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Catalytic Conversion of Biomass Derived Compounds (Carbohydrates, Furanic Derivatives, and...
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Catalytic Conversion of Biomass Derived Compounds (Carbohydrates, Furanic Derivatives, and Glycerol)

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

Deadline for manuscript submissions: closed (20 November 2021) | Viewed by 37985

Special Issue Editors

Prof. Dr. Karine De Oliveira Vigier

E-Mail Website
Guest Editor
IC2MP, UMR, CNRS, Université de Poitiers 7285, ENSIP 1 Rue Marcel Doré, TSA 41195, CEDEX 9, 86073 Poitiers, France
Interests: catalytic conversion of carbohydrates and furanic derivatives; control of the selectivity by using alternative media (DESs, ball milling, etc.)
Special Issues, Collections and Topics in MDPI journals
Dr. Mickael Capron

E-Mail Website
Guest Editor
UCCS, UMR CNRS 8181, Université de Lille, 59655 Villeneuve D’Ascq, France
Interests: biomass valorization for fine chemicals starting from polyols
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

For several decades now, the world and, more specifically, the scientific community has been working to mitigate the inevitable decrease in fossil resources. To do this, the valorization of renewable resources such as lignocellulosic biomass and vegetable oils have received a great deal of attention. This renewable carbon can be converted to fuels or fine chemicals. Among raw materials that can be obtained from biomass, carbohydrates, furan derivatives, and glycerol have been identified as having a particular interest, due to the high availability of these resources and the wide variety of derivatives that can be obtained from them. Despite the intensive and numerous studies that have emerged in recent years, a number of points remain to be addressed before the industrialization of certain processes can take place, such as the use of unrefined products, the high concentration of water in the medium, catalyst stability, and low cost processes. In order to solve these problems, research is still needed and is of prime importance. 

Prof. Dr. Karine De Oliveira Vigier
Dr. Mickael Capron
Guest Editors

Manuscript Submission Information

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Keywords

  • biomass
  • catalysis
  • carbohydrates
  • furan derivatives
  • glycerol

Related Special Issue

Published Papers (7 papers)

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Research

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19 pages, 6789 KiB  
Article
Catalytic Production of Glycolic Acid from Glycerol Oxidation: An Optimization Using Response Surface Methodology
by Claudia Patricia Tavera Ruiz, Franck Dumeignil and Mickaël Capron
Catalysts 2021, 11(2), 257; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11020257 - 15 Feb 2021
Cited by 8 | Viewed by 3245
Abstract
This study aimed at optimizing the production of glycolic acid from glycerol catalytic oxidation over a silver catalyst supported on a mixed cerium-zirconium oxide, to progress towards the industrialization of a derived process. Optimization of the operating conditions was performed using the response [...] Read more.
This study aimed at optimizing the production of glycolic acid from glycerol catalytic oxidation over a silver catalyst supported on a mixed cerium-zirconium oxide, to progress towards the industrialization of a derived process. Optimization of the operating conditions was performed using the response surface methodology. We concluded that the production of glycolic acid depends mainly of glycerol concentration, NaOH/glycerol ratio, catalyst/glycerol ratio, and O2/glycerol ratio. The optimal conditions we found were a temperature of 60 °C, a NaOH/glycerol molar ratio of 2, an O2/glycerol molar ratio of 0.23, and a catalyst/glycerol mass ratio of 0.07. With these optimal conditions, it was possible to increase the glycerol concentration from 0.3 M to 2 M, obtaining an increase in the concentration of glycolic acid in the liquid fraction, from 0.27 mol/L of glycolic acid (with initial glycerol solution 0.3 M) to 0.88 mol/L (with initial solution 2 M), while keeping a 100% glycerol conversion. Full article
(This article belongs to the Special Issue Catalytic Conversion of Biomass Derived Compounds (Carbohydrates, Furanic Derivatives, and Glycerol))
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21 pages, 5805 KiB  
Article
Glycerol Hydrogenolysis with In Situ Hydrogen Produced via Methanol Steam Reforming: The Promoting Effect of Pd on a Cu/ZnO/Al2O3 Catalyst
by Yuanqing Liu, Chau T. Q. Mai and Flora T. T. Ng
Catalysts 2021, 11(1), 110; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11010110 - 14 Jan 2021
Cited by 11 | Viewed by 2711
Abstract
The glycerol hydrogenolysis to produce 1,2-propanediol without using externally supplied hydrogen was investigated using methanol present in crude glycerol to provide in situ hydrogen via its steam reforming reaction. This paper focuses on the promoting effect of Pd on the reactivity of a [...] Read more.
The glycerol hydrogenolysis to produce 1,2-propanediol without using externally supplied hydrogen was investigated using methanol present in crude glycerol to provide in situ hydrogen via its steam reforming reaction. This paper focuses on the promoting effect of Pd on the reactivity of a Cu/Zn/Al2O3 catalyst. Adding 2 wt% Pd onto a Cu/ZnO/Al2O3 catalyst significantly improved the selectivity to 1,2-propanediol from 63.0% to 82.4% and the glycerol conversion from 70.2% to 99.4%. This enhancement on the catalytic activity by Pd is mainly due to the improved hydrogenation of acetol, which is the intermediate formed during the glycerol dehydration. The rapid hydrogenation of acetol can shift the reaction equilibrium of glycerol dehydration forward resulting in a higher glycerol conversion. The improved reducibility of the catalyst by Pd allows the catalyst to be reduced in situ during the reaction preventing any loss of catalyst activity due to any potential oxidation of the catalyst. The catalyst was slightly deactivated when it was firstly recycled resulting in a 5.4% loss of glycerol conversion due to the aggregation of Cu and the deactivation became less noticeable upon further recycling. Full article
(This article belongs to the Special Issue Catalytic Conversion of Biomass Derived Compounds (Carbohydrates, Furanic Derivatives, and Glycerol))
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13 pages, 1940 KiB  
Article
Acid Properties of GO and Reduced GO as Determined by Microcalorimetry, FTIR, and Kinetics of Cellulose Hydrolysis-Hydrogenolysis
by Van Chuc Nguyen, Sarah Kheireddine, Amar Dandach, Marion Eternot, Thi Thu Ha Vu and Nadine Essayem
Catalysts 2020, 10(12), 1393; https://0-doi-org.brum.beds.ac.uk/10.3390/catal10121393 - 30 Nov 2020
Cited by 8 | Viewed by 3710
Abstract
Graphene oxide addresses increasing interests as a solid acid catalyst working in water for carbohydrate conversion. If there is a general agreement to correlate its unique catalytic performances to its ability to adsorb sugars, the origin of its acidity remains controversial. In this [...] Read more.
Graphene oxide addresses increasing interests as a solid acid catalyst working in water for carbohydrate conversion. If there is a general agreement to correlate its unique catalytic performances to its ability to adsorb sugars, the origin of its acidity remains controversial. In this article, we study the acid strength of graphene oxide (GO) prepared by modified Hummers method and that of reduced GO by calorimetry of NH3 adsorption and by FTIR of pyridine adsorption. Very strong acid sites are detected on GO by calorimetry, while reduced graphene oxide (reGO) is not very acidic. The FTIR of pyridine adsorption shows the prevailing presence of Br∅nsted acid sites and a unique feature, the presence of pyridine coordinated by hydrogen bonds. This exceptionally strong Br∅nsted acidity is tentatively explained by the presence of graphene domains decorated by hydroxyl, carboxylic, or sulfonated groups within the GO sheet, resulting in a high mobility of the negative charges which makes the proton free and explains its strong acidity. Accordingly, only GO is active and selective for native cellulose hydrolysis, leading to 27% yield in glucose. Finally, we show that sugar alcohols cannot be formed directly from cellulose using GO combined with Pt/re-GO under hydrogen, explained by the reduction of oxygenated functions of GO. The instability of the functional groups of GO in a reducing atmosphere is the weak point of this peculiar solid acid. Full article
(This article belongs to the Special Issue Catalytic Conversion of Biomass Derived Compounds (Carbohydrates, Furanic Derivatives, and Glycerol))
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14 pages, 6261 KiB  
Article
Hydrodeoxygenation of Benzofuran over Bimetallic Ni-Cu/γ-Al2O3 Catalysts
by Tianhan Zhu, Hua Song, Feng Li and Yanguang Chen
Catalysts 2020, 10(3), 274; https://0-doi-org.brum.beds.ac.uk/10.3390/catal10030274 - 01 Mar 2020
Cited by 10 | Viewed by 2860
Abstract
Bimetallic NixCu(10−x)/γ-Al2O3 catalysts (where x is the mass fraction of Ni) with different Ni/Cu mass ratios were prepared. The catalysts were characterized by X-ray diffractometry, N2 adsorption–desorption, inductively coupled plasma mass spectrometry, X-ray [...] Read more.
Bimetallic NixCu(10−x)/γ-Al2O3 catalysts (where x is the mass fraction of Ni) with different Ni/Cu mass ratios were prepared. The catalysts were characterized by X-ray diffractometry, N2 adsorption–desorption, inductively coupled plasma mass spectrometry, X-ray photoelectron spectroscopy, H2-temperature programmed reduction, and transmission electron microscopy. The effect of Ni/Cu mass ratio on benzofuran hydrodeoxygenation was investigated in a fixed-flow reactor. Cu addition improved the NiO reducibility. The strong interaction of Ni and Cu led to the formation of smaller and highly dispersed CuO and NiO species over γ-Al2O3, which favors an improvement in catalytic activity. Among the as-prepared catalysts, the Ni5Cu5/γ-Al2O3 showed the highest deoxygenated product yield (79.9%) with an acceptable benzofuran conversion of 95.2%, which increased by 18.3% and 16.9% compared with that of the monometallic Ni/γ-Al2O3 catalyst. A possible reaction network was proposed, which would provide insight into benzofuran hydrodeoxygenation over the Ni5Cu5/γ-Al2O3 catalyst. Full article
(This article belongs to the Special Issue Catalytic Conversion of Biomass Derived Compounds (Carbohydrates, Furanic Derivatives, and Glycerol))
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10 pages, 2791 KiB  
Article
Effects of Additives and Metals on Crystallization of Nano-Sized HZSM-5 Zeolite for Glycerol Aromatization
by Wei Xu, Lijing Gao and Guomin Xiao
Catalysts 2019, 9(11), 899; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9110899 - 28 Oct 2019
Cited by 3 | Viewed by 2676
Abstract
Nano-sized HZSM-5 (n-HZSM-5) was synthesized and applied in the aromatization of glycerol. The effects of additives (carboxymethylcellulose sodium, NaCl, sodium alginate, etc.) on the chemical and physic properties of n-HZSM-5 during preparation were investigated. Metal modification was also investigated based on the synthesized [...] Read more.
Nano-sized HZSM-5 (n-HZSM-5) was synthesized and applied in the aromatization of glycerol. The effects of additives (carboxymethylcellulose sodium, NaCl, sodium alginate, etc.) on the chemical and physic properties of n-HZSM-5 during preparation were investigated. Metal modification was also investigated based on the synthesized n-HZSM-5. The results showed that the addition of carboxymethylcellulose sodium (CMC-Na), NaCl and sodium alginate (SA) led to forming smaller sizes of HZSM-5 and promoted the acid amounts of the catalysts, which increased its catalytic activities for obtaining BTX. The highest BTX yield of ~35% was obtained by SA derived n-HZSM-5, and the life of the catalyst were both obviously promoted by the additives with a highest of ~11 h by γ-(2,3-epoxypropoxy)propytrimethoxysilane (KH-560) derived n-HZSM-5. BTX yields could be improved by 40%by the addition of Zn and Cd in n-HZSM-5 while having little effect on the catalyst life. Full article
(This article belongs to the Special Issue Catalytic Conversion of Biomass Derived Compounds (Carbohydrates, Furanic Derivatives, and Glycerol))
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14 pages, 2747 KiB  
Article
ZIF-8 Metal Organic Framework for the Conversion of Glucose to Fructose and 5-Hydroxymethyl Furfural
by Ryan Oozeerally, Shivendra D. K. Ramkhelawan, David L. Burnett, Christiaan H. L. Tempelman and Volkan Degirmenci
Catalysts 2019, 9(10), 812; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9100812 - 27 Sep 2019
Cited by 34 | Viewed by 6280
Abstract
Herein, Zeolitic imidazolate framework-8 (ZIF-8) is considered as an easy and cheap to prepare alternative catalyst for the isomerization of glucose and production of 5-hydroxymethyl furfural (HMF). For the synthesis of the ZIF-8 catalysts two preparation methods were evaluated, being room temperature and [...] Read more.
Herein, Zeolitic imidazolate framework-8 (ZIF-8) is considered as an easy and cheap to prepare alternative catalyst for the isomerization of glucose and production of 5-hydroxymethyl furfural (HMF). For the synthesis of the ZIF-8 catalysts two preparation methods were evaluated, being room temperature and hydrothermal synthesis at 140 °C. Of these, the hydrothermal synthesis method yields a material with exceptionally high surface area (1967 m2·g−1). As a catalyst, the ZIF-8 materials generated excellent fructose yields. Specifically, ZIF-8 prepared by hydrothermal synthesis yielded a fructose selectivity of 65% with a glucose conversion of 24% at 100 °C in aqueous reaction medium. However, this selectivity dropped dramatically when the reactions were repeated at higher temperatures (~140 °C). Interestingly, greater quantities of mannose were produced at higher temperatures too. The lack of strong Brønsted acidity in both ZIF-8 materials resulted in poor HMF yields. In order to improve HMF yields, reactions were performed at a lower pH of 1.0. At 140 °C the lower pH was found to drive the reaction towards HMF and double its yield. Despite the excellent performance of ZIF-8 catalysts in batch reactions, their activity did not translate well to the flow reactor over a continuous run of 8 h, which was operating with a residence time of 6 min. The activity of ZIF-8 halved in the flow reactor at 100 °C in ~3 h, which implies that the catalyst’s stability was not maintained in the long run. Full article
(This article belongs to the Special Issue Catalytic Conversion of Biomass Derived Compounds (Carbohydrates, Furanic Derivatives, and Glycerol))
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Review

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32 pages, 6124 KiB  
Review
The Role of Glycerol and Its Derivatives in the Biochemistry of Living Organisms, and Their Prebiotic Origin and Significance in the Evolution of Life
by Maheen Gull and Matthew A. Pasek
Catalysts 2021, 11(1), 86; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11010086 - 10 Jan 2021
Cited by 16 | Viewed by 15332
Abstract
The emergence and evolution of prebiotic biomolecules on the early Earth remain a question that is considered crucial to understanding the chemistry of the origin of life. Amongst prebiotic molecules, glycerol is significant due to its ubiquity in biochemistry. In this review, we [...] Read more.
The emergence and evolution of prebiotic biomolecules on the early Earth remain a question that is considered crucial to understanding the chemistry of the origin of life. Amongst prebiotic molecules, glycerol is significant due to its ubiquity in biochemistry. In this review, we discuss the significance of glycerol and its various derivatives in biochemistry, their plausible roles in the origin and evolution of early cell membranes, and significance in the biochemistry of extremophiles, followed by their prebiotic origin on the early Earth and associated catalytic processes that led to the origin of these compounds. We also discuss various scenarios for the prebiotic syntheses of glycerol and its derivates and evaluate these to determine their relevance to early Earth biochemistry and geochemistry, and recapitulate the utilization of various minerals (including clays), condensation agents, and solvents that could have led to the successful prebiotic genesis of these biomolecules. Furthermore, important prebiotic events such as meteoritic delivery and prebiotic synthesis reactions under astrophysical conditions are also discussed. Finally, we have also highlighted some novel features of glycerol, including glycerol nucleic acid (GNA), in the origin and evolution of the life. Full article
(This article belongs to the Special Issue Catalytic Conversion of Biomass Derived Compounds (Carbohydrates, Furanic Derivatives, and Glycerol))
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