Catalysts

32 pages, 886 KB

Open AccessReview

Catalytic Technologies for Biodiesel Fuel Production and Utilization of Glycerol: A Review

by Le Tu Thanh¹, Kenji Okitsu^2,*, Luu Van Boi³ and Yasuaki Maeda^1,*

¹ Research Organization for University–Community Collaborations, Osaka Prefecture University, 1-2 Gakuen-cho, Naka-ku, Sakai 599-8531, Japan

² Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Japan

³ Faculty of Chemistry, Vietnam National University, 19 Le Thanh Tong St., Hanoi, Vietnam

Catalysts 2012, 2(1), 191-222; https://doi.org/10.3390/catal2010191 - 22 Mar 2012

Cited by 198 | Viewed by 19364

Abstract

More than 10 million tons of biodiesel fuel (BDF) have been produced in the world from the transesterification of vegetable oil with methanol by using acid catalysts (sulfuric acid, H₂SO₄), alkaline catalysts (sodium hydroxide, NaOH or potassium hydroxide, KOH), [...] Read more.

More than 10 million tons of biodiesel fuel (BDF) have been produced in the world from the transesterification of vegetable oil with methanol by using acid catalysts (sulfuric acid, H₂SO₄), alkaline catalysts (sodium hydroxide, NaOH or potassium hydroxide, KOH), solid catalysts and enzymes. Unfortunately, the price of BDF is still more expensive than that of petro diesel fuel due to the lack of a suitable raw material oil. Here, we review the best selection of BDF production systems including raw materials, catalysts and production technologies. In addition, glycerol formed as a by-product needs to be converted to useful chemicals to reduce the amount of glycerol waste. With this in mind, we have also reviewed some recent studies on the utilization of glycerol. Full article

(This article belongs to the Special Issue Catalysts for Biomass Conversion)

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20 pages, 408 KB

Open AccessArticle

Production of Bio-Hydrogenated Diesel by Hydrotreatment of High-Acid-Value Waste Cooking Oil over Ruthenium Catalyst Supported on Al-Polyoxocation-Pillared Montmorillonite

by Yanyong Liu^*

, Rogelio Sotelo-Boyás^†, Kazuhisa Murata, Tomoaki Minowa and Kinya Sakanishi

¹ Biomass Technology Research Center, National Institute of Advanced Industrial Science and Technology, AIST Tsukuba Center 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan

^† Current address: Instituto Politecnico Nacional, Mexico ESIQIE, Mexico D.F. 07738, Mexico

Catalysts 2012, 2(1), 171-190; https://doi.org/10.3390/catal2010171 - 14 Feb 2012

Cited by 57 | Viewed by 12229

Abstract

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, [...] Read more.

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-containing compounds. Full article

(This article belongs to the Special Issue Catalysts for Biomass Conversion)

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32 pages, 514 KB

Open AccessReview

Oxidation Catalysts for Elemental Mercury in Flue Gases—A Review

by Beatrice-Andreea Dranga^1,2,*, Liliana Lazar¹ and Heinz Koeser^2,*

¹ Department of Chemical Engineering, Faculty of Chemical Engineering and Environmental Protection, Gheorghe Asachi Technical University of Iasi, 73 Prof. D. Mangeron Street, Iasi 700050, Romania

² Environmental Protection Technology, Otto-von-Guericke University Magdeburg, c/o Engineering Sciences Centre, Martin-Luther University Halle-Wittenberg, Halle (Saale) D-06099, Germany

Catalysts 2012, 2(1), 139-170; https://doi.org/10.3390/catal2010139 - 13 Feb 2012

Cited by 93 | Viewed by 14574

Abstract

The removal of mercury from flue gases in scrubbers is greatly facilitated if the mercury is present as water-soluble oxidized species. Therefore, increased mercury oxidation upstream of scrubber devices will improve overall mercury removal. For this purpose heterogeneous catalysts have recently attracted a [...] Read more.

The removal of mercury from flue gases in scrubbers is greatly facilitated if the mercury is present as water-soluble oxidized species. Therefore, increased mercury oxidation upstream of scrubber devices will improve overall mercury removal. For this purpose heterogeneous catalysts have recently attracted a great deal of interest. Selective catalytic reduction (SCR), noble metal and transition metal oxide based catalysts have been investigated at both the laboratory and plant scale with this objective. A review article published in 2006 covers the progress in the elemental mercury (Hg^el) catalytic oxidation area. This paper brings the review in this area up to date. To this end, 110 papers including several reports and patents are reviewed. For each type of catalyst the possible mechanisms as well as the effect of flue gas components on activity and stability are examined. Advantages and main problems are analyzed. The possible future directions of catalyst development in this environmental research area are outlined. Full article

(This article belongs to the Special Issue Feature Papers)

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18 pages, 494 KB

Open AccessArticle

Influence of Gold on Ce-Zr-Co Fluorite-Type Mixed Oxide Catalysts for Ethanol Steam Reforming

by Julio Cesar Vargas¹, Svetlana Ivanova², Sébastien Thomas³, Anne-Cécile Roger⁴ and Véronique Pitchon^4,*

¹ Departamento de Ingeniería Química y Ambiental, Universidad Nacional de Colombia, Ciudad Universitaria, Avenida Carrera 30 No. 45-03, Bogotá Edificio 453, Colombia

² Instituto de Ciencia de Materiales de Sevilla, Centro Mixto Universidad de Sevilla—CSIC, Avenida Américo Vespucio, N° 49, Isla de la Cartuja, Sevilla 41092, Spain

³ Laboratoire Catalyse et Spectrochimie, ENSICAEN, Université de Caen, CNRS, 6 Boulevard Maréchal Juin, Caen Cedex 14050, France

⁴ Laboratoire des Matériaux, Surfaces et Procédés pour la Catalyse, ECPM, Université de Strasbourg, CNRS, 25 rue Becquerel, Strasbourg Cedex 2-67087, France

Catalysts 2012, 2(1), 121-138; https://doi.org/10.3390/catal2010121 - 3 Feb 2012

Cited by 12 | Viewed by 9449

Abstract

The effect of gold presence on carbon monoxide oxidation and ethanol steam reforming catalytic behavior of two Ce-Zr-Co mixed oxides catalysts with a constant Co charge and different Ce/Zr ratios was investigated. The Ce-Zr-Co mixed oxides were obtained by the pseudo sol-gel like [...] Read more.

The effect of gold presence on carbon monoxide oxidation and ethanol steam reforming catalytic behavior of two Ce-Zr-Co mixed oxides catalysts with a constant Co charge and different Ce/Zr ratios was investigated. The Ce-Zr-Co mixed oxides were obtained by the pseudo sol-gel like method, based on metallic propionates polymerization and thermal decomposition, whereas the gold-supported Ce-Zr-Co mixed oxides catalysts were prepared using the direct anionic exchange. The catalysts were characterized using XRD, TPR, and EDXS-TEM. The presence of Au in doped Ce-Zr-Co oxide catalyst decreases the temperature necessary to reduce the cobalt and the cerium loaded in the catalyst and favors a different reaction pathway, improving the acetaldehyde route by ethanol dehydrogenation, instead of the ethylene route by ethanol dehydration or methane re-adsorption, thus increasing the catalytic activity and selectivity into hydrogen. Full article

(This article belongs to the Special Issue Gold Catalysts)

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20 pages, 970 KB

Open AccessReview

Monometallic Supported Gold Catalysts in Organic Transformations: Ring Making and Ring Breaking

by Krisztián Csankó¹, Pál Sipos² and István Pálinkó^1,*

¹ Department of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged H-6720, Hungary

² Department of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 7, Szeged H-6720, Hungary

Catalysts 2012, 2(1), 101-120; https://doi.org/10.3390/catal2010101 - 1 Feb 2012

Cited by 4 | Viewed by 9253

Abstract

Supported gold catalysts are highly active in oxidation reactions. Beside the most frequently studied CO oxidation, they are readily applied in the epoxidation of more or less complex olefinic compounds using air or oxygen directly or other oxidants like peroxides of various kinds. [...] Read more.

Supported gold catalysts are highly active in oxidation reactions. Beside the most frequently studied CO oxidation, they are readily applied in the epoxidation of more or less complex olefinic compounds using air or oxygen directly or other oxidants like peroxides of various kinds. Less frequently though, the reverse reaction, ring opening with single or double C–O scission is also investigated. These and other ring making and breaking reactions are reviewed, and the catalytic roles of gold species are described. Full article

(This article belongs to the Special Issue Gold Catalysts)

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16 pages, 354 KB

Open AccessArticle

Hydrogenation of Anthracene in Supercritical Carbon Dioxide Solvent Using Ni Supported on Hβ-Zeolite Catalyst

by Endalkachew Sahle-Demessie^*, Venu Gopal Devulapelli and Ashraf Aly Hassan

U.S. Environmental Protection Agency, Office of Research & Development, National Risk Management Research Laboratory, 26 West, Martin Luther King Dr., Cincinnati, OH 45268, USA

Catalysts 2012, 2(1), 85-100; https://doi.org/10.3390/catal2010085 - 30 Jan 2012

Cited by 32 | Viewed by 13850

Abstract

Catalytic hydrogenation of anthracene was studied over Ni supported on Hβ-zeolite catalyst under supercritical carbon dioxide (sc-CO₂) solvent. Hydrogenation of anthracene in sc-CO₂ yielded 100% conversion at 100 °C, which is attributed to the reduced mass transfer limitations, and increased [...] Read more.

Catalytic hydrogenation of anthracene was studied over Ni supported on Hβ-zeolite catalyst under supercritical carbon dioxide (sc-CO₂) solvent. Hydrogenation of anthracene in sc-CO₂ yielded 100% conversion at 100 °C, which is attributed to the reduced mass transfer limitations, and increased solubility of H₂ and substrate in the reaction medium. The total pressure of 7 MPa was found to be optimum for high selectivity of octahydroanthracene (OHA). The conversion and selectivity for OHA increased with an increase in H₂ partial pressure, which is attributed to higher concentration of hydrogen atoms at higher H₂ pressures. The selectivity reduced the pressure below 7 MPa because of enhanced desorption of the tetrahydro-molecules and intermediates from Ni active sites, due to higher solubility of the surface species in sc-CO₂. The selectivity of OHA increased with the increase in catalyst weight and reaction time. The rate of hydrogenation of anthracene was compared with that found for napthalene and phenanthrene. The use of acetonitrile as co-solvent or expanded liquid with CO₂ decreased the catalytic activity. Full article

(This article belongs to the Special Issue Feature Papers)

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17 pages, 1507 KB

Open AccessArticle

One-Pot Liquid-Phase Catalytic Conversion of Ethanol to 1-Butanol over Aluminium Oxide—The Effect of the Active Metal on the Selectivity

by Toni Riittonen^1,*, Esa Toukoniitty^1,2, Dipak Kumar Madnani¹, Anne-Riikka Leino³, Krisztian Kordas³, Maria Szabo⁴, Andras Sapi⁴, Kalle Arve¹, Johan Wärnå¹ and Jyri-Pekka Mikkola^1,5

¹ Laboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre, Åbo Akademi University, Turku-Åbo FI-20500, Finland

² Helsinki Metropolia University of Applied Sciences, P.O. Box 4000 (Bulevardi 31), Metropolia FI-00079, Finland

³ Microelectronics and Materials Physics Laboratories, Department of Electrical and Information Engineering, University of Oulu, P.O. Box 4500, FI-90014, Finland

⁴ Applied and Environmental Chemistry Department, University of Szeged, Szeged 6723, Rerrich Béla tér 1, Hungary

⁵ Department of Chemistry, Technical Chemistry, Chemical-Biological Center, Umeå University, Umeå 90187, Sweden

Catalysts 2012, 2(1), 68-84; https://doi.org/10.3390/catal2010068 - 13 Jan 2012

Cited by 141 | Viewed by 19952

Abstract

Direct catalytic valorization of bioethanol to 1-butanol over different alumina supported catalysts was studied. Thirteen (13) heterogeneous catalysts were screened in search for the optimal material composition for direct one-pot conversion of ethanol to 1-butanol. For the most promising catalyst, a 25% ethanol [...] Read more.

Direct catalytic valorization of bioethanol to 1-butanol over different alumina supported catalysts was studied. Thirteen (13) heterogeneous catalysts were screened in search for the optimal material composition for direct one-pot conversion of ethanol to 1-butanol. For the most promising catalyst, a 25% ethanol conversion with 80% selectivity (among liquid carbon products) to 1-butanol could be reached at 250 °C. Additionally, the reaction kinetics and mechanisms were further investigated upon use of the most suitable catalyst candidate. Full article

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12 pages, 335 KB

Open AccessArticle

Hydrogen Evolution from Napiergrass by the Combination of Biological Treatment and a Pt-Loaded TiO₂-Photocatalytic Reaction

by Tsutomu Shiragami¹, Takayuki Tomo¹, Hikaru Tsumagari¹, Yasuyuki Ishii² and Masahide Yasuda^1,*

¹ Department of Applied Chemistry, Faculty of Engineering, University of Miyazaki, Gakuen-Kibanadai Nishi, Miyazaki 889-2192, Japan

² Department of Biological Production and Environmental Science, Faculty of Agriculture, University of Miyazaki, Gakuen-Kibanadai Nishi, Miyazaki 889-219, Japan

Catalysts 2012, 2(1), 56-67; https://doi.org/10.3390/catal2010056 - 22 Dec 2011

Cited by 12 | Viewed by 7028

Abstract

Ethanol and pentose were produced from lignocellulosic napiergrass by the simultaneous saccharification and fermentation process (SSF) using hydrolytic enzyme and S. Cerevisiae. After the ethanol was removed, the pentose solution was subjected to photocatalytic hydrogen evolution with Pt-loaded TiO₂ under UV-irradiation. [...] Read more.

Ethanol and pentose were produced from lignocellulosic napiergrass by the simultaneous saccharification and fermentation process (SSF) using hydrolytic enzyme and S. Cerevisiae. After the ethanol was removed, the pentose solution was subjected to photocatalytic hydrogen evolution with Pt-loaded TiO₂ under UV-irradiation. This process converted 100 g of napiergrass into 12.3 g of ethanol and 1.76 g of hydrogen whose total combustion energy of (∆H) was 615 kJ. This was close to the ∆H (639 kJ) of the pentose (13.6 g) and hexose (27.4 g) obtained by the cellulose-saccharification of 100 g of napiergrass. Full article

(This article belongs to the Special Issue Catalysts for Biomass Conversion)

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18 pages, 1072 KB

Open AccessArticle

The Influence of Base Metal (M) Oxidation State in Au-M-O/TiO₂ Systems on Their Catalytic Activity in Carbon Monoxide Oxidation

by Jan Mizera, Nika Spiridis

, Robert P. Socha

, Małgorzata Zimowska, Ryszard Grabowski^*, Katarzyna Samson and Józef Korecki

Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Niezapominajek 8, Cracow 30-239, Poland

Catalysts 2012, 2(1), 38-55; https://doi.org/10.3390/catal2010038 - 22 Dec 2011

Cited by 8 | Viewed by 9012

Abstract

Base metal promoted gold/titania catalysts were synthesized, characterized and tested in CO oxidation reaction. Catalysts containing dopant metals in higher oxidation states exhibited higher activity than catalysts containing dopants in reduced states. The activity of fresh catalysts promoted by Cu, Fe and Ni [...] Read more.

Base metal promoted gold/titania catalysts were synthesized, characterized and tested in CO oxidation reaction. Catalysts containing dopant metals in higher oxidation states exhibited higher activity than catalysts containing dopants in reduced states. The activity of fresh catalysts promoted by Cu, Fe and Ni was similar to the unpromoted one, but treatment in reducing and oxidizing atmospheres revealed the supremacy of the copper promoted catalyst. The sequential deposition method proved to be better than the co-deposition—precipitation method. An attempt to explain these differences using XPS, FTIR and H₂ TPR was performed. Full article

(This article belongs to the Special Issue Gold Catalysts)

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14 pages, 1600 KB

Open AccessReview

The Art of Manufacturing Gold Catalysts

by Laura Prati^* and Alberto Villa

Dipartimento di Chimica Inorganica Metallorganica e Analitica L.Malatesta, Università degli Studi di Milano, via Venezian 21, Milano 20133, Italy

Catalysts 2012, 2(1), 24-37; https://doi.org/10.3390/catal2010024 - 21 Dec 2011

Cited by 56 | Viewed by 10386

Abstract

Gold has been considered as an active catalyst only when suitable techniques of preparation provided high metal dispersion. A comprehensive survey of the different methods now available for preparing active gold catalysts is reported with particular attention to the role of the supporting [...] Read more.

Gold has been considered as an active catalyst only when suitable techniques of preparation provided high metal dispersion. A comprehensive survey of the different methods now available for preparing active gold catalysts is reported with particular attention to the role of the supporting material in determining catalyst characteristics. Full article

(This article belongs to the Special Issue Gold Catalysts)

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23 pages, 1617 KB

Open AccessArticle

Gold/Iron Carbonyl Clusters for Tailored Au/FeO_x Supported Catalysts

by Rosa Bonelli¹, Stefano Zacchini²

and Stefania Albonetti^1,*

¹ Dipartimento di Chimica Industriale e dei Materiali, Università di Bologna, Viale Risorgimento 4, Bologna 40136, Italy

² Dipartimento di Chimica Fisica ed Inorganica, Università di Bologna, Viale Risorgimento 4, Bologna 40136, Italy

Catalysts 2012, 2(1), 1-23; https://doi.org/10.3390/catal2010001 - 21 Dec 2011

Cited by 19 | Viewed by 8087

Abstract

A novel preparation method was developed for the preparation of gold/iron oxide supported catalysts using the bimetallic carbonyl cluster salts [NEt₄]₄[Au₄Fe₄(CO)₁₆] and [NEt₄][AuFe₄(CO)₁₆] as precursors of highly [...] Read more.

A novel preparation method was developed for the preparation of gold/iron oxide supported catalysts using the bimetallic carbonyl cluster salts [NEt₄]₄[Au₄Fe₄(CO)₁₆] and [NEt₄][AuFe₄(CO)₁₆] as precursors of highly dispersed nanoparticles over different supports. A series of catalysts with different metal loadings were prepared and tested in the complete oxidation of dichlorobenzene, toluene, methanol and in the preferential oxidation of CO in the presence of H₂ (PROX) as model reactions. The characterization by BET, XRD, TEM, H₂-TPR, ICP-AES and XPS point out the way the nature of the precursors and the thermal treatment conditions affected the dispersion of the active phase and their catalytic activity in the studied reactions. Full article

(This article belongs to the Special Issue Gold Catalysts)

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Catalysts, Volume 2, Issue 1 (March 2012) – 11 articles , Pages 1-222

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