (HA-TXBPAs). In the present study, HA-TXBPAs were prepared by catalytic oxidation with iron(III)-phthalocyanine-tetrasulfate as a model of oxidative enzymes. The stability of HA-TXBPAs was evaluated by incubating them under physicochemical conditions of landfills (pH 9 and 50 °C). For HA-TBBPA, 18-26% of TBBPA was released from HA-TBBPA, due to the acid dissociation of the loosely bound TBBPA. However, no additional release was observed, even after 30 days, indicating that 74-82% of the TBBPA was incorporated into the HA. For HA-TCBPA, 3-4% of TCBPA and a major byproduct, 4-(2-hydroxyisopropyl)-2,6-dichlorophenol, was found to be loosely incorporated into HA. For both TBBPA and TCBPA, covalently bound organo-halogens were not released during the 30 days of incubation. Inhibition of the growth of Chlamydomonas reinhardtii was indicated when trace levels of TXBPAs (approximately 0.1 μM) were present. These results suggest that HA-TXBPAs contain not only covalently incorporated TXBPAs but also loosely bound TXBPAs and halophenols. The latter in HA-TXBPAs have the potential to leach from landfills and affect aquatic ecosystems. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. Electrochemical reduction of oxygen on small platinum particles supported on carbon in concentrated phosphoric acid. 2. Effects of teflon content in the catalyst layer and baking temperature of the electrode

    Energy Technology Data Exchange (ETDEWEB)

    Maoka, T.

    1988-03-01

    A relation between hydrophobicity (or wettability) of a porous gas diffusion electrode for use in a phosphoric acid fuel cell and its cathode performance (activity toward electrochemical oxygen reduction) was examined. The hydrophobicity of the gas diffusion electrode was regulated by changing either the amount of Teflon (PTFE) content in the catalyst layer or baking temperature of the electrode. The Tafel slope or electrochemical oxygen reduction became twice as high as that of the ordinary electrode when the wettability of electrode toward phosphoric acid was high. This fact supports a flooded agglomerate model as the mode of this type of porous gas diffusion electrode.

  9. Highly Efficient and Stable Novel NanoBiohybrid Catalyst to Avert 3,4-Dihydroxybenzoic Acid Pollutant in Water.

    Science.gov (United States)

    Das, Rasel; Hamid, Sharifah Bee Abd; Annuar, Mohamad Suffian Mohamad

    2016-10-10

    The present study reported for the first time covalent immobilization of protocatechuate 3,4-dioxygenase (3,4-POD) onto functionalized multi-walled carbon nanotubes (F-MWCNT) for degrading the toxic 3,4-dihydroxybenzoic acid (3,4-DHBA) pollutant in water. The F-MWCNTs had a maximum 3,4-POD loading of 1060 μg/mg. Immobilized 3,4 POD had 44% of relative structural changes to its free configurations. Nevertheless, >90% of relative activity and about 50% of catalytic efficiency were retained to the free enzyme. Immobilized 3,4-POD demonstrated higher alkaline stability and thermostability than the free 3,4-POD. The free and immobilized 3,4-POD lost 82% and 66% of relative activities, respectively after 180 min of incubations at 90 °C. Excellent shelf-life was observed for the immobilized 3,4-POD with residual activity of 56% compared with 41% and 39% of the free 3,4-POD at 4 °C and 25 °C over 30 days storage. Immobilized 3,4-POD showed >60% of catalytic activity retention even after ten-cycle uses, defraying the expenses of free 3,4-POD productions for long term uses. Finally, the immobilized 3,4-POD removed 71% of 3,4-DHBA from water in <4 h, paving its future application for water purification with reduced costs and time.

  10. Alternative alkali resistant deNOx catalysts

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Kristensen, Steffen Buus; Due-Hansen, Johannes

    2012-01-01

    by onepot sol–gel method. All catalysts were characterized by BET, XRPD and NH3-TPD. Initial SCR activities of 8 out of 9 catalysts showed higher NO conversion at least at one temperature in the temperature range 300–500 ◦C compared to the conventional V2O5-WO3/TiO2 catalyst. After potassium poisoning (100......Alternative alkali resistant deNOx catalysts were prepared using three different supports ZrO2, TiO2 and Mordenite zeolite. The majority of the catalysts were prepared by incipient wetness impregnation of a commercial support, with vanadium, copper or iron precursor, one catalyst was prepared......–130 µmol of K/g of catalyst) the relative drop in SCR activity and acidity was lower for all the alternative catalysts compared to the industrial V2O5-WO3/TiO2 catalyst. Furthermore, Cu/MOR and Nano-V2O5/Sul-TiO2 catalysts showed 8–16 times higher SCR activities than the conventional even after high...

  11. In-situ hydrodeoxygenation of phenol by supported Ni catalyst-explanation for catalyst performance

    DEFF Research Database (Denmark)

    Wang, Ze; Zeng, Ying; Lin, Weigang

    2017-01-01

    In-situ hydrodeoxygenation of phenol with aqueous hydrogen donor over supported Ni catalyst was investigated. The supported Ni catalysts exerted very poor performance, if formic acid was used as the hydrogen donor. Catalyst modification by loading K, Na, Mg or La salt could not make the catalyst...... performance improved. If gaseous hydrogen was used as the hydrogen source the activity of Ni/Al2O3 was pretty high. CO2 was found poisonous to the catalysis, due to the competitive adoption of phenol with CO2. If formic acid was replaced by methanol, the catalyst performance improved remarkably, with major...... products of cyclohexanone and cyclohexanol. The better effect of methanol enlightened the application of the supported Ni catalyst in in-situ hydrodeoxygenation of phenol....

  12. One-pot hydrothermal synthesis and characterization of CoFe{sub 2}O{sub 4} nanoparticles and its application as magnetically recoverable catalyst in oxidation of alcohols by periodic acid

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Bappi; Purkayastha, Debraj Dhar; Dhar, Siddhartha Sankar, E-mail: ssd_iitg@hotmail.com

    2016-09-15

    A novel and facile approach for one-pot synthesis of spinel cobalt ferrite (CoFe{sub 2}O{sub 4}) nanoparticles (NPs) is presented here. The synthesis involves homogeneous chemical precipitation followed by hydrothermal heating, using tributylamine (TBA) as a hydroxylating agent. Polyethylene glycol (PEG) 4000 was used as surfactant. As-synthesized CoFe{sub 2}O{sub 4} NPs were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), N{sub 2} adsorption-desorption isotherm (BET) and vibrating sample magnetometry (VSM). TEM image showed formation of spherical particles of sizes 2–30 nm. These NPs were used as magnetically recoverable catalyst in oxidation of alcohols to their corresponding aldehydes by periodic acid. This oxidative procedure is found to be highly efficient affording products in very high yield and selectivity. The easy magnetic separation of the catalyst and efficient reusability are key features of this methodology. - Highlights: • Hydrothermal synthesis of CoFe{sub 2}O{sub 4} NPs with (C{sub 4}H{sub 9}){sub 3}N as hydroxylating agent. • The TEM images showed the particles to be spherical in shape with sizes 2–30 nm. • CoFe{sub 2}O{sub 4} was used as recyclable catalyst for oxidation of alcohols by periodic acid.

  13. One-pot hydrothermal synthesis and characterization of CoFe2O4 nanoparticles and its application as magnetically recoverable catalyst in oxidation of alcohols by periodic acid

    International Nuclear Information System (INIS)

    Paul, Bappi; Purkayastha, Debraj Dhar; Dhar, Siddhartha Sankar

    2016-01-01

    A novel and facile approach for one-pot synthesis of spinel cobalt ferrite (CoFe 2 O 4 ) nanoparticles (NPs) is presented here. The synthesis involves homogeneous chemical precipitation followed by hydrothermal heating, using tributylamine (TBA) as a hydroxylating agent. Polyethylene glycol (PEG) 4000 was used as surfactant. As-synthesized CoFe 2 O 4 NPs were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), N 2 adsorption-desorption isotherm (BET) and vibrating sample magnetometry (VSM). TEM image showed formation of spherical particles of sizes 2–30 nm. These NPs were used as magnetically recoverable catalyst in oxidation of alcohols to their corresponding aldehydes by periodic acid. This oxidative procedure is found to be highly efficient affording products in very high yield and selectivity. The easy magnetic separation of the catalyst and efficient reusability are key features of this methodology. - Highlights: • Hydrothermal synthesis of CoFe 2 O 4 NPs with (C 4 H 9 ) 3 N as hydroxylating agent. • The TEM images showed the particles to be spherical in shape with sizes 2–30 nm. • CoFe 2 O 4 was used as recyclable catalyst for oxidation of alcohols by periodic acid.

  14. Resin catalysts and method of preparation

    Science.gov (United States)

    Smith, L.A. Jr.

    1986-12-16

    Heat stabilized catalyst compositions are prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

  15. Porous nitrogen-enriched carbonaceous material from marine waste: chitosan-derived layered CNX catalyst for aerial oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid

    Data.gov (United States)

    U.S. Environmental Protection Agency — Chitosan-derived, porous and layered nitrogen-enriched carbonaceous CNx catalyst (PLCNx) has been synthesized from marine waste and its use demonstrated in a...

  16. Synthesis H-Zeolite catalyst by impregnation KI/KIO3 and performance test catalyst for biodiesel production

    Science.gov (United States)

    Widayat, W.; Rizky Wicaksono, Adit; Hakim Firdaus, Lukman; Okvitarini, Ndaru

    2016-02-01

    The objective of this research is to produce H-catalyst catalyst that was impregnated with KI/KIO3. The catalyst was analyzed about surface area, X-Ray Diffraction (XRD) and performance test of catalyst for biodiesel production. An H-Zeolite catalyst was synthesized from natural zeolite with chemical treatment processing, impregnation KI/KIO3 and physical treatment. The results shows that the surface area of the catalyst by 27.236 m2/g at a concentration of 5% KI. XRD analysis shows peak 2-θ at 23.627o indicating that KI was impregnated on H-zeolite catalyst. The catalyst was tested in production of biodiesel using palm oil with conventional methods for 3 hour at temperature of 70-80 oC. The result for conversion Fatty Acid Methyl Ester (FAME) reached maximum value on 87.91% under production process using catalyst 5% KIO3-H zeolite.

  17. Simultaneous determination of rutin and ascorbic acid in a sequential injection lab-at-valve system.

    Science.gov (United States)

    Al-Shwaiyat, Mohammed Khair E A; Miekh, Yuliia V; Denisenko, Tatyana A; Vishnikin, Andriy B; Andruch, Vasil; Bazel, Yaroslav R

    2018-02-05

    A green, simple, accurate and highly sensitive sequential injection lab-at-valve procedure has been developed for the simultaneous determination of ascorbic acid (Asc) and rutin using 18-molybdo-2-phosphate Wells-Dawson heteropoly anion (18-MPA). The method is based on the dependence of the reaction rate between 18-MPA and reducing agents on the solution pH. Only Asc is capable of interacting with 18-MPA at pH 4.7, while at pH 7.4 the reaction with both Asc and rutin proceeds simultaneously. In order to improve the precision and sensitivity of the analysis, to minimize reagent consumption and to remove the Schlieren effect, the manifold for the sequential injection analysis was supplemented with external reaction chamber, and the reaction mixture was segmented. By the reduction of 18-MPA with reducing agents one- and two-electron heteropoly blues are formed. The fraction of one-electron heteropoly blue increases at low concentrations of the reducer. Measurement of the absorbance at a wavelength corresponding to the isobestic point allows strictly linear calibration graphs to be obtained. The calibration curves were linear in the concentration ranges of 0.3-24mgL -1 and 0.2-14mgL -1 with detection limits of 0.13mgL -1 and 0.09mgL -1 for rutin and Asc, respectively. The determination of rutin was possible in the presence of up to a 20-fold molar excess of Asc. The method was applied to the determination of Asc and rutin in ascorutin tablets with acceptable accuracy and precision (1-2%). Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Alkali resistant Cu/zeolite deNOx catalysts for flue gas cleaning in biomass fired applications

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Riisager, Anders; Fehrmann, Rasmus

    2011-01-01

    to investigate the redox and acidic properties of the catalysts. The poisoning resistivity seems to be due to a combination of high surface area and strong acidity of the Cu/zeolite catalysts. The catalysts might be attractive alternatives to conventional catalysts for deNOx of flue gases from biomass fired...... power plants and other stationary industrial installations....

  19. Characterization of alumina supported molybdenum catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Pastura, N M; Carmo, L M.P.M.; Sachett, C M.M.; Lam, Y L [Instituto Militar de Engenharia, Rio de Janeiro (Brazil). Secao de Quimica

    1983-10-01

    In order to optimize a bifunctional catalyst (acid and hydrogenating) of Mo/Al/sub 2/O/sub 3/, oxygen adsorption at 195 K and ethanol dehydration at 480-520 K were carried out using a series of these catalysts. The increase of Mo content increased the quantity of adsorbed oxygen, thus indicating that the number of hydrogenating sites also increased. The specific activity of ethanol dehydration varied slightly, indicating that the number of acid sites remains almost constant. On the other hand, the selectivity in ethylene (versus ether) increased markedly. This may be attributed to the increase in acid force of the acid sites.

  20. Characterization of alumina supported molybdenum catalysts

    International Nuclear Information System (INIS)

    Pastura, N.M.; Carmo, L.M.P.M.; Sachett, C.M.M.; Lam, Y.L.

    1983-01-01

    In order to optimize a bifunctional catalyst (acid and hydrogenating) of Mo/Al 2 O 3 , oxygen adsorption at 195 K and ethanol dehydration at 480-520 K were carried out using a series of these catalysts. The increase of Mo content increased the quantity of adsorbed oxygen, thus indicating that the number of hydrogenating sites also increased. The specific activity of ethanol dehydration varied slightly, indicating that the number of acid sites remains almost constant. On the other hand, the selectivity in ethylene (versus ether) increased markedly. This may be attributed to the increase in acid force of the acid sites. (C.L.B.) [pt

  1. Hydrodenitrogenation of heavy oil--1. Survey of hydrodenitrogenation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Nakamura, M.; Ono, T.; Togari, O.

    1979-11-01

    Forty catalysts consisting of binary oxides of silica/alumina, zirconium dioxide, titanium dioxide, or magnesium oxide or alumina/boron oxide, titanium dioxide, zirconium dioxide, or phosphorus pentoxide in various proportions, or of alumina alone, were screened for their activity for hydrodenitrogenation (kn) and hydrodesulfurization (ks) of a Gach Saran vacuum gas oil containing 0.16Vertical Bar3< nitrogen and 2.0Vertical Bar3< sulfur. The activities were correlated with the acid amount and acid strength of the catalysts as measured by temperature-programed desorption of ammonia. The mixed oxides of silica had low kn and low ks, and the kn was proportional to the acidity. The unmixed alumina catalysts showed low kn and high ks and no obvious relationship between activity and acidity. The binary alumina catalysts showed high kn and high ks and no obvious correlation between acidity and activity. Generally, catalysts with high acid strength had the lowest kn, especially the unmixed alumina.

  2. Hantzsch reaction and quinoxaline synthesis using 1-methyl-3-(2-(sulfooxyethyl-1H-imidazol-3-ium chloride as a new, efficient and BrØnsted acidic ionic liquid catalyst

    Directory of Open Access Journals (Sweden)

    Sami Sajjadifar

    2013-10-01

    Full Text Available In this work, the efficiency, generality and applicability of new BrØnsted acidic ionic liquid (BAIL 1-methyl-3-(2-(sulfooxyethyl-1H-imidazol-3-ium chloride {[Msei]Cl} as heterogeneous and green catalyst for organic transformations are studied. Herein, the following one-pot multi-component reactions in the presence of [Msei]Cl are investigated: (i the synthesis of quinoxaline derivatives from the reaction of phenylenediamines and 1,2-diketones in EtOH under mild conditions (room temperature, (ii the preparation of 1,4-dihydropyridines from one-pot multi component condensation of 1,3-dicarbonyl compounds, NH4OAcand aldehydes under solvent-free conditions at moderate temperature (90 °C. High yields, relatively short reaction times, efficiency, generality, clean process, simple methodology, low cost, easy work-up, ease of preparation and regeneration of the catalyst and green conditions (in the synthesis of the quinoxaline derivatives are advantages of the application of [Mesi]Cl as catalyst in the above organic reactions.

  3. Influence of generated intermediates’ interaction on heterogeneous Fenton's degradation of an azo dye 1-diazo-2-naphthol-4-sulfonic acid by using sludge based carbon as catalyst

    International Nuclear Information System (INIS)

    Gu, Lin; Huang, Shouqiang; Zhu, Nanwen; Zhang, Daofang; Yuan, Haiping; Lou, Ziyang

    2013-01-01

    Highlights: • End-products have higher tendency to be adsorbed on SC than primarily-formed. • Higher initial H 2 O 2 dosage results in intermediates with strong polarity. • 9 model intermediates differ in their behavior on interactions with catalysts. • Polar surface area dominated their adsorption on SC while K ow acts as a key role on HSC. -- Abstract: Sewage sludge based carbons have recently been used as novel catalyst in heterogeneous Fenton's reactions to degrade azo dye molecules. The carbons, functioning as both catalyst and adsorbent, play an important role in pollutants elimination, especially for those simultaneously generated organic intermediates. Different factors, i.e., H 2 O 2 concentration, may influence the type and properties of those intermediates and may have great impacts on their elimination through the interactions with catalysts’ surface. Thus, techniques including Temperature Programmed Desorption-Mass Spectrometer (TPD-MS), N 2 adsorption isotherm and Scanning Electron Microscope (SEM) were used to probe the ways of the interaction between oxidation products and catalyst by using different initial H 2 O 2 concentrations (10 and 20 mM). The higher Chemical Oxygen Demand (COD) removal with 20 mM H 2 O 2 was found to be related not only to the higher hydroxyl radicals but also the specific interactions between the intermediates and catalyst’ surface. The deep oxidation occurred in the conditions with higher oxidant amount enhances the intermediates’ adsorption on catalyst, thus increasing the COD removal by large margin. Simulated adsorption experiments by using six primarily formed intermediates and three deeply mineralized products on three different catalysts also confirmed the assumption. Results suggested close relations between adsorption capacities and intermediates’ properties such as polar surface area and octanol-water partition coefficient

  4. Polymer-Supported Cinchona Alkaloid-Derived Ammonium Salts as Recoverable Phase-Transfer Catalysts for the Asymmetric Synthesis of α-Amino Acids

    Directory of Open Access Journals (Sweden)

    Carmen Nájera

    2004-04-01

    Full Text Available Alkaloids such as cinchonidine, quinine and N-methylephedrine have been N-alkylated using polymeric benzyl halides or co-polymerized and then N-alkylated, thus affording a series of polymer-supported chiral ammonium salts which have been employed as phase-transfer catalysts in the asymmetric benzylation of an N-(diphenylmethyleneglycine ester. These new polymeric catalysts can be easily recovered by simple filtration after the reaction and reused. The best ee’s were achieved when Merrifield resin-anchored cinchonidinium ammonium salts were employed.

  5. Calcium and lanthanum solid base catalysts for transesterification

    Science.gov (United States)

    Ng, K. Y. Simon; Yan, Shuli; Salley, Steven O.

    2015-07-28

    In one aspect, a heterogeneous catalyst comprises calcium hydroxide and lanthanum hydroxide, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g. In another aspect, a heterogeneous catalyst comprises a calcium compound and a lanthanum compound, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g, and a total basicity of about 13.6 mmol/g. In further another aspect, a heterogeneous catalyst comprises calcium oxide and lanthanum oxide, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g. In still another aspect, a process for preparing a catalyst comprises introducing a base precipitant, a neutral precipitant, and an acid precipitant to a solution comprising a first metal ion and a second metal ion to form a precipitate. The process further comprises calcining the precipitate to provide the catalyst.

  6. A Mild and Green Route for Regio-selective Amination of Oxiranes Using Nanomagnetic Supported Ferrous Ion as a Solid Lewis Acid Catalyst in Water

    Directory of Open Access Journals (Sweden)

    Fariborz Mansouri

    2016-07-01

    Full Text Available A mild, green and highly efficient route for regio-selective amination of oxiranes was developed via incorporation of Mn(II, Fe(II, Co(II, Ni(II, Cu(II and Zn(II cations onto the surface of hydroxyapatite-encapsulated γ-Fe2O3 nanoparticles (γ-Fe2O3@HAp. Among six magnetically recoverable catalytic systems denoted as [γ-Fe2O3@HAp-MII], the catalyst in which M designated as Fe(II showed the best efficiency as well as regio-selectivity in amination of oxiranes under an ambient reaction condition. A wide variety of aromatic and aliphatic amines were reacted with epoxides using magnetically separable iron catalyst to give the corresponding amino alcohols in excellent yields and selectivities in water as solvent at room temperature. In addition, recovery of the catalyst was successfully carried out in subsequent runs without any decrease in activity even after 5 runs. High regio-selectivity toward terminal ring-opening, efficient catalyst reusability using simple magnetic separation, high yields, simplicity in operation and diversity for various substrates are of advantages of this study.

  7. Continuous-flow hydration–condensation reaction: Synthesis of α,β-unsaturated ketones from alkynes and aldehydes by using a heterogeneous solid acid catalyst

    Directory of Open Access Journals (Sweden)

    Magnus Rueping

    2011-12-01

    Full Text Available A simple, practical and efficient continuous-flow hydration–condensation protocol was developed for the synthesis of α,β-unsaturated ketones starting from alkynes and aldehydes by employing a heterogeneous catalyst in a flow microwave. The procedure presents a straightforward and convenient access to valuable differently substituted chalcones and can be applied on multigram scale.

  8. Breaking the Fischer–Tropsch synthesis selectivity : Direct conversion of syngas to gasoline over hierarchical Co/H-ZSM-5 catalysts

    NARCIS (Netherlands)

    Sartipi, S.; Parashar, K.; Makkee, M.; Gascon, J.; Kapteijn, F.

    2012-01-01

    We report the combination of Fischer–Tropsch catalyst with acid functionality in one single catalyst particle. The resulting bifunctional catalyst is capable of producing gasoline range hydrocarbons from synthesis gas in one catalytic step with outstanding activities and selectivities.

  9. Catalysts for conversion of syngas to liquid motor fuels

    Science.gov (United States)

    Rabo, Jule A.; Coughlin, Peter K.

    1987-01-01

    Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst composition capable of ensuring the production of only relatively minor amounts of heavy products boiling beyond the diesel oil range. The catalyst composition, having desirable stability during continuous production operation, employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component. The latter component is a steam-stabilized zeolite Y catalyst of hydrophobic character, desirably in acid-extracted form.

  10. 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...... catalyst. The results from the screening were experimentally verified for CO hydrogenation, CO2 hydrogenation, and simultaneous CO and CO2 hydrogenation by bimetallic Ni-Fe catalysts. These catalysts were found to be highly active and selective. The Co-Ni and Co-Fe systems were investigated for CO...... 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...

  11. Solid acid catalysis from fundamentals to applications

    CERN Document Server

    Hattori, Hideshi

    2014-01-01

    IntroductionTypes of solid acid catalystsAdvantages of solid acid catalysts Historical overviews of solid acid catalystsFuture outlookSolid Acids CatalysisDefinition of acid and base -Brnsted acid and Lewis acid-Acid sites on surfacesAcid strengthRole of acid sites in catalysisBifunctional catalysisPore size effect on catalysis -shape selectivity-Characterization of Solid Acid Catalysts Indicator methodTemperature programmed desorption (TPD) of ammoniaCalorimetry of adsorption of basic moleculesInfrare

  12. Attrition resistant gamma-alumina catalyst support

    Science.gov (United States)

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    2006-03-14

    A .gamma.-alumina catalyst support having improved attrition resistance produced by a method comprising the steps of treating a particulate .gamma.-alumina material with an acidic aqueous solution comprising water and nitric acid and then, prior to adding any catalytic material thereto, calcining the treated .gamma.-alumina.

  13. Synthesis and characterization of MCM-41-supported nano zirconia catalysts

    Directory of Open Access Journals (Sweden)

    Mohamed S. Abdel Salam

    2015-03-01

    Full Text Available Series of MCM-41 supported sulfated Zirconia (SZ catalysts with different loadings (2.5–7.5% wt. were prepared using direct impregnation method. The acquired solid catalysts were characterized structurally and chemically using X-RD, HRTEM, BET, FT-IR, Raman spectroscopy and TPD analysis. The acidity of the solid catalysts was investigated through cumene cracking and isopropanol dehydration at different temperatures. As the SZ loading increases, the surface acidity of the mesoporous catalysts was enhanced, this was reflected by the higher catalytic activity toward cumene cracking and isopropanol dehydration.

  14. A simple and efficient approach for synthesis of 1,4-dihydro-pyridines using nano-crystalline solid acid catalyst

    Directory of Open Access Journals (Sweden)

    A. Moatari

    2013-09-01

    Full Text Available A simple highly versatile and efficient synthesis of various 1,4-dihydropyridines in the condensation of aromatic aldehydes with β-dicarbonyl compounds and ammonium acetate in the presence of nano-sulfated zirconia, nano-structured ZnO, nano-γ-alumina and nano-ZSM-5 zeolites, as catalyst in the ethanol at moderate temperature is presented. The advantages of method are short reaction times and milder conditions and easy work-up. The catalysts can be recovered for the subsequent reactions and reused without any appreciable loss of efficiency.DOI: http://dx.doi.org/10.4314/bcse.v27i3.12

  15. Sulfated polyborate: A mild, efficient catalyst for synthesis of N-tert ...

    Indian Academy of Sciences (India)

    chemsci

    trityl protected amides via Ritter reaction of nitriles with tertiary alcohols in the presence of a sulfated polyborate catalyst under solvent-free conditions is described. The catalyst has the advantage of Lewis as well as Bronsted acidity and.

  16. A green route to methyl acrylate and acrylic acid by an aldol condensation reaction over H-ZSM-35 zeolite catalysts.

    Science.gov (United States)

    Ma, Zhanling; Ma, Xiangang; Liu, Hongchao; He, Yanli; Zhu, Wenliang; Guo, Xinwen; Liu, Zhongmin

    2017-08-10

    A one-step aldol condensation reaction to produce MA and AA is a green and promising strategy. Here, the aldol condensation reaction was first conducted with DMM and MAc over different types of zeolite catalysts. The H-ZSM-35 zeolite demonstrates excellent catalytic performance with a DMM conversion of 100% and a MA + AA selectivity of up to 86.2% and superior regeneration ability, with great potential for industrial operation.

  17. Electro-oxidation of ethanol and ethylene glycol on carbon-supported nano-Pt and -PtRu catalyst in acid solution

    International Nuclear Information System (INIS)

    Chatterjee, Moitrayee; Chatterjee, Abhik; Ghosh, Susanta; Basumallick, I.

    2009-01-01

    Present paper reports kinetics of electro-oxidation of ethanol (EtOH) and ethylene glycol (EG) onto Pt and PtRu nanocatalysts of different compositions in the temperature range of 298-318 K. These catalysts have been characterized by SEM, EDX, XRD, CV and amperometry. It has been observed that apparent activation energies for oxidation of EtOH and EG pass through a minimum at about 15-20 at.% of Ru in the PtRu alloy catalysts. Anodic peak current vs. composition curve also shows a maximum around this composition. The results have been explained by a geometric model, which proposes requirement of an ensemble of three Pt atoms with an adjacent Ru atom onto PtRu surface for an efficient electro-oxidation of EtOH or EG. This is further supported from statistical data analysis of probability of occurrence of such ensembles onto PtRu alloy surface. Present results also suggest that electro-oxidation of EG onto nano-PtRu catalyst surfaces follows a different path from that of EtOH at alloy composition less than 15 at.% of Ru.

  18. Electro-oxidation of ethanol and ethylene glycol on carbon-supported nano-Pt and -PtRu catalyst in acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Chatterjee, Moitrayee; Chatterjee, Abhik; Ghosh, Susanta [Electrochemical Laboratory, Department of Chemistry, Visva-Bharati University, Santiniketan 731235 (India); Basumallick, I., E-mail: ibasumallick@yahoo.co.u [Electrochemical Laboratory, Department of Chemistry, Visva-Bharati University, Santiniketan 731235 (India)

    2009-12-01

    Present paper reports kinetics of electro-oxidation of ethanol (EtOH) and ethylene glycol (EG) onto Pt and PtRu nanocatalysts of different compositions in the temperature range of 298-318 K. These catalysts have been characterized by SEM, EDX, XRD, CV and amperometry. It has been observed that apparent activation energies for oxidation of EtOH and EG pass through a minimum at about 15-20 at.% of Ru in the PtRu alloy catalysts. Anodic peak current vs. composition curve also shows a maximum around this composition. The results have been explained by a geometric model, which proposes requirement of an ensemble of three Pt atoms with an adjacent Ru atom onto PtRu surface for an efficient electro-oxidation of EtOH or EG. This is further supported from statistical data analysis of probability of occurrence of such ensembles onto PtRu alloy surface. Present results also suggest that electro-oxidation of EG onto nano-PtRu catalyst surfaces follows a different path from that of EtOH at alloy composition less than 15 at.% of Ru.

  19. Mineralization of phthalic acid by solar photoelectro-Fenton with a stirred boron-doped diamond/air-diffusion tank reactor: Influence of Fe3+ and Cu2+ catalysts and identification of oxidation products

    International Nuclear Information System (INIS)

    Garcia-Segura, Sergi; Salazar, Ricardo; Brillas, Enric

    2013-01-01

    Highlights: • Almost total mineralization of phthalic acid by solar photoelectro-Fenton with Fe 3+ , Cu 2+ and Fe 3+ –Cu 2+ mixtures. • Hydroxyl radical generation from photo-Fenton reaction under solar radiation. • Enhancement of the mineralization rate using Fe 3+ and small amounts of Cu 2+ . • Detection of eleven aromatic intermediates and six short-linear carboxylic acids. • Oxidation of Cu(II)-carboxylate complexes with ·OH and photolysis of Fe(III)-carboxylate species. -- Abstract: Here, the substrate decay and mineralization rate for 100 cm 3 of a 2.0 mM phthalic acid solution in 0.10 M Na 2 SO 4 of pH 3.0 have been studied by electro-Fenton (EF) and solar photoelectro-Fenton (SPEF). The electrochemical cell was a stirred tank reactor containing a 3 cm 2 boron-doped diamond (BDD) anode and a 3 cm 2 air-diffusion cathode that generates H 2 O 2 . Cu 2+ and/or Fe 3+ were added as catalysts with total concentration of 0.50 mM and a constant current density of 33.3 mA cm −2 was applied. In EF with Cu 2+ or Fe 3+ alone and SPEF with only Cu 2+ , phthalic acid decayed slowly and poor mineralization was reached because the main oxidant was ·OH produced at the BDD surface from water oxidation. In contrast, the substrate destruction was largely enhanced using SPEF with 0.50 mM Fe 3+ since a high quantity of oxidant ·OH was produced in the bulk induced by photo-Fenton reaction. This treatment led to an almost total mineralization by the photolysis of generated Fe(III)-carboxylate complexes. In all cases, the decay of phthalic acid obeyed a pseudo-first-order reaction. The combination of Cu 2+ and Fe 3+ as catalysts accelerated the mineralization process in SPEF because Cu(II)-carboxylate complexes were also removed with ·OH formed from photo-Fenton reaction. The best SPEF process was found for 0.125 mM Cu 2+ + 0.375 mM Fe 3+ , giving rise to 99% mineralization with 40% current efficiency and 0.294 kWh g −1 TOC energy consumption. Eleven aromatics

  20. Influence of the acid and basic properties of rhenium oxide supported on alumina catalyst on the catalytic performance in olefin metathesis; Influence des proprietes acido-basiques de l`oxyde de rhenium supporte sur les performances catalytiques en metathese des olefines

    Energy Technology Data Exchange (ETDEWEB)

    Nahama, F.

    1996-11-30

    The aim of this work is to study the influence of the acid-basic properties of rhenium oxide supported on alumina catalyst on the catalytic performance in olefin metathesis. The literature data indicate that the environment of the active site does possess acid properties. However, the nature of the acid sites is still matter of debate. Concerning the Re O{sub x} - Al{sub 2}O{sub 3} interactions, we have shown that perrhenate ions are electrostatically absorbed on alumina. The uptake of rhenium is favoured at acidic pH (below 4), and the absorbed rhenium is in equilibrium with rhenium in solution. The results of rhenium extraction by water strongly suggest that the surface compounds of the calcined Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3} materials is aluminium perrhenate. Characterization of surface acidity of the catalyst by infrared spectroscopy reveals that the initiation of the metathesis reaction is governed essentially by Lewis acidity. This strongly supports the role of Lewis acidity, which is exalted by the increase of the rhenium content and the calcination temperature. Finally, we point out by ammonia adsorption-thermodesorption a band at 1320 cm{sup -1} characteristic of the Lewis acidity of aluminium perrhenate. This result is a second indication of the presence of aluminium perrhenate on the Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3} catalyst surface. (author)