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Catalysis of Biomass-Derived Molecules
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Catalysis of Biomass-Derived Molecules

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Biomass Catalysis".

Deadline for manuscript submissions: closed (31 July 2017) | Viewed by 47991

Special Issue Editor

Prof. Dr. Christophe Len

E-Mail Website
Guest Editor
1. Sorbonne Universités, Université de Technologie de Compiegne, F-60203 Compiegne, France
2. Chimie ParisTech, CNRS, PSL University, F-75005 Paris, France
Interests: fine chemistry from natural substances: carbohydrates, cyclodextrins, nucleosides, lipids; chemistry and processes for the sustainable development; organic chemistry in green solvents; homogeneous, heterogeneous, and micellar catalysis; continuous flow applied to organic chemistry; organic chemistry under microwave activation
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The new challenges of the 21st century are important for society. Indeed, future generations will face several dilemmas: (i) the decreasing of resources, food and water associated with an increasing population; (ii) decreasing fossil fuel resources combined with increasing energy demand. In this perspective, the concept of biorefineries and the development of renewable resources, such as biomass and waste, are considered as promising alternatives to replace the products issued from fossil resources. From the biomass (lignocellulose, hemicellulose, oil, etc.) and in accordance with the principles of green chemistry and sustainable development, the production of molecule platforms (furfural, hydroxymethylfurfural, glycerol, etc.) allows interest in the industrial sector in the field of polymers, energy materials, and so on.

The aim of this Special Issue is to cover promising recent research and novel trends in the field of (i) novel catalytic reactions (homogeneous, heterogeneous, and enzymatic, as well as their combinations) applied to bio-based compounds or using bio-based reagents, either in a sequential way or in a one-pot combined synthesis; (ii) novel catalytic reactions (homogeneous, heterogeneous and enzymatic as well as their combinations) using green solvents (e.g., water, ionic liquids, deep eutectic, critical fluids, etc.); and (iii) new ambitious technologies using flow chemistry, enzymes, microwaves, microreactors, nanocatalysts, and, more remarkably, novel combinations of these technologies.

Prof. Dr. Christophe Len
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • biomass
  • green chemistry
  • chemical catalysis
  • enzymatic catalysis
  • alternative technologies
  • microwave
  • sonochemistry
  • continuous flow
  • green solvent

Published Papers (7 papers)

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Research

2151 KiB  
Article
Cross-Aldol Condensation of Acetone and n-Butanol into Aliphatic Ketones over Supported Cu Catalysts on Ceria-Zirconia
by Minseok Kim, Jongha Park, Hari Prasad Reddy Kannapu and Young-Woong Suh
Catalysts 2017, 7(9), 249; https://doi.org/10.3390/catal7090249 - 24 Aug 2017
Cited by 18 | Viewed by 9164
Abstract
A long-chain hydrocarbon biofuel of jet fuel range can be produced via aldol condensation of fermented products such as acetone and alcohols over the catalysts containing both metallic sites for the dehydrogenation of alcohols and basic sites for the condensation reaction. However, an [...] Read more.
A long-chain hydrocarbon biofuel of jet fuel range can be produced via aldol condensation of fermented products such as acetone and alcohols over the catalysts containing both metallic sites for the dehydrogenation of alcohols and basic sites for the condensation reaction. However, an efficient catalyst system has not been studied widely yet the route is promising for biofuel production. In this work, Cu catalysts supported on ceria-zirconia (Cu/xCeZr) were prepared using coprecipitated CexZr1-xO2 supports with different Ce/Zr ratios for the cross-aldol condensation of acetone and n-butanol into mono- and di-alkylated aliphatic ketones, 2-heptanone and 6-undecanone. The acetone conversion and 6-undecanone selectivity increased with specific Cu surface area due to formation of the dehydrogenation product butyraldehyde at a higher concentration. The total yield of cross-aldol condensation products was strongly dependent on a combination of Cu sites and basic sites. This was confirmed by the results in the reaction between acetone and butyraldehyde over supported Cu catalysts that additionally examined the adsorbed acyl species on Cu surface taking part in the aldol condensation reaction. The best catalytic performance was achieved with Cu/0.8CeZr showing the largest Cu surface and the highest base site density among Cu/xCeZr catalysts. While the activity of Cu/0.8CeZ was comparable to or a little higher than that of Cu/MgO, the former catalyst was more stable than the latter suffering from the transformation of MgO to Mg(OH)2 by the reaction. Consequently, it is suggested that Cu supported on ceria-zirconia of ceria rich contains such a dual function that it can efficiently catalyze the cross-aldol condensation of acetone and n-butanol. Full article
(This article belongs to the Special Issue Catalysis of Biomass-Derived Molecules)
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2736 KiB  
Article
Facile, One-Pot, Two-Step, Strategy for the Production of Potential Bio-Diesel Candidates from Fructose
by Guo Qiu, Xincheng Wang, Chongpin Huang, Yingxia Li and Biaohua Chen
Catalysts 2017, 7(8), 237; https://doi.org/10.3390/catal7080237 - 17 Aug 2017
Cited by 10 | Viewed by 4552
Abstract
The production of bio-diesel fuels from carbohydrates is a promising alternative to fossil fuels with regard to the growing severity of the environmental problem and energy crisis. Potential bio-diesel candidates or additives, such as 5-(hydroxymethyl)-2-(dimethoxymethyl) furan (HDMF), 2-(dimethoxymethyl)-5-(methoxymethyl) furan (DMMF), and 5-(methoxymethyl)-2-furaldehyde (MMF) [...] Read more.
The production of bio-diesel fuels from carbohydrates is a promising alternative to fossil fuels with regard to the growing severity of the environmental problem and energy crisis. Potential bio-diesel candidates or additives, such as 5-(hydroxymethyl)-2-(dimethoxymethyl) furan (HDMF), 2-(dimethoxymethyl)-5-(methoxymethyl) furan (DMMF), and 5-(methoxymethyl)-2-furaldehyde (MMF) could be produced from the alcoholic solutions of both 5-HMF and fructose in the presence of solid acid catalysts. In the present study, a readily prepared, silica, gel-supported nitric acid (SiO2-HNO3) catalyst was found to be exceptionally reactive for the production of HDMF from fructose. A DMSO-methanol biphasic solvent system was developed and HDMF, DMMF, and MMF were observed at 150 °C, with maximum yields of 34%, 34%, and 25%, respectively. Meanwhile, a maximum HDMF yield of 77% was obtained from 5-HMF in methanol. Moreover, a sequential, one-pot, two-step dehydration/acetalization process, involving the dehydration of fructose to 5-HMF in dimethylsulfoxide (DMSO) at 150 °C, and followed by adding a certain amount of methanol to react with the formed 5-HMF to HDMF at 100 °C, was developed to promote the yield of HDMF. The optimum yield of HDMF reached 70% with the complete conversion of fructose. The reaction mechanisms of dehydration and acetalization have been proposed for the conversion of 5-HMF to HDMF. The two-step design allows for facile catalyst recycling while supplying as a promising method for the production of biodiesel from complex carbohydrates. Full article
(This article belongs to the Special Issue Catalysis of Biomass-Derived Molecules)
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3199 KiB  
Article
Conversion of Cellulose to Lactic Acid by Using ZrO2–Al2O3 Catalysts
by Panya Wattanapaphawong, Osamu Sato, Koichi Sato, Naoki Mimura, Prasert Reubroycharoen and Aritomo Yamaguchi
Catalysts 2017, 7(7), 221; https://doi.org/10.3390/catal7070221 - 21 Jul 2017
Cited by 27 | Viewed by 6482
Abstract
Lactic acid has a wide range of applications in many industries, both as an ingredient and as an intermediate. Here, we investigated the catalytic conversion of cellulose to lactic acid by using heterogeneous mixed-oxide catalysts containing ZrO2. Although pure ZrO2 [...] Read more.
Lactic acid has a wide range of applications in many industries, both as an ingredient and as an intermediate. Here, we investigated the catalytic conversion of cellulose to lactic acid by using heterogeneous mixed-oxide catalysts containing ZrO2. Although pure ZrO2 has catalytic activity for the conversion of cellulose to lactic acid, the yield of lactic acid obtained is not satisfactory. In contrast, a series of ZrO2–Al2O3 catalysts containing various percentages of ZrO2 provided higher yields of lactic acid. The ZrO2–Al2O3 catalysts had more Lewis acid sites and far fewer base sites than ZrO2. This suggests that the Lewis acid sites on ZrO2–Al2O3 catalysts are more important than the base sites for the conversion of cellulose to lactic acid. Full article
(This article belongs to the Special Issue Catalysis of Biomass-Derived Molecules)
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1414 KiB  
Article
Insights into the Metal Salt Catalyzed 5-Ethoxymethylfurfural Synthesis from Carbohydrates
by Xin Yu, Xueying Gao, Ruili Tao and Lincai Peng
Catalysts 2017, 7(6), 182; https://doi.org/10.3390/catal7060182 - 08 Jun 2017
Cited by 22 | Viewed by 5378
Abstract
The use of common metal salts as catalysts for 5-ethoxymethylfurfural (EMF) synthesis from carbohydrate transformation was performed. Initial screening suggested AlCl3 as an efficient catalyst for EMF synthesis (45.0%) from fructose at 140 °C. Interestingly, CuSO4 and Fe2(SO4)3 were found to yield comparable [...] Read more.
The use of common metal salts as catalysts for 5-ethoxymethylfurfural (EMF) synthesis from carbohydrate transformation was performed. Initial screening suggested AlCl3 as an efficient catalyst for EMF synthesis (45.0%) from fructose at 140 °C. Interestingly, CuSO4 and Fe2(SO4)3 were found to yield comparable EMF at lower temperature of 110 to 120 °C, and high yields of ethyl levulinate (65.4–71.8%) were obtained at 150 °C. However, these sulfate salts were inactive in EMF synthesis from glucose and the major product was ethyl glucoside with around 80% yield, whereas EMF of 15.2% yield could be produced from glucose using CrCl3. The conversion of sucrose followed the accumulation of the reaction pathways of fructose and glucose, and a moderate yield of EMF could be achieved. Full article
(This article belongs to the Special Issue Catalysis of Biomass-Derived Molecules)
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1118 KiB  
Communication
Mechanocatalytic Production of Lactic Acid from Glucose by Ball Milling
by Luyang Li, Lulu Yan, Feng Shen, Mo Qiu and Xinhua Qi
Catalysts 2017, 7(6), 170; https://doi.org/10.3390/catal7060170 - 01 Jun 2017
Cited by 9 | Viewed by 4467
Abstract
A solvent-free process was developed for the direct production of lactic acid from glucose in a mechanocatalytic process in the presence of Ba(OH)2, and a moderate lactic acid yield of 35.6% was obtained. Glucose conversion and lactic acid formation were favorable [...] Read more.
A solvent-free process was developed for the direct production of lactic acid from glucose in a mechanocatalytic process in the presence of Ba(OH)2, and a moderate lactic acid yield of 35.6% was obtained. Glucose conversion and lactic acid formation were favorable at higher catalyst/glucose mass ratios. However, at relatively lower catalyst/glucose mass ratios, they were greatly inhibited, and the promotion of fructose formation was observed. The mechanocatalytic process was applicable for various carbohydrates such as C5 sugars, C6 sugars, and disaccharides with 20–36% lactic acid yields achieved. This work provides a new pathway for the production of value-added chemicals from biomass resources. Full article
(This article belongs to the Special Issue Catalysis of Biomass-Derived Molecules)
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1491 KiB  
Article
A Simple and Efficient Process for Large Scale Glycerol Oligomerization by Microwave Irradiation
by Rémi Nguyen, Nicolas Galy, Abhishek K. Singh, Florian Paulus, Daniel Stöbener, Cathleen Schlesener, Sunil K. Sharma, Rainer Haag and Christophe Len
Catalysts 2017, 7(4), 123; https://doi.org/10.3390/catal7040123 - 19 Apr 2017
Cited by 17 | Viewed by 7041
Abstract
Herein, an optimized method for 100 g scale synthesis of glycerol oligomers using a microwave multimode source and the low priced K2CO3 as catalyst is reported. This method allows the complete conversion of glycerol to its oligomers in only 30 [...] Read more.
Herein, an optimized method for 100 g scale synthesis of glycerol oligomers using a microwave multimode source and the low priced K2CO3 as catalyst is reported. This method allows the complete conversion of glycerol to its oligomers in only 30 min, yielding molecular weights up to 1000 g mol−1. Furthermore, a simple iterative purification process, involving the precipitation of the crude product in acetone and methanol, affords a final product composed of larger oligomers with a narrow dispersity (D < 1.5). Full article
(This article belongs to the Special Issue Catalysis of Biomass-Derived Molecules)
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Figure 1

6661 KiB  
Article
Catalytic Dehydration of Glycerol to Acrolein over a Catalyst of Pd/LaY Zeolite and Comparison with the Chemical Equilibrium
by Israel Pala Rosas, José Luis Contreras, José Salmones, Carlos Tapia, Beatriz Zeifert, Juan Navarrete, Tamara Vázquez and Diana Carolina García
Catalysts 2017, 7(3), 73; https://doi.org/10.3390/catal7030073 - 25 Feb 2017
Cited by 37 | Viewed by 10194
Abstract
Glycerol dehydration to acrolein was studied with three catalysts using zeolite-Y. This zeolite in its protonic form (HY), with La (LaY) and Pd with La (Pd/LaY), was characterized by X-ray diffraction (XRD), Fourier-transform-infrared spectroscopy (FTIR) with pyridine, BET, Scanning Electron Microscope (SEM)–Energy-Dispersive Spectroscopy [...] Read more.
Glycerol dehydration to acrolein was studied with three catalysts using zeolite-Y. This zeolite in its protonic form (HY), with La (LaY) and Pd with La (Pd/LaY), was characterized by X-ray diffraction (XRD), Fourier-transform-infrared spectroscopy (FTIR) with pyridine, BET, Scanning Electron Microscope (SEM)–Energy-Dispersive Spectroscopy X-ray (EDS) and the catalytic activity tests were carried out under H2 atmosphere. It was found that La ions exchanged in the zeolite-Y resulted in the improvement of both glycerol conversion and yield to acrolein, also a relatively constant glycerol conversion was achieved up to three hours, due to the presence of Pd on the catalyst and H2 in the feed. The comparison of the calculated and experimental yields obtained from the catalytic tests of the Pd/LaY catalyst indicates a greater activity for the reaction to acrolein than for the reaction to acetol. The calculated equilibrium yields of the dehydration reaction from glycerol to acrolein, acetol, ethanal, methanol, and water and the experimental yields of a Pd/LaY catalyst were compared. Thermodynamically, a complete conversion of glycerol can be achieved since the general system remains exothermic and promotes the path to acetol below 480 K. Above this temperature the system consumes energy and favors the production of acrolein, reaching its maximum concentration at 600 K. Full article
(This article belongs to the Special Issue Catalysis of Biomass-Derived Molecules)
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