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

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.

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

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.

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....

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.

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.

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

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)

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.

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.

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)

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.

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.

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.

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....

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)

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.

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

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.

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.

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....

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.

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.

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.

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.

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

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.

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.

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.

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.

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...

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)

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.

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

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.

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.

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.

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.

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.

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.

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

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....

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

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....

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.

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.

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.

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.

Application of strong phosphoric acid to radiochemistry

International Nuclear Information System (INIS)

Terada, Kikuo

1977-01-01

Not only inorganic and organic compounds but also natural substrances, such as accumulations in soil, are completely decomposed and distilled by heating with strong phosphoric acid for 30 to 50 minutes. As applications of strong phosphoric acid to radiochemistry, determination of uranium and boron by use of solubilization effect of this substance, titration of uranyl ion by use of sulfuric iron (II) contained in this substance, application to tracer experiment, and determination of radioactive ruthenium in environmental samples are reviewed. Strong phosphoric acid is also applied to activation analysis, for example, determination of N in pyrographite with iodate potassium-strong phosphoric acid method, separation of Os and Ru with sulfuric cerium (IV) - strong phosphoric acid method or potassium dechromate-strong phosphoric acid method, analysis of Se, As and Sb rocks and accumulations with ammonium bromide, sodium chloride and sodium bromide-strong phosphoric acid method. (Kanao, N.)

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.

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.

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

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.

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.

Effect of Calcination Temperatures and Mo Modification on Nanocrystalline (γ-χ-Al2O3 Catalysts for Catalytic Ethanol Dehydration

Directory of Open Access Journals (Sweden)

Tharmmanoon Inmanee

2017-01-01

Full Text Available The mixed gamma and chi crystalline phase alumina (M-Al catalysts prepared by the solvothermal method were investigated for catalytic ethanol dehydration. The effects of calcination temperatures and Mo modification were elucidated. The catalysts were characterized by X-ray diffraction (XRD, N2 physisorption, transmission electron microscopy (TEM, and NH3-temperature programmed desorption (NH3-TPD. The catalytic activity was tested for ethylene production by dehydration reaction of ethanol in gas phase at atmospheric pressure and temperature between 200°C and 400°C. It was found that the calcination temperatures and Mo modification have effects on acidity of the catalysts. The increase in calcination temperature resulted in decreased acidity, while the Mo modification on the mixed phase alumina catalyst yielded increased acidity, especially in medium to strong acids. In this study, the catalytic activity of ethanol dehydration to ethylene apparently depends on the medium to strong acid. The mixed phase alumina catalyst calcined at 600°C (M-Al-600 exhibits the complete ethanol conversion having ethylene yield of 98.8% (at 350°C and the Mo-modified catalysts promoted dehydrogenation reaction to acetaldehyde. This can be attributed to the enhancement of medium to strong acid with metal sites of catalyst.

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.

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.

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

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.

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

Bio-oil hydrodeoxygenation catalysts produced using strong electrostatic adsorption

Science.gov (United States)

We synthesized hydrothermally stable metal catalysts with controlled particle size and distribution, with the goal of determining which catalyst(s) can selectively catalyze the production of aromatics from bio-oil (from pyrolysis of biomass). Both precious and base transition metal catalysts (Ru, Pt...

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.

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.

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, ...

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.

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.

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.

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

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.)

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.

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.

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.

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.

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.

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.

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.

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)

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

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

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)

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.

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...

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

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

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.

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)

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....

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.

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

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.

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...

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)

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

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%.

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.

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%.

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.

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

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

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.

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

Science.gov (United States)

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

2015-11-01

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

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.

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.

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

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.

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

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.

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...

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)

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...

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 ...

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.

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.

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.

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.

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.

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.

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.

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...

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

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...

Heterogenization of Homogeneous Catalysts: the Effect of the Support

Energy Technology Data Exchange (ETDEWEB)

Earl, W.L.; Ott, K.C.; Hall, K.A.; de Rege, F.M.; Morita, D.K.; Tumas, W.; Brown, G.H.; Broene, R.D.

1999-06-29

We have studied the influence of placing a soluble, homogeneous catalyst onto a solid support. We determined that such a 'heterogenized' homogeneous catalyst can have improved activity and selectivity for the asymmetric hydrogenation of enamides to amino acid derivatives. The route of heterogenization of RhDuPhos(COD){sup +} cations occurs via electrostatic interactions with anions that are capable of strong hydrogen bonding to silica surfaces. This is a novel approach to supported catalysis. Supported RhDuPhos(COD){sup +} is a recyclable, non-leaching catalyst in non-polar media. This is one of the few heterogenized catalysts that exhibits improved catalytic performance as compared to its homogeneous analog.

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.

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)

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

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)

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.

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.

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.

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.

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 

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.

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...

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)

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.

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.

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.

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.

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

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.

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 ...

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.

Regeneration of a deactivated USY alkylation catalyst using supercritical isobutane

Energy Technology Data Exchange (ETDEWEB)

Daniel M. Ginosar; David N. Ghompson; Kyle C. Burch

2005-01-01

Off-line, in-situ alkylation activity recovery from a completely deactivated solid acid catalyst was examined in a continuous-flow reaction system employing supercritical isobutane. A USY zeolite catalyst was initially deactivated during the liquid phase alkylation of butene with isobutane in a single-pass reactor and then varying amounts of alkylation activity were recovered by passing supercritical isobutane over the catalyst bed at different reactivation conditions. Temperature, pressure and regeneration time were found to play important roles in the supercritical isobutane regeneration process when applied to a completely deactivated USY zeolite alkylation catalyst. Manipulation of the variables that influence solvent strength, diffusivity, surface desorption, hydride transfer rates, and coke aging, strongly influence regeneration effectiveness.

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.

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.

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

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.

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

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.

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.

Titanium Dioxide as a Catalyst Support in Heterogeneous Catalysis

Science.gov (United States)

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

2014-01-01

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

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...

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)

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.

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.

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

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.

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.

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

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

The development of isomerization catalysts for production of high-octane products

Energy Technology Data Exchange (ETDEWEB)

Pedrosa, A.M. Garrido; Melo, D.M.A.; Araujo, A.S. [Universidade Federal do Rio Grande do Norte, Natal, RN (Brazil). Dept. de Quimica; Souza, M.J.B.; Silva, A.O.S. [Universidade Federal do Rio Grande do Norte, Natal, RN (Brazil). Dept. de Engenharia Quimica

2004-07-01

In current petroleum industry, paraffins larger than C5 are used for catalytic reform. The catalytic reform is one of the most important processes for petroleum refine in reason of all reactions they drive to production of high-octane products. Reformate has high-octane products, but they contain 60% aromatics. Isomerization of C5- C7 can improve the octane number. The octane number of n-heptane is zero and increases after isomerization. For tri branched C7, the octane number reaches 113, which is higher than that of benzene. So, isomerization of C5-C7 is suggested to be a reasonable way to replace or partly replace the catalytic reforming process. It can decrease aromatics content with enhancement of octane number. Liquid acid catalysts were widely used in chemical industry in past decades. However, they face strong environmental challenges. The heavy corrosion of the reactor system is one of the main problems. Thus, solid acid catalysts are investigated for the isomerization reactions. The aim of this work is to develop a catalysts for the production of reformate products. Isomerization is catalyzed by metal-acid bifunctional catalysts. The metal components aid in hydrogenation, while the support, such as, zirconium, clays or zeolites, is the acidic component. (author)

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.

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....

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.

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

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.

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.

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...

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.

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.

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)

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.

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

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.

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...

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

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

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.

Electrocatalytic Activity and Stability of M-Fe Catalysts Synthesized by Polymer Complex Method for PEFC Cathode

KAUST Repository

Ou, Yiwei

2011-11-01

The polymerized complex (PC) method was used to synthesize highly dispersed iron-based catalysts for the oxygen reduction reaction (ORR). The catalysts were prepared with an addition of 1,10-phenanthroline (Phen) and transition metals (M), such as Ta, Ti, and W, in an attempt to enhance the ORR activity and durability of the catalysts. The composition and properties of the catalysts were characterized by thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst components, after extensive dissolution in a strong acid solution, were characterized by inductively coupled plasma mass spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ti-Fe catalyst showed improved ORR performance, and the Ta-Fe catalyst showed enhanced stability towards ORR in acidic solution. The catalytic activity and stability for ORR was observed by adding Ti or Ta into the catalyst formulation, suggesting that the interaction between added hetero-ions (Ti and Ta) and ionic Fe active sites was beneficial for the ORR. A single-cell test with the synthesized catalyst in the cathode initially generated a high power density, but the low stability remains an issue to be solved.

Electrocatalytic Activity and Stability of M-Fe Catalysts Synthesized by Polymer Complex Method for PEFC Cathode

KAUST Repository

Ou, Yiwei; Kumagai, Hiromu; Yin, Fengxiang; Okada, Saori; Hatasawa, Haruna; Morioka, Hiroyuki; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

2011-01-01

The polymerized complex (PC) method was used to synthesize highly dispersed iron-based catalysts for the oxygen reduction reaction (ORR). The catalysts were prepared with an addition of 1,10-phenanthroline (Phen) and transition metals (M), such as Ta, Ti, and W, in an attempt to enhance the ORR activity and durability of the catalysts. The composition and properties of the catalysts were characterized by thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst components, after extensive dissolution in a strong acid solution, were characterized by inductively coupled plasma mass spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ti-Fe catalyst showed improved ORR performance, and the Ta-Fe catalyst showed enhanced stability towards ORR in acidic solution. The catalytic activity and stability for ORR was observed by adding Ti or Ta into the catalyst formulation, suggesting that the interaction between added hetero-ions (Ti and Ta) and ionic Fe active sites was beneficial for the ORR. A single-cell test with the synthesized catalyst in the cathode initially generated a high power density, but the low stability remains an issue to be solved.

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.

A novel hybrid catalyst for the esterification of high FFA in Jatropha oil for biodiesel production

International Nuclear Information System (INIS)

Mushtaq, M.; Tan, I.M.; Sagir, M.; Suleman Tahir, M.; Pervaiz, M.

2016-01-01

The synthesis and application of a hybrid catalyst for the esterification of free fatty acids (FFA) in Jatropha oil is reported. Three catalysts, namely silica sulfuric acid, silica supported boron trifluoride and a combination of the two in the weight ratio of 1:1, the hybrid catalyst, were investigated. Jatropha oil samples with a wide range of FFA values i.e. 6.64 to 45.64% were prepared and utilized for the experimental work. This study revealed that silica sulfuric acid and silica supported boron trifluoride were not very effective when used independently. However, a strong synergistic effect was noted in the catalytic activity of the hybrid catalyst which reduced the FFA value from 45.64 to 0.903% with a conversion efficiency of 98%. Reusability of the catalyst was also tested and the results were promising in up to three cycles of use when used with lower amounts of FFA (6.64%) in the oil. Under the influence of the catalyst, the reaction was found to follow first order kinetics. Activation energy was calculated to be 45.42 KJ·mol−1 for 2 wt.% of hybrid catalyst. The products were analyzed by FT-IR and NMR spectroscopic techniques and the results are reported. [es

Speciation analysis and leaching behaviors of selected trace elements in spent SCR catalyst.

Science.gov (United States)

Dai, Zejun; Wang, Lele; Tang, Hao; Sun, Zhijun; Liu, Wei; Sun, Yi; Su, Sheng; Hu, Song; Wang, Yi; Xu, Kai; Liu, Liang; Ling, Peng; Xiang, Jun

2018-09-01

This study investigated heavy metal chemical speciation and leaching behavior from a board-type spent selective catalytic reduction (SCR) catalyst containing high concentrations of vanadium, chromium, nickel, copper, zinc, and lead. A three-step sequential extraction method, standard toxicity characteristic leaching procedure (TCLP), and leaching characteristic tests have been performed. It was found that the mobility of six heavy metals in the spent SCR catalyst was significantly different. The mobility of the six heavy metals exhibited the following order: Ni > Zn > V > Cr > As > Cu. Meanwhile, TCLP test results revealed relatively high Zn and Cr leaching rate of 83.20% and 10.35%, respectively. It was found that leaching rate was positively correlated with available contents (sum of acid soluble, reducible and oxidizable fractions). Leaching characteristics tests indicated that pH substantially affected the leaching of these heavy metals. In particular, the leaching of Cr, Ni, Cu, and Zn was positively influenced by strong acid, while V and As were easily released in the presence of strong acid and strong alkali (pH 11). In terms of kinetics, the leaching of Cr, Ni, Cu, Zn, and As within the spent catalyst was dominated by erosion and dissolution processes, which were rapid reaction processes. V was released in large amounts within 1 h, but its leaching amount sharply decreased with time due to readsorption. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

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.

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

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.

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.

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...

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.

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.

Immunity of the Fe-N-C catalysts to electrolyte adsorption: phosphate but not perchloric anions

DEFF Research Database (Denmark)

Hu, Yang; Jensen, Jens Oluf; Pan, Chao

2018-01-01

often carried out, like for Pt-based catalysts, in dilute perchloric acid by assuming its non-adsorbing nature on the active sites. The assumption is however not true. In this work, a typical Fe-N-C catalyst was first synthesized by high-pressure pyrolysis in the presence of carbon support...... and thoroughly characterized in terms of morphology, structure and active site distribution. The subsequent electrochemical characterization of the catalyst shows strong adsorption and poisoning effect of, in addition to the known Cl-, perchloric anions on the oxygen reduction reaction (ORR) activity...

Ammonia and water sorption properties of the mineral-layered nanomaterials used as the catalysts for NOx removal from exhaust gases

International Nuclear Information System (INIS)

Olszewska, D.

2006-01-01

The object of the study is the influence of acidity and hydrophilic properties of the surface of catalyst of the selective catalytic reduction (SCR) of nitrogen oxides by NH 3 . A series of catalysts prepared with the ZrO 2 -pillared montmorillonite from Jelsovy Potok have been promoted with manganese oxides. A part of the Na + -montmorillonite form has provisionally been treated with the 20% HCl. The acidity of materials was studied by the ammonia adsorption method at the temperature of 273 and 373K. Acidic properties of catalysts depend on the step of the support preparation-the acidic activation. The activity of the SCR reaction of acid untreated support and the catalyst with MnO x which had few stronger acid centres was lower than the activity of the acid pre-treated catalyst. In this case the support had more strong acid centres. The active material of MnO x increased the NO conversion but not the influence on the amount of ammonia sorption. These centres are probably not acidic centers. The hydrophilic properties were studied by water vapour sorption at the temperature of 298K. All the samples adsorbed the same amount of water, which suggests that the NO conversion does not influence hydrophilic properties. Water molecules were physically sorbed on the surface of materials and they were replaced with NH 3 in the presence of ammonia. (author)

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...

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.

Synthesis and stability of strongly acidic benzamide derivatives

DEFF Research Database (Denmark)

Diness, Frederik; Bjerrum, Niels J.; Begtrup, Mikael

2018-01-01

Reactivity studies of strong organic acids based on the replacement of one or both of the oxygens in benzoic acids with the trifluoromethanesulfonamide group are reported. Novel derivatives of these types of acids were synthesized in good yields. The generated N-triflylbenzamides were further...... functionalized through cross-coupling and nucleophilic aromatic substitution reactions. All compounds were stable in dilute aqueous solutions. Studies of stability under acidic and basic conditions are also reported....

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.

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.

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

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.

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.

Catalytic cracking of iso-hexene over sapo-34 catalyst

International Nuclear Information System (INIS)

Nawaz, Z.; Shu, Q.

2009-01-01

The catalytic cracking of model feed compound, iso-hexene (2-methyl-1-pentene) was experimentally studied over 100% pure SAPO-34 zeolite catalyst. The critical focus was given to obtain maximum propylene selectivity. The product distributions were analyzed at temperature between 450-600 degree C. time-on-stream (TOS) from 1 to 5 min. and at WHSV = 7.9 h/sub -1/ The reaction behavior was quantified on both direct and indirect carbenium ion mechanisms owing to catalyst's small pore diameter with respect to 2-methyl-l-pentene kinetic diameter. The propylene yield and selectivity obtained was 41.2% and 43.1% respectively. with higher overall olefins selectivity 90.3%. The small pore size and week surface acid sites of 1000 percent pure SAPO-34 catalyst were found to be suitable for light olefins production and eliminate chances of bimolecular reactions. It was observed that both conversion and selectivity were strongly effected by TOS, as coke precursors become dominant and deactivate catalyst at higher TOS. (author)

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.

Photochemical decomposition of perfluorooctanoic acid mediated by iron in strongly acidic conditions

Energy Technology Data Exchange (ETDEWEB)

Ohno, Masaki, E-mail: mohno@hiroshima-u.ac.jp [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan); Ito, Masataka; Ohkura, Ryouichi [Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences, 265-1, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Mino A, Esteban R. [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan); Kose, Tomohiro [Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences, 265-1, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Okuda, Tetsuji [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan); Nakai, Satoshi [Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527 (Japan); Kawata, Kuniaki [Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences, 265-1, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Nishijima, Wataru [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan)

2014-03-01

Highlights: • Perfluorooctanoic acid (PFOA) was decomposed based on ferric ion performance. • Complete decomposition of PFOA was confirmed in strongly acidic conditions. • Fe{sup 2+} changed to Fe{sup 3+} to restore chemical equilibrium in this condition. • Fe{sup 3+} was only produced from Fe{sup 2+} by hydroxyl radical in weakly acidic conditions. • The Fe{sup 3+} regeneration mechanisms resulted in the performance of Fe{sup 3+} for PFOA. - Abstract: The performance of a ferric ion mediated photochemical process for perfluorooctanoic acid (PFOA) decomposition in strongly acidic conditions of pH 2.0 was evaluated in comparison with those in weakly acidic conditions, pH 3.7 or pH 5.0, based on iron species composition and ferric ion regeneration. Complete decomposition of PFOA under UV irradiation was confirmed at pH 2.0, whereas perfluoroheptanoic acid (PFHpA) and other intermediates were accumulated in weakly acidic conditions. Iron states at each pH were evaluated using a chemical equilibrium model, Visual MINTEQ. The main iron species at pH 2.0 is Fe{sup 3+} ion. Although Fe{sup 3+} ion is consumed and is transformed to Fe{sup 2+} ion by photochemical decomposition of PFOA and its intermediates, the produced Fe{sup 2+} ion will change to Fe{sup 3+} ion to restore chemical equilibrium. Continuous decomposition will occur at pH 2.0. However, half of the iron cannot be dissolved at pH 3.7. The main species of dissolved iron is Fe(OH){sup 2+}. At pH 3.7 or higher pH, Fe{sup 3+} ion will only be produced from the oxidation of Fe{sup 2+} ion by hydroxyl radical produced by Fe(OH){sup 2+} under UV irradiation. These different mechanisms of Fe{sup 3+} regeneration that prevail in strongly and weakly acidic conditions will engender different performances of the ferric ion.

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...

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.

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

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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

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

A Comparative Study of Solvothermal and Sol-Gel-Derived Nanocrystalline Alumina Catalysts for Ethanol Dehydration

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Mingkwan Wannaborworn

2015-01-01

Full Text Available The ethanol dehydration to ethylene over alumina catalysts prepared by solvothermal and sol-gel methods was investigated. Also, a commercial alumina was used for comparison purposes. The results showed that the catalytic activity depends on the properties of catalyst derived from different preparation methods and reaction temperature. The alumina synthesized by solvothermal method exhibited the highest activity. This can be attributed to the higher surface area and larger amount of acid site, especially the ratio of weak/strong acid strength as determined by N2 physisorption and NH3-TPD studies. The solvothermal-derived catalyst exhibited an excellent performance with complete ethanol conversion and 100% selectivity to ethylene at 350°C in comparison with other ones. In addition, we further studied the catalytic dehydration of alumina catalyst modified with Fe. The presence of 10 wt.% Fe decreased both conversion and ethylene selectivity. However, the acetaldehyde selectivity apparently increased. It was related to the dehydrogenation pathway that takes place on Fe species.

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.

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

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.)

Hydrodeoxygenation of Guaiacol Over Pt/Al-SBA-15 Catalysts.

Science.gov (United States)

Yu, Mi Jin; Park, Sung Hoon; Jeon, Jong-Ki; Ryu, Changkook; Sohn, Jung Min; Kim, Sang Chai; Park, Young-Kwon

2015-01-01

Upgrading of bio-oil through catalytic hydrodeoxygenation (HDO) reaction was investigated for guaiacol as a model compound. A batch reactor was used for the reaction condition of 40 bar and 250 degrees C. The target product was cyclohexane. Pt/Al-SBA-15 with the Si/Al ratios of 20, 40, and 80 and Pt/HZSM-5 were used as the catalyst. The SBA-15 catalysts were characterized by N2 adsorption-desorption, X-ray diffraction analysis, and temperature programmed desorption of ammonia. The order of cyclohexane yield was Pt/Al-SBA-15 (Si/Al = 20) > Pt/Al-SBA-15(40) > Pt/Al-SBA-15 (80), indicating that the quantity of acid sites plays an important role in the HDO reaction. On the other hand, Pt/HZSM-5 led to a very low cyclohexane yield, in spite of its abundant strong acid sites, due to its small pore size.

Biodiesel production from Silybum marianum L. seed oil with high FFA content using sulfonated carbon catalyst for esterification and base catalyst for transesterification

International Nuclear Information System (INIS)

Fadhil, Abdelrahman B.; Aziz, Akram M.; Al-Tamer, Marwa H.

2016-01-01

Highlights: • PET was converted to activated carbon and then sulfonated to prepare carbon acid catalyst. • Carbon acid catalyst was used for esterification of high acid value Silybum marianum L. seed oil. • Biodiesel was obtained with 96.98% efficiency. - Abstract: In this research work, waste of polyethylene terephthalate (PET) was converted into activated carbon and the latter was used in the preparation of a carbon acid catalyst. Waste of PET was converted into activated carbon via carbonization and steam activation, then the activated carbon was sulfonated using fuming sulfuric acid in order to produce the carbon acid catalyst. The prepared carbon acid catalyst was tested for esterification of high acid value non-edible oil, Silybum marianum L. seed oil (SMSO) via optimized protocol. Amount of the carbon acid catalyst, methanol to oil molar ratio, temperature and time were the experimental variables optimized. Esterification of SMSO with methanol using the prepared carbon acid catalyst reduced its parent acid value (20.0 mg KOH/g) to the acceptable limits for base-catalyzed transesterification (<2.0 mg KOH/g) using 6.0% w/w of the catalyst, 15:1 methanol to oil molar ratio, 68 °C reaction temperature and 180 min of reaction. The performance of the catalyst was reduced gradually during its recycling and reached to 60.0% at the 5th cycle. Kinetics of esterification of SMSO using the prepared carbon acid catalyst followed pseudo first order kinetics, and the activation energy was found to be 70.98 kJ/mol. The esterified oil was converted to biodiesel through optimized base-catalyzed transesterification with methanol. Biodiesel with (96.98% yield and purity of 96.69% w/w) yield was obtained using 0.80% KOH w/w, 6:1 methanol to oil molar ratio, 60 °C reaction temperature, 75 min of reaction and 600 rpm rate of stirring. The biodiesel properties were within the recommended biodiesel standards as prescribed by ASTM D 6751 and EN 14214. Transesterification of

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.

Use of Biomass as a Sustainable and Green Fuel with Alkali-Resistant DeNOx Catalysts based on Sulfated or Tungstated Zirconia

DEFF Research Database (Denmark)

Due-Hansen, Johannes; Fehrmann, Rasmus; Christensen, Claus H.

poisons is the use of supports with highly acidic properties, which would interact stronger with potassium than the vanadium species. Among those, sulfated and tungstated zirconica appears very attractive, since their surface acidity can be tuned in a wide range by varying the preparation procedure, WOX......, sulfated, and tungstated zirconia were prepared and tested. The influence of potassium additives on the acidity and activity was studied and the results were compared with traditional V2O5-WO3/TiO2 catalyst. Resistance of the catalysts towards poisoning with potassium was found to depend dramatically...... on the crystallinity and surface acidity of the support used. Better resistance of the samples based on sulfated and tungstated zirconia seems to be connected with the fact that a significant part of the potassium on the surface of the catalyst preferentially interact with strong acid sites of the support thus...

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.

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

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.

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

In situ FTIRS study of ethanol electro-oxidation on anode catalysts in direct ethanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Wang, Q.; Sun, G.; Jiang, L.; Zhu, M.; Yan, S.; Wang, G.; Xin, Q. [Chinese Academy of Sciences, Dalian (China). Dalian Inst. of Chemical Physics; Chen, Q.; Li, J.; Jiang, Y.; Sun, S. [Xiamen Univ., Xiamen (China). State Key Lab. for Physical Chemistry of Solid Surfaces

2006-07-01

The low activation of ethanol oxidation at lower temperatures is an obstacle to the development of cost-effective direct ethanol fuel cells (DEFCs). This study used a modified polyol method to prepare carbon-supported platinum (Pt) based catalysts. Carbon supported Pt-based catalysts were fabricated by a modified polyol method and characterized through transmission electron spectroscopy (TEM) and X-ray diffraction (XRD). Results of the study showed that the particles in the Pt/C and PtRu/C and PtSn/C catalysts were distributed on the carbon support uniformly. Diffraction peaks of the Pt shifted positively in the PtRu/C catalysts and negatively in the PtSn/C catalysts. In situ Fourier Transform Infra-red spectroscopy (FTIR) was used to investigate the adsorption and oxidation process of ethanol on the catalysts. Results showed that the electrocatalytic activity of ethanol oxidation on the materials was enhanced. Linear bonded carbon monoxide (CO) was the most strongly absorbed species, and the main products produced by the catalysts were carbon dioxide (CO{sub 2}), acetaldehyde, and acetic acid. Results showed that the PtRu/C catalyst broke the C-C bond more easily than the Pt/C and PtSn/C compounds. However, the results of a linear sweep voltammogram analysis showed that ethanol oxidation of the PtSn/C was enhanced. Bands observed on the compound indicated the formation of acetic acid and acetaldehyde. It was concluded that the enhancement of PtSn/C for ethanol oxidation was due to the formation of acetic acid and acetaldehyde at lower potentials. 4 refs., 1 fig.

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.

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

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.

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

Hydrogen production from raw bioethanol steam reforming: optimization of catalyst composition with improved stability against various impurities

International Nuclear Information System (INIS)

Le Valant, A.; Can, F.; Bion, N.; Epron, F.; Duprez, D.

2009-01-01

Usually, ethanol steam reforming is performed using pure ethanol, whereas the use of raw bioethanol is of major importance for a cost effective industrial application. Raw bioethanol contains higher alcohols as the main impurities and also aldehydes, amines, acids and esters. The effect of these impurities on the catalytic performances for ethanol steam reforming (ESR) has been studied, using a reference catalyst, Rh/MgAl 2 O 4 . It was shown that the aldehyde, the amine and methanol has no negative effect on the catalytic performances, contrary to the ester, acid and higher alcohols. The deactivation is mainly explained by coke formation favored by the presence of these impurities in the feed. In order to improve the stability of the catalyst and its performances in the presence of these deactivating impurities, the catalyst formulation, i.e. the composition of the support and of the metallic phase, was modified. The addition of rare earth elements instead of magnesium to the alumina support leads to a decrease of the strong and medium acid sites and to an increase of the basicity. On these modified supports, the dehydration reaction, leading to olefins, which are coke precursors, is disfavored, the ethanol conversion and the hydrogen yield are increased. The best catalytic performances were obtained with Rh/Y-Al 2 O 3 . Then, the metallic phase was also modified by adding a second metal (Ni, Pt or Pd). The Rh-Ni/Y-Al 2 O 3 catalyst leads to the highest hydrogen yield. This catalyst, tested in the presence of raw bioethanol during 24h was very stable compared to the reference catalyst Rh/MgAl 2 O 4 , which was strongly deactivated after 2h of time-on-stream. (author)

Alkali-Resistant Mechanism of a Hollandite DeNOx Catalyst.

Science.gov (United States)

Hu, Pingping; Huang, Zhiwei; Gu, Xiao; Xu, Fei; Gao, Jiayi; Wang, Yue; Chen, Yaxin; Tang, Xingfu

2015-06-02

A thorough understanding of the deactivation mechanism by alkalis is of great importance for rationally designing improved alkali-resistant deNOx catalysts, but a traditional ion-exchange mechanism cannot often accurately describe the nature of the deactivation, thus hampering the development of superior catalysts. Here, we establish a new exchange-coordination mechanism on the basis of the exhaustive study on the strong alkali resistance of a hollandite manganese oxide (HMO) catalyst. A combination of isothermal adsorption measurements of ammonia with X-ray absorption near-edge structure spectra and X-ray photoelectron spectra reveals that alkali metal ions first react with protons from Brønsted acid sites of HMO via the ion exchange. Synchrotron X-ray diffraction patterns and extended X-ray absorption fine structure spectra coupled with theoretical calculations demonstrate that the exchanged alkali metal ions are subsequently stabilized at size-suitable cavities in the HMO pores via a coordination model with an energy savings. This exchange-coordination mechanism not only gives a wholly convincing explanation for the intrinsic nature of the deactivation of the reported catalysts by alkalis but also provides a strategy for rationally designing improved alkali-resistant deNOx catalysts in general.

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

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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.

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.

Preparation and characterization Al3+-bentonite Turen Malang for esterification fatty acid (palmitic acid, oleic acid and linoleic acid)

Science.gov (United States)

Abdulloh, Abdulloh; Aminah, Nanik Siti; Triyono, Mudasir, Trisunaryanti, Wega

2016-03-01

Catalyst preparation and characterization of Al3+-bentonite for esterification of palmitic acid, oleic acid and linoleic acid has been done. Al3+-bentonite catalyst was prepared from natural bentonite of Turen Malang through cation exchange reaction using AlCl3 solution. The catalysts obtained were characterized by XRD, XRF, pyridine-FTIR and surface area analyser using the BET method. Catalyst activity test of Al3+-bentonite for esterification reaction was done at 65°C using molar ratio of metanol-fatty acid of 30:1 and 0.25 g of Al3+-bentonite catalyst for the period of ½, 1, 2, 3, 4 and 5 hours. Based on the characterization results, the Al3+-bentonite Turen Malang catalyst has a d-spacing of 15.63 Ǻ, acid sites of Brönsted and Lewis respectively of 230.79 µmol/g and 99.39 µmol/g, surface area of 507.3 m2/g and the average of radius pore of 20.09 Å. GC-MS analysis results of the oil phase after esterification reaction showed the formation of biodiesel (FAME: Fatty acid methyl ester), namely methyl palmitate, methyl oleate and methyl linoleate. The number of conversions resulted in esterification reaction using Al3+-bentonite Turen Malang catalyst was 74.61%, 37.75%, and 20, 93% for the esterification of palmitic acid, oleic acid and linoleic acid respectively.

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.

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.

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.

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.).

Coupled Metal/Oxide Catalysts with Tunable Product Selectivity for Electrocatalytic CO2 Reduction.

Science.gov (United States)

Huo, Shengjuan; Weng, Zhe; Wu, Zishan; Zhong, Yiren; Wu, Yueshen; Fang, Jianhui; Wang, Hailiang

2017-08-30

One major challenge to the electrochemical conversion of CO 2 to useful fuels and chemical products is the lack of efficient catalysts that can selectively direct the reaction to one desirable product and avoid the other possible side products. Making use of strong metal/oxide interactions has recently been demonstrated to be effective in enhancing electrocatalysis in the liquid phase. Here, we report one of the first systematic studies on composition-dependent influences of metal/oxide interactions on electrocatalytic CO 2 reduction, utilizing Cu/SnO x heterostructured nanoparticles supported on carbon nanotubes (CNTs) as a model catalyst system. By adjusting the Cu/Sn ratio in the catalyst material structure, we can tune the products of the CO 2 electrocatalytic reduction reaction from hydrocarbon-favorable to CO-selective to formic acid-dominant. In the Cu-rich regime, SnO x dramatically alters the catalytic behavior of Cu. The Cu/SnO x -CNT catalyst containing 6.2% of SnO x converts CO 2 to CO with a high faradaic efficiency (FE) of 89% and a j CO of 11.3 mA·cm -2 at -0.99 V versus reversible hydrogen electrode, in stark contrast to the Cu-CNT catalyst on which ethylene and methane are the main products for CO 2 reduction. In the Sn-rich regime, Cu modifies the catalytic properties of SnO x . The Cu/SnO x -CNT catalyst containing 30.2% of SnO x reduces CO 2 to formic acid with an FE of 77% and a j HCOOH of 4.0 mA·cm -2 at -0.99 V, outperforming the SnO x -CNT catalyst which only converts CO 2 to formic acid in an FE of 48%.

Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

Energy Technology Data Exchange (ETDEWEB)

Conrad Ingram; Mark Mitchell

2006-09-30

The addition of hydrothermally-aged zeolite Y precursor to an SBA-15 synthesis mixture under a mildly acidic condition resulted in the formation of mesoporous aluminosilicate catalyst, Al-SBA-15, containing strong Broensted acid sites and aluminum (Al) stabilized in a totally tetrahedral coordination. The physicochemical characteristics of the catalyst varied as a function of the synthesis conditions. The catalyst possessed surface areas ranging between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm, and pore volumes up 1.03 cm{sup 3}, which were comparable to the parent SBA-15 synthesized under similar conditions. Two wt% Al was present in the catalyst that was obtained from the reaction mixture that contained the highest Al content. The Al remained stable in totally tetrahedral coordination after calcination at 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and the activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. In preparation for the final phase of the project, the catalyst was embedded into psuedoboemite alumina (catapal B) matrix and then formed into pellets. In the final phase of the project, the pelletized catalyst will be evaluated for the conversion of heavy petroleum feedstocks to naphtha and middle distillates.

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.

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

Production of liquid alkanes by controlling reactivity of sorbitol hydrogenation with a Ni/HZSM-5 catalyst in water

International Nuclear Information System (INIS)

Zhang, Qing; Wang, Tiejun; Xu, Ying; Zhang, Qi; Ma, Longlong

2014-01-01

Graphical abstract: MCM-41-modified Ni/HZSM-5 catalyst was developed by impregnation method with high catalytic performance for sorbitol hydrogenation in water. Appropriate amount of MCM-41 addition can distinctly promote the improvement in the surface structure and modulation of acidic sites of the catalyst. The scission of C–O bond in the sorbitol molecule into liquid alkanes was easily carried out on the catalyst containing more Lewis acidic sites. - Highlights: • Ni/HZSM-5 promoted with MCM-41 is active for sorbitol hydrogenation to liquid alkanes. • Lewis acidic sites of Ni/HZSM-5 can be modulated by pure silica MCM-41. • MCM-41 added can distinctly decrease carbon deposition on the catalyst surface. - Abstract: Liquid fuels derived from renewable biomass are of great importance on the potential substitution for diminishing fossil fuels. The conversion of sorbitol (a product of biomass-derived glucose hydrogenation) into liquid alkanes such as pentane and hexane over the Ni/HZSM-5 catalysts with or without MCM-41 addition was investigated in the presence of hydrogen in water medium. The production distribution of sorbitol hydrogenation can be controlled by adjusting the acidity of the catalyst. The scission of C–C bond in the sorbitol molecule into light C 1 –C 4 alkanes was mainly carried out over Ni/HZSM-5 containing strong Brønsted acid sites, while C–O bond scission into heavier alkanes was dominated over the catalysts added by MCM-41 containing weak Lewis acid sites. The sorbitol conversion and total liquid alkanes selectivity were found to be 67.1% and 98.7% over 2%Ni/HZSM-5 modified by 40 wt% of MCM-41, whereas the corresponding value was 40% and 35.6% over 2%Ni/HZSM-5 in the absence of MCM-41. The effect of MCM-41 on the structure, acidity, and reducibility of Ni/HZSM-5 was investigated by using XRD, Py-IR, IR, and H 2 -TPR. Meanwhile, the resistance of carbon deposition over the catalyst modified by MCM-41 was studied by using TG�

Dielectric loss property of strong acids doped polyaniline (PANi)

Science.gov (United States)

Amalia, Rianti; Hafizah, Mas Ayu Elita; Andreas, Manaf, Azwar

2018-04-01

In this study, strong acid doped polyaniline (PANi) has been successfully fabricated through the chemical oxidative polymerization process with various polymerization times. Nonconducting PANi resulting from the polymerization process at various polymerization times were then doped by a strong acid HClO4 to generate dielectric properties. Ammonium Persulfate (APS) as an initiator was used during Polymerization process to develop dark green precipitates which then called Emeraldine Base Polyaniline (PANi-EB). The PANi-EB was successively doped by strong acid HClO4 with dopant and PANi ratio 10:1 to enhance the electrical conductivity. The conductivity of doped PANi was evaluated by Four Point Probe. Results of evaluation showed that the conductivity values of HClO4 doped PANi were in the range 337-363 mS/cm. The dielectric properties of doped PANi were evaluated by Vector Network Analyzer (VNA) which suggested that an increase in the permittivity value in the conducting PANi. It is concluded that PANi could be a potential candidate for electromagnetic waves absorbing materials.

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...

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.

Modification of the performance of WO3-ZrO2 catalysts by metal addition in hydrocarbon reactions

Directory of Open Access Journals (Sweden)

Gerardo Carlos Torres

2012-01-01

Full Text Available A study of the different hydrocarbon reactions over Ni doped WO3-ZrO2 catalysts was performed. Ni was found as NiO at low Ni concentration while at high Ni concentrations a small fraction was present as a metal. For both cases, Ni strongly modified total acidity and concentration of strong acid sites. In the cyclohexane dehydrogenation reaction, Ni addition promotes both benzene and methyl cyclopentane production. The hydroconversion activity (n-butane and n-octane increases with the augment of total acidity produced by Ni. The selectivity to reaction products is modified according to the acid strength distribution changes produced by Ni addition.

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.

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.

How strong are strong poly(sulfonic acids)? An example of the poly(2-acrylamido-2-methyl-1-propanesulfonic acid)

Czech Academy of Sciences Publication Activity Database

Gospodinova, Natalia; Tomšík, Elena; Omelchenko, Olga

2016-01-01

Roč. 74, January (2016), s. 130-135 ISSN 0014-3057 R&D Projects: GA ČR(CZ) GA15-14791S Institutional support: RVO:61389013 Keywords : polyelectrolytes * strong poly(acids) * proton conductors Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.531, year: 2016

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...

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

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.

Strong activation of bile acid-sensitive ion channel (BASIC) by ursodeoxycholic acid

Science.gov (United States)

Wiemuth, Dominik; Sahin, Hacer; Lefèvre, Cathérine M.T.; Wasmuth, Hermann E.; Gründer, Stefan

2013-01-01

Bile acid-sensitive ion channel (BASIC) is a member of the DEG/ENaC gene family of unknown function. Rat BASIC (rBASIC) is inactive at rest. We have recently shown that cholangiocytes, the epithelial cells lining the bile ducts, are the main site of BASIC expression in the liver and identified bile acids, in particular hyo- and chenodeoxycholic acid, as agonists of rBASIC. Moreover, it seems that extracellular divalent cations stabilize the resting state of rBASIC, because removal of extracellular divalent cations opens the channel. In this addendum, we demonstrate that removal of extracellular divalent cations potentiates the activation of rBASIC by bile acids, suggesting an allosteric mechanism. Furthermore, we show that rBASIC is strongly activated by the anticholestatic bile acid ursodeoxycholic acid (UDCA), suggesting that BASIC might mediate part of the therapeutic effects of UDCA. PMID:23064163

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.

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.

Electrochemical characterization of nano-sized Pd-based catalysts as cathode materials in direct methanol fuel cells.

Science.gov (United States)

Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

2011-01-01

To improve the catalytic activity of palladium (Pd) as a cathode catalyst in direct methanol fuel cells (DMFCs), we prepared palladium-titanium oxide (Pd-TiO2) catalysts which the Pd and TiO2 nanoparticles were simultaneously impregnated on carbon. We selected Pd and TiO2 as catalytic materials because of their electrochemical stability in acid solution. The crystal structure and the loading amount of Pd and TiO2 on carbon were characterized by X-ray diffraction (XRD) and energy dispersive X-ray microanalysis (EDX). The electrochemical characterization of Pd-TiO2/C catalysts for the oxygen reduction reaction was carried out in half and single cell systems. The catalytic activities of the Pd-TiO2 catalysts were strongly influenced by the TiO2 content. In the single cell test, the Pd-TiO2 catalysts showed very comparable performance to the Pt catalyst.

Some physico-chemical properties and catalytic activity of sulfate ion supported on WO3/SnO2 catalyst

Directory of Open Access Journals (Sweden)

M.N. Alaya

2017-02-01

Full Text Available Solid acid catalyst 15 wt%WO3/SnO2 was synthesized and loaded with 15 wt%SO4. The obtained catalyst was calcined at 400, 500, 650 and 800 °C. The prepared catalysts were characterized by TG-DTA, XRD, FTIR and N2 adsorption at −196 °C. The surface acidity was measured by non aqueous potentiometric titration and FT-IR spectra of chemisorbed pyridine. The catalytic performance was evaluated on the esterification of propionic acid with n-butanol in liquid phase. The TG-DTA analysis shows that the decomposition of sulfate species occurred at >500 °C. XRD measurements showed that WO3 dispersed completely on the surface of SnO2 and that the sulfating of WO3/SnO2 tends to hinder the crystallization of SnO2. The specific surface area, total pore volume and micropore volume are increased with increasing thermal treatment up to 500 °C, and then decreased gradually with a further increase in calcination temperature. The prepared catalysts possess very strong acid sites and contain both Brønsted and Lewis acid sites. The total surface acidity decreased with raising of the calcination temperature. The highest conversion of propionic acid was for 400 °C product, and decreased with an increase in calcination temperature. The effect of the reaction parameters, i.e., time of reaction, reaction temperature, and reactant molar ratio and the weight of the catalyst were also studied. The reaction obeys the second order kinetic equation with respect to propionic acid concentration. Brønsted and Lewis acid sites appeared to be needed for catalytic activity in n-butyl propionate formation.

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.

High-performance bimetallic alloy catalyst using Ni and N co-doped composite carbon for the oxygen electro-reduction.

Science.gov (United States)

Jung, Won Suk

2018-03-15

In this study, a novel synthesis method for the bimetallic alloy catalyst is reported, which is subsequently used as an oxygen reduction catalyst in polymer electrolyte membrane fuel cells (PEMFCs). The support prepared from the Ni-chelate complex shows a mesoporous structure with a specific surface area of ca. 400 m 2  g -1 indicating the suitable support for PEMFC applications. Ethylenediamine is converted to the nitrogen and carbon layers to protect the Ni particles which will diffuse into the Pt lattice at 800 °C. The PtNi/NCC catalyst with PtNi cores and Pt-rich shells is successfully formed when acid-treated as evidenced by line scan profiles. The catalyst particles thus synthesized are well-dispersed on the N-doped carbon support, while the average particle size is ca. 3 nm. In the PEMFC test, the maximum power density of the PtNi/NCC catalyst shows approximately 25% higher than that of the commercial Pt/C catalyst. The mass activity of the PtNi/NCC catalyst showed approximately 3-fold higher than that of the commercial Pt/C catalyst. The mass activity strongly depends on the ratio of Pt to Ni since the strain effect can be strong for catalysts due to the mismatch of lattice parameters of the Ni and Pt. Copyright © 2017 Elsevier Inc. All rights reserved.

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

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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.

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.

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.

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.

Effects of precursor and sulfation on OMS-2 catalyst for oxidation of ethanol and acetaldehyde at low temperatures.

Science.gov (United States)

Wang, Renhu; Li, Junhua

2010-06-01

Volatile organic compounds (VOCs) emitted from many industrial processes and transportation activities are major organic pollutants in the atmosphere and toxic to human health. Octahedral molecular sieve (OMS-2) catalysts with different precursors and sulfate-acidified OMS-2 catalysts were synthesized using refluxing methods. The catalysts were investigated on complete oxidation of ethanol and acetaldehyde, and both demonstrated good reactivity. However, acidification resulted in a decrease in activity. OMS-2 catalyst using MnSO(4) as precursor exhibited the best catalytic performance and, thus, was selected for catalyst deactivation by sulfur dioxide. The results of this study suggested that the Mn-O bond of OMS-2 catalysts was the main determinant of the catalytic activity toward oxygenated VOC oxidation and weaker acid sites benefited higher acetaldehyde selectivity. Catalyst deactivation resulted from a strong but slow chemical interaction between the Mn-O bond and sulfur dioxide, probably forming manganese sulfate.

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

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.

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.

Hydroisomerization of n-dodecane over Pt/Al-MCM-48 catalysts.

Science.gov (United States)

Yun, Soyoung; Park, Young-Kwon; Jeong, Soon-Yong; Han, Jeongsik; Jeon, Jong-Ki

2014-04-01

The objective of this study is to evaluate the catalytic potential of Pt/Al-MCM-48 catalysts in hydroisomerization of n-dodecane. The effects of the Si/Al ratio and platinum loading on the acid characteristics of Al-MCM-48 and the catalytic performance in n-dodecane hydroisomerization were analyzed. The catalysts were characterized by X-ray diffraction, nitrogen adsorption, infrared spectroscopy of pyridine adsorption, and temperature programmed desorption of ammonia. The number of weak strength acid sites on Al-MCM-48 increased with 0.5 wt% platinum loading. The weak strength acid sites of Pt/Al-MCM-48 catalysts were ascribed to Lewis acid sites, which can be confirmed by NH3-TPD and FTIR spectra of pyridine adsorption. Iso-dodecane can be produced with high selectivity in n-dodecane hydrosisomerization over Pt/Al-MCM-48 catalysts. This is attributed to the mild acidic properties of Pt/Al-MCM-48 catalysts.

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.

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.

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.

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

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...

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.

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.

Modification of the performance of WO{sub 3}-ZrO{sub 2} catalysts by metal addition in hydrocarbon reactions

Energy Technology Data Exchange (ETDEWEB)

Torres, Gerardo Carlos; Manuale, Debora Laura; Benitez, Viviana Monica; Vera, Carlos Roman; Yori, Juan Carlos, E-mail: jyori@fiq.unl.edu.ar [Instituto de Investigaciones en Catalisis y Petroquimica, Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Consejo Nacional de Investigaciones Cientifica y Tecnicas, Santiago del Estero Santa Fe (Argentina)

2012-07-01

A study of the different hydrocarbon reactions over Ni doped WO{sub 3}-ZrO{sub 2} catalysts was performed. Ni was found as NiO at low Ni concentration while at high Ni concentrations a small fraction was present as a metal. For both cases, Ni strongly modified total acidity and concentration of strong acid sites. In the cyclohexane dehydrogenation reaction, Ni addition promotes both benzene and methyl cyclopentane production. The hydroconversion activity (n-butane and n-octane) increases with the augment of total acidity produced by Ni. The selectivity to reaction products is modified according to the acid strength distribution changes produced by Ni addition. (author)

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.

Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

Science.gov (United States)

González, J.; Chen, L. F.; Wang, J. A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J. L.

2016-08-01

A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H2O2 as oxidant. ODS activity was found to be proportional to the V5+/(V4+ + V5+) values of the catalysts, indicating that the surface vanadium pentoxide (V2O5) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V2O5) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V2O5/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

A built-in radiotracer (24Na) for measuring circulation catalyst rates

International Nuclear Information System (INIS)

Domondon, D.B; Berbano, M.C.

1975-01-01

A local petroleum refinery intended to calibrate its catalyst flow measuring instrument (propeller blade) using the radioactive tracer technique (RTT). For this purpose, a method of incorporating a suitable radiotracer in commercial catalyst beads had to be found. Two methods of labelling are described. One method involved the incorporation of the radiotracer in a gel of the same composition as the commercial catalyst and subsequent conversion of the gel into a from like that of the commercial catalyst beads. Another method utilized the strong adsorptive properties of the commercial catalyst beads for the chosen isotopes, e.g., 144 Cs, 46 Sc. To effect quantitative adsorption, commercial catalyst beads were simply stirred in a slightly acidic (pH4) chloride solution of the radiotracers for some time. The radiotracers were found to distribute almost uniformly over the entire catalyst surface and no evidence of volatilization of the isotopes from the catalyst surface under condition of use in commercial units was observed. Another probable method was suggested by the Research and Development Division, Philippine Atomic Energy Commission. Aluminium is a major component of the ceramic catalyst beads and sodium is present as impurity. Hence, a radiotracer ( 24 Na) can be formed in the beads by the reaction 23 Na (n,gamma) 24 Na, 27 Al (n,alpha) 24 Na. This possible method of simply irradiating the commercial catalyst beads in the reactor thereby inducing the radiotracer. 24 Na in situ fulfils all the criteria for the selection of an appropriate radiotracer. The method is very simple but reliable

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.

Magnetic Vinylphenyl Boronic Acid Microparticles for Surface Catalytic Performance in Esterification of Propionic Acid with Methanol

Directory of Open Access Journals (Sweden)

Ali Kara

2016-12-01

Full Text Available Magnetic vinylphenyl boronic acid microparticles, poly(ethylene glycol dimethacrylate-vinylphenyl boronic acid [m-poly(EGDMA-VPBA], produced by suspension polymerization, was found to be efficient solid acid catalyst for the esterification of methanol and propionic acid. Characterization techniques such as FT-IR, Elemental analyses, ICP-AES, ESR, SEM and N2 sorption showed that both of Fe3O4 and H2SO4 are bonded to the polymer successfully. Esterification was studied for different molar percentages of H2SO4 at temperature range of 50-70 oC. The apparent activation energy was found to be 27.7 kj.mol-1 for 10% H2SO4 doped m-poly(EGDMA-VPBA. Combining of strong acid H2SO4 with m-poly(EGDMA-VPBA, leads to materials with different functional properties. In addition, H2SO4 species could be introduced into the structure as acid centers, therefore this micro-dimensional catalyst has potential candidate for applications in the catalytic esterifications such as propionic acid with methanol.

Catalytic Hydrogenation of Levulinic Acid in Water into g-Valerolactone over Bulk Structure of Inexpensive Intermetallic Ni-Sn Alloy Catalysts

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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  

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

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

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...

Rape oil transesterification over heterogeneous catalysts

Energy Technology Data Exchange (ETDEWEB)

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

2010-11-15

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

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.

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

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

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.

Alkali promotion effect in Fischer-Tropsch cobalt-alumina catalyst

Energy Technology Data Exchange (ETDEWEB)

Eliseev, O.L.; Tsapkina, M.V.; Davydov, P.E.; Kazantsev, R.V. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry; Belousova, O.S.; Lapidus, A.L. [Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation)

2011-07-01

Promoting Co-alumina Fischer-Tropsch synthesis catalysts with alkali and alkaline-earth metals was studied. XRD, oxygen titration and CO chemisorption were used for the characterization of the catalysts. The best results in terms of catalyst selectivity and long-chain alkanes content in synthesized products were obtained with K-promoted catalyst. Catalytic performance strongly depends on K:Co atomic ratio as well as preparation procedure. Effect of K loading on selectivities is non-linear with extreme point at K:Co=0.01. Significant increase in C{sub 5+} selectivity of K-promoted catalyst may be explained as a result of strong CO adsorption on the catalyst surface, as was confirmed in CO chemisorption experiments. (orig.)

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.

CATALYSTS NHI Thermochemical Systems FY 2009 Year-End Report

International Nuclear Information System (INIS)

Ginosar, Daniel M.

2009-01-01

Fiscal Year 2009 work in the Catalysts project focused on advanced catalysts for the decomposition of sulfuric acid, a reaction common to both the Sulfur-Iodine (S-I) cycle and the Hybrid Sulfur cycle. Prior years effort in this project has found that although platinum supported on titanium oxide will be an acceptable catalyst for sulfuric acid decomposition in the integrated laboratory scale (ILS) project, the material has short comings, including significant cost and high deactivation rates due to sintering and platinum evaporation. For pilot and larger scale systems, the catalyst stability needs to be improved significantly. In Fiscal Year 2008 it was found that at atmospheric pressure, deactivation rates of a 1 wt% platinum catalyst could be reduced by 300% by adding either 0.3 wt% iridium (Ir) or 0.3 wt% ruthenium (Ru) to the catalyst. In Fiscal Year 2009, work focused on examining the platinum group metal catalysts activity and stability at elevated pressures. In addition, simple and complex metal oxides are known to catalyze the sulfuric acid decomposition reaction. These metal oxides could offer activities comparable to platinum but at significantly reduced cost. Thus a second focus for Fiscal Year 2009 was to explore metal oxide catalysts for the sulfuric acid decomposition reaction. In Fiscal Year 2007 several commercial activated carbons had been identified for the HI decomposition reaction; a reaction specific to the S-I cycle. Those materials should be acceptable for the pilot scale project. The activated carbon catalysts have some disadvantages including low activity at the lower range of reactor operating temperature (350 to 400 C) and a propensity to generate carbon monoxide in the presence of water that could contaminate the hydrogen product, but due to limited funding, this area had low priority in Fiscal Year 2009. Fiscal Year 2009 catalyst work included five tasks: development, and testing of stabilized platinum based H2SO4 catalysts

Uniformly active phase loaded selective catalytic reduction catalysts (V_2O_5/TNTs) with superior alkaline resistance performance

International Nuclear Information System (INIS)

Wang, Haiqiang; Wang, Penglu; Chen, Xiongbo; Wu, Zhongbiao

2017-01-01

Highlights: • VOSO_4 exhibited better synergistic effect with titanate nanotubes than NH_4VO_3. • Ion-exchange reaction occurs between VOSO_4 and titanate nanotubes. • Ion-exchange resulting in uniformly vanadium distribution on titanate nanotubes. • VOSO_4-based catalyst exhibited impressive SCR activity and alkaline resistance. - Abstract: In this work, protonated titanate nanotubes was performed as a potential useful support and different vanadium precursors (NH_4VO_3 and VOSO_4) were used to synthesize deNO_x catalysts. The results showed that VOSO_4 exhibited better synergistic effect with titanate nanotubes than NH_4VO_3, which was caused by the ion-exchange reaction. Then high loading content of vanadium, uniformly active phase distribution, better dispersion of vanadium, more acid sites, better V"5"+/V"4"+ redox cycles and superior oxygen mobility were achieved. Besides, VOSO_4-based titanate nanotubes catalysts also showed enhanced alkaline resistance than particles (P25) based catalysts. It was strongly associated with its abundant acid sites, large surface area, flexible redox cycles and oxygen transfer ability. For the loading on protonated titanate nanotubes, active metal with cation groups was better precursors than anion ones. V_2O_5/TNTs catalyst was a promising substitute for the commercial vanadium catalysts and the work conducted herein provided a useful idea to design uniformly active phase loaded catalyst.

Synthesis of Dicyclopentadiene Oligomer Over Nanoporous Al-MCM-41 Catalysts.

Science.gov (United States)

Park, Eunseo; Kim, Jinhan; Yim, Jin-Heong; Han, Jeongsik; Kwon, Tae Soo; Park, Y K; Jeon, Jong-Ki

2016-05-01

One step reaction composed of DCPD oligomerization and DCPD oligomer isomerization was investigated over nanoporous Al-MCM-41 catalysts. The effects of aluminum grafting over MCM-41 on the catalyst characteristics were studied with respect to the synthesis of TCPD isomer. Physical and chemical properties of the catalysts were analyzed by N2 adsorption, temperature-programmed desorption of ammonia, and infrared spectroscopy of adsorbed pyridine. The overall number of acid sites as well as the number of Lewis acid sites increased with increasing of aluminum content over MCM-41. When utilizing MCM-41 and Al-MCM-41 as the catalyst, DCPD oligomerization reaction activity greatly increased compared to the thermal reaction. The highest TCPD isomer selectivity over the Al-MCM-41 catalyst with the highest aluminum content could be ascribed to the largest amount of acid sites. This study showed an increased level of TCPD isomer selectivity by an increasing level of Lewis acid sites through aluminum addition over MCM-41.

Methanol conversion to hydrocarbons using modified clinoptilolite catalysts. Investigation of catalyst lifetime and reactivation

Energy Technology Data Exchange (ETDEWEB)

Hutchings, G J; Themistocleous, T; Copperthwaite, R G

1988-10-17

A study of the deactivation and reactivation of modified clinoptilolite catalysts for methanol conversion to hydrocarbons is reported. Clinoptilolite catalysts, modified by either ammonium ion exchange or hydrochloric acid treatment, exhibit a short useful catalyst lifetime for this reaction (ca. 2-3 h) due to a high rate of coke deposition (3-5.10/sup -3/ g carbon/g catalyst/h). A comparative study of reactivation using oxygen, nitrous oxide and ozone/oxygen as oxidants indicated that nitrous oxide reactivation gives improved catalytic performance when compared to the activity and lifetime of the fresh catalyst. Both oxygen and ozone/oxygen were found to be ineffective for the reactivation of clinoptilolite. Initial studies of in situ on-line reactivation are also described. 3 figs., 15 refs., 4 tabs.

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.

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.

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.

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....

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.

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)

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)

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.

The use of niobium based catalysts for liquid fuel production

Directory of Open Access Journals (Sweden)

Reguera Frank Martin

2004-01-01

Full Text Available The catalytic properties of niobium based catalysts were investigated in the conversion of oleic acid to liquid fuels at atmospheric pressure and at 623 K. The catalytic tests were performed in a fixed bed and continuous flow reactor using an acid to catalyst ratio equal to 4 and N2 as carrier gas. The reaction products were analyzed by gas chromatography and acidity measurements. NH3 temperature programmed desorption, N2 adsorption-desorption (BET method and Xray diffraction were also performed in order to determine the structural and acidic properties of the catalysts. From the catalytic tests, it was detected the formation of compounds in the range of gasoline, diesel and lubricant oils. Higher catalytic activity and selectivity for diesel fuel were observed for the catalysts NbOPO4 and H3PO4/Nb2O5 that possesses higher acidities and surface areas.

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.

Catalytic dehydration of ethanol using transition metal oxide catalysts.

Science.gov (United States)

Zaki, T

2005-04-15

The aim of this work is to study catalytic ethanol dehydration using different prepared catalysts, which include Fe(2)O(3), Mn(2)O(3), and calcined physical mixtures of both ferric and manganese oxides with alumina and/or silica gel. The physicochemical properties of these catalysts were investigated via X-ray powder diffraction (XRD), acidity measurement, and nitrogen adsorption-desorption at -196 degrees C. The catalytic activities of such catalysts were tested through conversion of ethanol at 200-500 degrees C using a catalytic flow system operated under atmospheric pressure. The results obtained indicated that the dehydration reaction on the catalyst relies on surface acidity, whereas the ethylene production selectivity depends on the catalyst chemical constituents.

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.

Alkali resistant Ni-loaded yolk-shell catalysts for direct internal reforming in molten carbonate fuel cells

Science.gov (United States)

Jang, Won-Jun; Hong, Young Jun; Kim, Hak-Min; Shim, Jae-Oh; Roh, Hyun-Seog; Kang, Yun Chan

2017-06-01

A facile and scalable spray pyrolysis process is applied to synthesize multi-shelled Ni-loaded yolk-shell catalysts on various supports (Al2O3, CeO2, ZrO2, and La(OH)3). The prepared catalysts are applied to direct internal reforming (DIR) in a molten carbonate fuel cell (MCFC). Even on exposure to alkali hydroxide vapors, the Ni-loaded yolk-shell catalysts remain highly active for DIR-MCFCs. The Ni@Al2O3 microspheres show the highest conversion (92%) of CH4 and the best stability among the prepared Ni-loaded yolk-shell catalysts. Although the initial CH4 conversion of the Ni@ZrO2 microspheres is higher than that of the Ni@CeO2 microspheres, the Ni@CeO2 microspheres are more stable. The catalytic performance is strongly dependent on the surface area and acidity and also partly dependent on the reducibility. The acidic nature of Al2O3 combined with its high surface area and yolk-shell structure enhances the adsorption of CH4 and resistance against alkali poisoning, resulting in efficient DIR-MCFC reactions.

Observation of ionomer in catalyst ink of polymer electrolyte fuel cell using cryogenic transmission electron microscopy

International Nuclear Information System (INIS)

Takahashi, Shinichi; Shimanuki, Junichi; Mashio, Tetsuya; Ohma, Atsushi; Tohma, Hajime; Ishihara, Ayumi; Ito, Yoshiko; Nishino, Yuri; Miyazawa, Atsuo

2017-01-01

Optimizing the catalyst layer structure is one of the key issues for improving performance despite lower platinum loading. The catalyst ink, consisting of platinum-loaded carbon particles and ionomer dispersed in an aqueous solvent, is a key factor for controlling the structure of the catalyst layer because the catalyst layer is prepared in a wet coating process. For that purpose, we visualized the nanostructure of the ionomer in the catalyst ink by cryogenic electron microscopy, especially cryogenic transmission electron microscopy (cryo-TEM). By cryo-TEM, it was revealed that ionomer molecules formed rod-like aggregates macro-homogeneously in the solvent, and a similar morphology was observed in a carbon-particle-containing solvent. In contrast, ionomer aggregates in the catalyst ink containing platinum nanoparticles loaded on carbon particles were denser in the vicinity of the platinum-loaded carbon particles. That can be attributed to strong interaction between platinum nanoparticles and sulfonic acid groups in the ionomer. It also implies that a good understanding of ionomer morphology in the catalyst ink can play an important role in controlling the catalyst layer microstructure for reducing platinum loading.

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.

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

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.

Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

International Nuclear Information System (INIS)

González, J.; Chen, L.F.; Wang, J.A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J.L.

2016-01-01

Highlights: • Oxidative desulfurization of model diesel was tested in a biphasic system. • ODS activity was proportional to the V 5+ /(V 4+ + V 5+ ) values of the catalysts. • Lewis acidity was related to vanadium content and catalytic activity. • 99.9% DBT was oxidized using 25%V 2 O 5 /Ti-MCM-41 at 60 °C within 60 min. - Abstract: A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H 2 O 2 as oxidant. ODS activity was found to be proportional to the V 5+ /(V 4+ + V 5+ ) values of the catalysts, indicating that the surface vanadium pentoxide (V 2 O 5 ) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V 2 O 5 ) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V 2 O 5 /Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

Acidic ionic liquids for n-alkane isomerization in a liquid-liquid or slurry-phase reaction mode

Energy Technology Data Exchange (ETDEWEB)

Meyer, C.; Hager, V.; Geburtig, D.; Kohr, C.; Wasserscheid, P. [Erlangen-Nuernberg Univ. (Germany). Lehrstuhl fuer Chemische Reaktionstechnik; Haumann, M. [Chemical Reaction Engineering, FAU Busan Campus, Korea (Korea, Republic of)

2011-07-01

Highly acidic ionic liquid (IL) catalysts offer the opportunity to convert n-alkanes at very low reaction temperatures. The results of IL catalyzed isomerization and cracking reactions of pure n-octane are presented. Influence of IL composition, [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / H{sub 2}SO{sub 4} and [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / 1-chlorooctane, on catalyst activity and selectivities to branched alkanes was investigated. Acidic chloroaluminate IL catalysts form liquid-liquid biphasic systems with unpolar organic product mixtures. Thus, recycling of the acidic IL is enabled by simple phase separation in the liquid-liquid biphasic reaction mode or the IL can be immobilized on an inorganic support with a large specific surface area. These supported ionic liquid phase (SILP) catalysts offer the advantage to get a macroscopically heterogeneous system while still preserving all benefits of the homogeneous catalyst which can be used for the slurry-phase n-alkane isomerization. The interaction of the solid support and acidic IL influences strongly the catalytic activity. (orig.)

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

Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

Energy Technology Data Exchange (ETDEWEB)

Conrad Ingram; Mark Mitchell

2007-03-31

The addition of hydrothermally-aged zeolite Y precursor to an SBA-15 synthesis mixture under a mildly acidic condition resulted in the formation of a mesoporous aluminosilicate catalyst, AlSBA-15. The Al-SBA-15 mesoporous catalyst contains strong Br{umlt o}nsted acid sites and aluminum (Al) stabilized in a totally tetrahedral coordination. The physicochemical characteristics of the catalyst varied as a function of the synthesis conditions. The catalyst possessed surface areas ranging between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm, and pore volumes up 1.03 cm{sup 3}, which were comparable to the parent SBA-15 synthesized under similar conditions. Two wt % Al was present in the catalyst that was obtained from the reaction mixture that contained the highest Al content. The Al remained stable in totally tetrahedral coordination after calcination at a temperature of 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and the activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. In preparation for the final phase of the project, the catalyst was embedded into a psuedoboemite alumina (catapal B) matrix and then formed into pellets. In the final phase of the project, the pelletized catalyst is being evaluated for the conversion of a heavy petroleum feedstock to naphtha and middle distillates. This phase was significantly delayed during the past six months due to a serious malfunction of the fume hoods in the Clark Atlanta University's Research Center for Science and Technology, where the project is being conducted. The fume hood system was repaired and the catalyst evaluation is now underway.

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)

Treatment of infectious skin defects or ulcers with electrolyzed strong acid aqueous solution.

Science.gov (United States)

Sekiya, S; Ohmori, K; Harii, K

1997-01-01

A chronic ulcer with an infection such as methicillin-resistant Staphylococcus aureus is hard to heal. Plastic and reconstructive surgeons often encounter such chronic ulcers that are resistant to surgical or various conservative treatments. We applied conservative treatment using an electrolyzed strong acid aqueous solution and obtained satisfactory results. The lesion was washed with the solution or soaked in a bowl of the solution for approximately 20 min twice a day. Fresh electrolyzed strong acid aqueous solution is unstable and should be stored in a cool, dark site in a sealed bottle. It should be used within a week after it has been produced. Here we report on 15 cases of infectious ulcers that were treated by electrolyzed strong acid aqueous solution. Of these cases, 7 patients were healed, 3 were granulated, and in 5, infection subsided. In most cases the lesion became less reddish and less edematous. Discharge or foul odor from the lesion was decreased. Electrolyzed strong acid aqueous solution was especially effective for treating a chronic refractory ulcer combined with diabetes melitus or peripheral circulatory insufficiency. This clinically applied therapy of electrolyzed strong acid aqueous solution was found to be effective so that this new therapeutic technique for ulcer treatment can now be conveniently utilized.

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.)

Exfoliated Pd/HNb{sub 3}O{sub 8} nanosheet as highly efficient bifunctional catalyst for one-pot cascade reaction

Energy Technology Data Exchange (ETDEWEB)

Lee, Nahaeng; Chung, Young-Min, E-mail: ymchung@kunsan.ac.kr

2016-05-01

Graphical abstract: - Highlights: • Ultrathin and highly acidic HNb{sub 3}O{sub 8} nanosheet was prepared by exfoliation of layered niobium oxide. • Pd/HNb{sub 3}O{sub 8} nanosheet showed excellent catalytic performance for one-pot cascade reaction. • The reaction performance of Pd/HNb{sub 3}O{sub 8} nanosheet is 7.1 and 1.2 times higher than that of layered Pd/KNb{sub 3}O{sub 8} or Pd/HNb{sub 3}O{sub 8}, respectively. • Significant promoting effect of support acidity on the reaction performance was observed. - Abstract: Ultrathin two-dimensional metal oxide nanosheets have drawn attention as potential solid acid catalysts owing to their strong acidity, attributed to the bridged OH groups formed on the nanosheets. In this study, a new class of bifunctional acid–metal catalyst was realized by the deposition of Pd on layered niobium oxide (KNb{sub 3}O{sub 8} and HNb{sub 3}O{sub 8}) or its exfoliated nanosheet (Pd/HNb{sub 3}O{sub 8}-NS) and applied to one-pot cascade deacetalization and hydrogenation. It was found that the acid strength of the support exerted a large influence not only on the promotion of the first deacetalization step, but also on the acceleration of the subsequent hydrogenation step. Comparative experiments using a series of Pd/HZSM-5 catalysts with different acidities reconfirmed the crucial role of acid strength on hydrogenation. However, the superior catalytic activity of Pd/HNb{sub 3}O{sub 8}-NS for hydrogenation compared to that of Pd/HZSM-5 of similar acidity suggests a more efficient ensemble effect of the strong acid sites with the nearby metal sites on the nanosheet surface. Among the catalysts used, Pd/HNb{sub 3}O{sub 8}-NS showed the best catalytic performance for one-pot cascade reaction affording the desired product (benzyl alcohol) in approximately 92% yield, which was 7.1 and 1.2 times higher than that of layered Pd/KNb{sub 3}O{sub 8} or Pd/HNb{sub 3}O{sub 8}, respectively. The excellent catalytic performance of Pd/HNb{sub 3

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

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

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

Polyphosphoric acid supported on Ni0.5Zn0.5Fe2O4 nanoparticles as a magnetically-recoverable green catalyst for the synthesis of pyranopyrazoles

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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.

Facile and Low-Cost Preparation of Nb/Al Oxide Catalyst with High Performance for the Conversion of Kiwifruit Waste Residue to Levulinic Acid

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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.

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

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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.

Synthesis and characterization of MCM-41-supported nano zirconia catalysts

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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.

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.

The electrocatalytic properties of carbon supported PtRu/C nanoalloys in oxidation of small organic molecules: Comparison with Pt/C catalyst

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Lović Jelena D.

2012-01-01

Full Text Available The electrocatalytic activity of carbon supported PtRu/C catalysts, with different composition, toward the electrooxidation of methanol, CO and formic acid were examined in acid and alkaline solution at ambient temperature using thin-film rotating disk electrode (RDE method and compared with activity of Pt/C. The catalysts were characterized by XRD, AFM and STM techniques. XRD pattern revealed that PtRu-1/C catalyst is consisted of two structures e.g. Pt-Ru-fcc and Ru-hcp (the solid solution of Ru in Pt and the small amount of Ru or solid solution of Pt in Ru, as opposed to PtRu-2/C catalyst which is consisted of one structure mostly, Pt-Ru-fcc. According to STM images, PtRu as well as Pt, particles size were between 2 and 6 nm, which is in a good agreement with the mean particles size determined by XRD. To establish the activity and stability of the catalysts potentiodynamic and quasi steady-state measurements were performed. It was found that the activity of Pt and PtRu for CO and methanol oxidation is a strong function of pH of solution. The kinetics are much higher in alkaline than in acid solution and the difference between Pt/C and PtRu/C is much less pronounced in alkaline media. Results presented in this work indicate that activity of PtRu catalysts depends on catalyst composition, e.g. on Pt/Ru atomic ratio, as well as on alloying degree of catalysts. Comparison of CO, methanol and formic acid oxidation on PtRu-2/C, PtRu-1/C and Pt/C catalysts revealed that PtRu-2/C is the most active one. It was shown that the PtRu-2/C catalyst, due to fact that it is consisted of only one phase, with high alloying degree, through the bifunctional mechanism improved by electronic effect, achieve the activity two times higher related to PtRu-1/C in the oxidation of all organic molecules investigated, and about three times higher compared to Pt/C in the oxidation of methanol and CO, and five times higher in formic acid oxidation.

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

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.

Origin of Life and the Phosphate Transfer Catalyst

Science.gov (United States)

Piast, Radosław W.; Wieczorek, Rafał M.

2017-03-01

In this paper, we revisit several issues relevant to origin-of-life research and propose a Phosphate Transfer Catalyst hypothesis that furthers our understanding of some of the key events in prebiotic chemical evolution. In the Phosphate Transfer Catalyst hypothesis, we assume the existence of hypothetical metallopeptides with phosphate transfer activity that use abundant polyphosphates as both substrates and energy sources. Nonspecific catalysis by this phosphate transfer catalyst would provide a variety of different products such as phosphoryl amino acids, nucleosides, polyphosphate nucleotides, nucleic acids, and aminoacylated nucleic acids. Moreover, being an autocatalytic set and metabolic driver at the same time, it could possibly replicate itself and produce a collective system of two polymerases; a nucleic acid able to catalyze peptide bond formation and a peptide able to polymerize nucleic acids. The genetic code starts at first as a system that reduces the energy barrier by bringing substrates (2'/3' aminoacyl-nucleotides) together, an ancestral form of the catalysis performed by modern ribosomes.

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.

Selective Ring Opening of 1-Methylnaphthalene Over NiW-Supported Catalyst Using Dealuminated Beta Zeolite.

Science.gov (United States)

Kim, Eun-Sang; Lee, You-Jin; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

2016-02-01

Nanoporous Beta zeolite was dealuminated by weak acid treatment for reducing the acidity. Bi-functional catalysts were prepared using commercial Beta zeolites and the dealuminated zeolites for acidic function, NiW for metallic function. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction has been investigated using the prepared bi-functional catalysts with different acidity in fixed bed reaction system. The dealuminated Beta zeolites, which crystal structure and nanoporosity were maintained, showed the higher SiO2/Al2O3 ratio and smaller acidity than their original zeolite. NiW-supported catalyst using the dealuminated Beta zeolite with SiO2/Al203 mole ratio of 55 showed the highest performance for the selective ring opening. The acidity of catalyst seemed to play an important role as active sites for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. The acidity of Beta zeolite could be controlled by the acid treatment and the catalyst with the optimum acidity for the selective ring opening could be prepared.

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)

Hydrous titanium oxide-supported catalysts

International Nuclear Information System (INIS)

Dosch, R.G.; Stohl, F.V.; Richardson, J.T.

1990-01-01

Catalysts were prepared on hydrous titanium oxide (HTO) supports by ion exchange of an active metal for Na + ions incorporated in the HTO support during preparation by reaction with the parent Ti alkoxide. Strong active metal-HTO interactions as a result of the ion exchange reaction can require significantly different conditions for activation as compared to catalysts prepared by more widely used incipient wetness methods. The latter catalysts typically involve conversion or while the HTO catalysts require the alteration of electrostatic bonds between the metal and support with subsequent alteration of the support itself. In this paper, the authors discuss the activation, via sulfidation or reduction, of catalysts consisting of Co, Mo, or Ni-Mo dispersed on HTO supports by ion exchange. Correlations between the activation process and the hydrogenation, hydrodeoxygenation, and hydrodesulfurization activities of the catalysts are presented

Synthesis of MoVTeNb Oxide Catalysts with Tunable Particle Dimensions

DEFF Research Database (Denmark)

Kolenko, Yury V.; Zhang, Wei; d'Alnoncourt, Raoul Naumann

2011-01-01

Reliable procedures for the controlled synthesis of phase-pure MoVTeNb mixed oxides with M1 structure (ICSD 55097) and tunable crystal dimensions were developed to study the structure sensitivity of the selective oxidation of propane to acrylic acid. A series of powdered M1 catalysts...... catalysts were studied in the selective oxidation of propane to acrylic acid, revealing that active sites appear on the entire M1 surface and illustrating the high sensitivity of catalyst performance on the catalyst synthesis method....

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...

Biodiesel fuel production from waste cooking oil using radiation-grafted fibrous catalysts

Science.gov (United States)

Ueki, Yuji; Saiki, Seiichi; Hoshina, Hiroyuki; Seko, Noriaki

2018-02-01

Waste cooking oil, which can be used as a raw material for biodiesel fuel (BDF), contains two kinds of oil components: triglycerides (TGs) and free fatty acids (FFAs). Therefore, both alkaline-type and acid-type catalysts are needed to produce BDF from waste cooking oil. In this study, an alkaline-type grafted fibrous catalyst bearing OH- ions was synthesized by radiation-induced emulsion grafting of 4-chloromethylstyrene onto a polyethylene-coated polypropylene (PE/PP) nonwoven fabric, amination with trimethylamine, and further treatment with NaOH. Furthermore, an acid-type catalyst bearing H+ ions was synthesized by radiation-induced emulsion grafting of ethyl p-styrenesulfonate onto a PE/PP nonwoven fabric, saponification with NaOH, and protonation with HNO3. The OH- and H+ densities of the grafted fibrous catalysts were controlled by the grafting yield. The maximum OH- and H+ densities of the catalysts were 3.6 mmol-OH-/g-catalyst and 3.4 mmol-H+/g-catalyst, respectively. The performances of the catalysts were evaluated in the batchwise transesterification of TGs and ethanol, and the batchwise esterification of FFAs and ethanol. In both cases, TGs and FFAs were gradually converted into BDF. The mixed oil and four actual waste cooking oils, which contained both TGs and FFAs, were completely converted into BDF by sequential catalytic reactions with the acid-type grafted fibrous catalyst and then the alkaline-type grafted fibrous catalyst.

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

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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.

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.

Isobutane/2-butene alkylation over potential heterogeneous catalysts in a slurry reactor

Energy Technology Data Exchange (ETDEWEB)

Roervik, T.

1996-12-31

The trend towards more effective use of fossil fuels and reduced environmental pollution represents a major task of improvement within the refinery processes. The highly isomerized and high octane paraffins produced from isobutane and light olefins by alkylation fulfill all the requirements for reformulated gasoline. This doctoral thesis discusses new catalyst systems because of their potential in alkylation. A slurry reactor apparatus for solid-acid catalysed isobutane/butene alkylation was developed and used to investigate the performance of various heterogeneous catalysts. The selected materials were mainly zeolite types with faujasite structures. The samples were characterized by various methods before alkylation. In general, the order of decreasing catalyst activity after 3 h of reaction at 80{sup o}C was found to be: H-EMT >> H-FAU, dealuminated H-FAU >> NS.500, TA-Y, CeY-98 > Nafion-H. The order of decreasing alkylate selectivity of the catalysts was: H-EMT >> dealuminated H-FAU > H-FAU >> Nafion-H > CeY-98 > TA-Y > H-SAPO-37, NS.500. H-EMT was the most promising system for further development, also because of the very low formation of the undesirable isooctenes and a high selectivity towards isooctanes among the alkylates. A high density of accessible strong acid sites was found to be essential for a high alkylation activity and selectivity. Open structure, like hexagonal faujasite, was advantageous. The distribution of trimethylpentanes formed in zeolites was ascribed to pore restrictions as a major factor. The effect of operating conditions on catalyst performance was investigated statistically, and a high dilution of butene in the slurry reactor was found to be very important. 153 refs., 40 figs., 12 tabs.

Ethanolysis conversion of spent frying oils over aluminium, calcium-phosphate based bi-functional formulated catalysts. Catalytic activity assessment study

Energy Technology Data Exchange (ETDEWEB)

Al-Zaini, Essam O.; Chesterfield, Dean; Adesina, Adesoji A. [The Univ. of New South Wales, Sydney (Australia). Reactor Engineering and Technology Group; Olsen, John [The Univ. of New South Wales, Sydney (Australia). School of Mechanical and Manufacturing Engineering

2013-06-01

The current study compares the catalytic performance of two bi-functional solid catalysts for the transesterification of waste cooking vegetable oil in presence of bio-ethanol acyl-acceptor. The two catalysts were aluminum oxide and seashell-derived calcium oxide supported K{sub 3}PO{sub 4}. The catalytic activity of the produced catalyst samples were assessed and evaluated in terms of their textural and surface chemical properties. Evaluative runs showed that increased amounts of K{sub 3}PO{sub 4} have differently controlled the textural and surface chemical property of the finally synthesised catalyst samples. The behaviour revealed a strong correlation between the percentage yield of ethyl esters EEY% and acid-base site density and strength between the two types of catalysts. Possible leaching test of the catalysts was also used as a measure of performance and as a result, the optimum catalyst, on the basis of both ester yield and resistance to leaching was identified as the sample containing between 10 and 15wt% of K{sub 3}PO{sub 4} on AlO{sub 3} and CaO respectively. (orig.)

Anion-π Catalysts with Axial Chirality.

Science.gov (United States)

Wang, Chao; Matile, Stefan

2017-09-04

The idea of anion-π catalysis is to stabilize anionic transition states by anion-π interactions on aromatic surfaces. For asymmetric anion-π catalysis, π-acidic surfaces have been surrounded with stereogenic centers. This manuscript introduces the first anion-π catalysts that operate with axial chirality. Bifunctional catalysts with tertiary amine bases next to π-acidic naphthalenediimide planes are equipped with a bulky aromatic substituent in the imide position to produce separable atropisomers. The addition of malonic acid half thioesters to enolate acceptors is used for evaluation. In the presence of a chiral axis, the selective acceleration of the disfavored but relevant enolate addition was much better than with point chirality, and enantioselectivity could be observed for the first time for this reaction with small-molecule anion-π catalysts. Enantioselectivity increased with the π acidity of the π surface, whereas the addition of stereogenic centers around the aromatic plane did not cause further improvements. These results identify axial chirality of the active aromatic plane generated by atropisomerism as an attractive strategy for asymmetric anion-π catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface chemistry and catalytic properties of VO{sub X}/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

Energy Technology Data Exchange (ETDEWEB)

González, J. [ESIQIE, Instituto Politécnico Nacional, Av. Instituto Politécnico Nacional s/n, 07738 Col. Zacatenco, Mexico City (Mexico); Chen, L.F., E-mail: lchen@ipn.mx [ESIQIE, Instituto Politécnico Nacional, Av. Instituto Politécnico Nacional s/n, 07738 Col. Zacatenco, Mexico City (Mexico); Wang, J.A.; Manríquez, Ma.; Limas, R. [ESIQIE, Instituto Politécnico Nacional, Av. Instituto Politécnico Nacional s/n, 07738 Col. Zacatenco, Mexico City (Mexico); Schachat, P.; Navarrete, J. [Dirección de Investigación, Instituto Mexicano del Petróleo, Eje Lázaro Cárdenas 152, 07730 México D.F. (Mexico); Contreras, J.L. [Laboratorio de Catálisis y Polímeros, División de Ciencias Básicas e Ingeniería, Universidad Autónoma Metropolitana-A, Av. San Pablo No. 180, 02200 México D.F. (Mexico)

2016-08-30

Highlights: • Oxidative desulfurization of model diesel was tested in a biphasic system. • ODS activity was proportional to the V{sup 5+}/(V{sup 4+} + V{sup 5+}) values of the catalysts. • Lewis acidity was related to vanadium content and catalytic activity. • 99.9% DBT was oxidized using 25%V{sub 2}O{sub 5}/Ti-MCM-41 at 60 °C within 60 min. - Abstract: A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H{sub 2}O{sub 2} as oxidant. ODS activity was found to be proportional to the V{sup 5+}/(V{sup 4+} + V{sup 5+}) values of the catalysts, indicating that the surface vanadium pentoxide (V{sub 2}O{sub 5}) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V{sub 2}O{sub 5}) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V{sub 2}O{sub 5}/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

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

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

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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.

PREPARATION, CHARACTERIZATIONS AND MODIFICATION OF Ni-Pd/NATURAL ZEOLITE CATALYSTS

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Wega Trisunaryanti

2010-06-01

Full Text Available Preparation, and modification of Ni-Pd/natural zeolite as well as their characterizations had been carried out. The aim of this research for the fututure is to prepare the best characters catalyst for the conversion of waste plastics fraction to gasoline fraction (C5-C12 hydrocarbons. The preparation of catalysts was performed by reacting a natural zeolite with the precursor of Ni(NO32. 9H2O and PdCl2 in an ammonia solution (25%. The modifications were performed by varying the rasio of Ni/Pd loaded to the zeolite, whereas the Pd was previously loaded and total metal content was 1 wt.% based on the zeolite. The characterization of catalysts included determination of acidity gravimetrically by adsorption of ammonia or pyridine vapour  base method, metal content by Atomic Adsorption Spectrophotometer (AAS and X-ray Fluoresence (XRF and crystallinity by X-ray Diffraction (XRD. The treatment of catalysts using Etilene Diamine Tetra Acetic acid  (EDTA was performed to study the metal distribution on the outer or inner surface of the zeolite. The characterization results showed that the loading of metals to the zeolite increased its acidity and decreased its spesific surface area, however, did not defect its crystallnity.  The metals loaded on the zeolite were distributed inside the pore and at outer surface of the zeolite. For all catalyst samples, the acidities determined using ammonia were higher than those of pyridine, and the acidities determined before the EDTA treatment was lower than those after the treatment.  Metal contents of the zeolite before the EDTA treatment were higher than those after the treatment. The EDTA treatment enhanced the crystallinity of the sampel. The relationship between the metal rasio towards the acidity of the catalyst samples were in variation. Catalyst samples produced in this research have good characters, thus promisingly can be used for conversion process of waste plastics to gasoline fraction.    Keywords

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

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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.

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.

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.

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....

Silica sulfuric acid: a reusable solid catalyst for one pot synthesis of densely substituted pyrrole-fused isocoumarins under solvent-free conditions

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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.

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

KAUST Repository

van der Voort, Pascal

2017-11-08

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

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

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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.

Pt Nanostructures/N-Doped Carbon hybrid, an Efficient Catalyst for Hydrogen Evolution/Oxidation Reactions: Enhancing its Base Media Activity through Bifunctionality of the Catalyst.

Science.gov (United States)

Barman, Sudip; Kundu, Manas; Bhowmik, Tanmay; Mishra, Ranjit

2018-06-04

Design and synthesis of active catalyst for HER/HOR are important for the development of hydrogen based renewable technologies. We report synthesis of Pt nanostructures-N-doped carbon hybrid (Pt-(PtO2)-NSs/C) for HER/HOR applications. The HER activity of this Pt-(PtOx)-NSs/C catalyst is 4 and 6.5 times better than commercial Pt/C in acid and base. The catalyst exhibits a current density of 10 mA/cm2 at overpotentials of 5 and 51 mV with tafel slopes of 29 and 64mV/dec in in 0.5 M H2SO4 and 0.5 M KOH. This catalyst also showed superior HOR activity at all pH values. The HER/HOR activity of Pt-(PtOx)-NSs/C and PtOx-free Pt-Nanostructures/C (PtNSs/C) catalysts are comparable in acid. The presence of PtOx in Pt-(PtOx)-NSs/C makes this Pt-catalyst more HER/HOR active in base media. The activity of Pt-(PtOx)NSs/C catalyst is 5 fold higher than that of PtNSs/C catalyst in basic medium although their activity is comparable in acid. Hydrogen binding energy and oxophilicity are the two equivalent descriptors for HER/HOR in basic media. We propose a bi-functional mechanism for the enhanced alkaline HER/HOR activity of Pt(PtOx)-NSs/C catalyst. In bi-functional Pt-(PtOx)-NSs/C catalyst, PtOx provide an active site for OH- adsorption to form OHads which reacts with hydrogen intermediate (Hads), present at neighbouring Pt sites to form H2O leading to enhancement of HOR activity in basic medium This work may provide opportunity to develop catalysts for various renewable energy technologies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal-mediated aminocatalysis provides mild conditions: Enantioselective Michael addition mediated by primary amino catalysts and alkali-metal ions

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Matthias Leven

2013-01-01

Full Text Available Four catalysts based on new amides of chiral 1,2-diamines and 2-sulfobenzoic acid have been developed. The alkali-metal salts of these betaine-like amides are able to form imines with enones, which are activated by Lewis acid interaction for nucleophilic attack by 4-hydroxycoumarin. The addition of 4-hydroxycoumarin to enones gives ee’s up to 83% and almost quantitative yields in many cases. This novel type of catalysis provides an effective alternative to conventional primary amino catalysis were strong acid additives are essential components.

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.

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.

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,

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)

Influence of mo-doping on VPO catalyst for partial oxidation of Ethane

International Nuclear Information System (INIS)

Fakeeha, A. H.; Soliman, M. A.; Alwahabi, S. M; Fahmy, Y. M; Ibrahim, A. A.

2005-01-01

Six MoVPO catalysts were prepared with Mo/V ratios of 0.0, 0.05, 0.1, 0.2, 0.3, 0.5 and P/V of 1.15 for all catalyst, using an isobutanol-benzylacohol solvent. Molydenum was introduced to the VPO catalyst by impregnation. XRD, ICP, BET and SEM were used for the catalyst characterization. A maximum acetic acid yield of 1.1% was obtained using contact time of 3.6 sec. at 573 K and 1360 kPa using VPO catalyst with Mo/V ratio of 0.2 calcined at 723 K under nitrogen flow. At these conditions the ethane conversion was 2.8% and acetic acid and ethylene selectivities were about equal at 37%. Mo has the effect of decreasing the ethane conversion and increasing acetic acid selectively with the initial increase of Mo/V ratio then the selectivity drop to zero at Mo/V ratio then the selectivity drop to zero at Mo/V=o.5. It was found that exposing the catalyst to a reactant mixture lean in ethane at elevated temperature overnight before starting the reaction resulted in an increase in acetic acid selectivity. (author)

Uniformly active phase loaded selective catalytic reduction catalysts (V{sub 2}O{sub 5}/TNTs) with superior alkaline resistance performance

Energy Technology Data Exchange (ETDEWEB)

Wang, Haiqiang; Wang, Penglu [Key Laboratory of Environment Remediation and Ecological Health, Ministry of Education, College of Environmental & Resources Science, Zhejiang University, 310058 Hangzhou (China); Zhejiang Provincial Engineering Research Center of Industrial Boiler & Furnace Flue Gas Pollution Control, Hangzhou 310027 (China); Chen, Xiongbo [South China Institute of Environmental Sciences, Ministry of Environmental Protection, Guangzhou 510655 (China); Wu, Zhongbiao, E-mail: zbwu@zju.edu.cn [Key Laboratory of Environment Remediation and Ecological Health, Ministry of Education, College of Environmental & Resources Science, Zhejiang University, 310058 Hangzhou (China); Zhejiang Provincial Engineering Research Center of Industrial Boiler & Furnace Flue Gas Pollution Control, Hangzhou 310027 (China)

2017-02-15

Highlights: • VOSO{sub 4} exhibited better synergistic effect with titanate nanotubes than NH{sub 4}VO{sub 3}. • Ion-exchange reaction occurs between VOSO{sub 4} and titanate nanotubes. • Ion-exchange resulting in uniformly vanadium distribution on titanate nanotubes. • VOSO{sub 4}-based catalyst exhibited impressive SCR activity and alkaline resistance. - Abstract: In this work, protonated titanate nanotubes was performed as a potential useful support and different vanadium precursors (NH{sub 4}VO{sub 3} and VOSO{sub 4}) were used to synthesize deNO{sub x} catalysts. The results showed that VOSO{sub 4} exhibited better synergistic effect with titanate nanotubes than NH{sub 4}VO{sub 3}, which was caused by the ion-exchange reaction. Then high loading content of vanadium, uniformly active phase distribution, better dispersion of vanadium, more acid sites, better V{sup 5+}/V{sup 4+} redox cycles and superior oxygen mobility were achieved. Besides, VOSO{sub 4}-based titanate nanotubes catalysts also showed enhanced alkaline resistance than particles (P25) based catalysts. It was strongly associated with its abundant acid sites, large surface area, flexible redox cycles and oxygen transfer ability. For the loading on protonated titanate nanotubes, active metal with cation groups was better precursors than anion ones. V{sub 2}O{sub 5}/TNTs catalyst was a promising substitute for the commercial vanadium catalysts and the work conducted herein provided a useful idea to design uniformly active phase loaded catalyst.

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.

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