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Glycerol Conversion by Heterogeneous Catalysis
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Glycerol Conversion by Heterogeneous Catalysis

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

Deadline for manuscript submissions: closed (15 November 2017) | Viewed by 52826

Special Issue Editor

Prof. Dr. Charles Xu

E-Mail Website
Guest Editor
School of Energy and Environment, City University of Hong Kong, Kowloon, Hong Kong, China
Interests: catalytic conversion of lignocellulosic biomass for fuels; chemicals and materials; catalytic conversion of cellulose, starch or sugars into chemicals and materials; catalytic conversion of glycerol; green chemistry and engineering
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Although the plunge in crude oil prices in recent years has caused a downfall in bio-diesel production, it had increased dramatically in different parts of the world, resulting in a large amount of glycerol as byproduct from the process. The increased amount of glycerol in the market had become a burden to the biodiesel producers who have limited options for managing this byproduct. Valorization of glycerol is thus needed to enhance the sustainability of the biodiesel industry.

Glycerol, the simplest tri-hydroxy alcohol has many potential applications. The multi-functionality of glycerol makes it a promising precursor for the production of high-value bio-renewable fuel/chemical products through various processes involving heterogeneous catalysis, e.g., esterification, etherification, oxidation, dehydration, acetalization, hydrogenolysis, chlorination and catalytic reforming. The glycerol-derived fuel/chemical products include liquid/gaseous fuels, fuel additives (e.g., solketal) and chemicals (e.g., glycerol mono-esters, glyceric acid, 1,3-dihydroxyacetone (DHA), epichlorohydrin, glycidol, tartronic acid, lactic acid, acrylonitrile, 1,2-propanediol and1,3-propanediol, etc.). The main challenge in catalytic conversion of glycerol in batch or continuous-flow processes is associated with deactivation of catalysts over time. Catalyst deactivation over time is the main issue in most reported processes for glycerol conversion. Thus, intense research is underway to develop catalysts of high activity and superb stability.

This Special Issue aims to cover recent progress and trends in conversion of glycerol into high-value bio-renewable fuel/chemical products through heterogeneous catalysis, including the designing, synthesizing, characterizing and evaluating heterogeneous catalysts for glycerol conversion.

Prof. Dr. Chunbao (Charles) Xu
Guest Editor

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Published Papers (7 papers)

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Research

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13 pages, 2739 KiB  
Article
Exploring the Effect of Au/Pt Ratio on Glycerol Oxidation in Presence and Absence of a Base
by Alberto Villa, Andrea Jouve, Felipe J. Sanchez Trujillo, Davide Motta, Laura Prati and Nikolaos Dimitratos
Catalysts 2018, 8(2), 54; https://doi.org/10.3390/catal8020054 - 31 Jan 2018
Cited by 24 | Viewed by 5289
Abstract
Bimetallic AuPt nanoparticles with different Au:Pt ratios (molar ratio: 9-1, 8-2, 6-4, 2-8, 1-9) and the corresponding Au and Pt monometallic ones were prepared by sol immobilization and immobilized on commercial TiO2 (P25). The catalytic activity was evaluated in the liquid phase [...] Read more.
Bimetallic AuPt nanoparticles with different Au:Pt ratios (molar ratio: 9-1, 8-2, 6-4, 2-8, 1-9) and the corresponding Au and Pt monometallic ones were prepared by sol immobilization and immobilized on commercial TiO2 (P25). The catalytic activity was evaluated in the liquid phase glycerol oxidation in presence and absence of a base (NaOH). It was found that the Au:Pt molar ratio and reaction conditions strongly influence the catalytic performance. In the presence of NaOH, Au-rich catalysts were more active than Pt-rich ones, with the highest activity observed for Au9Pt1/TiO2 (6575 h−1). In absence of a base, a higher content of Pt is needed to produce the most active catalyst (Au6Pt4/TiO2, 301 h−1). In terms of selectivity, in presence of NaOH, Au-rich catalysts showed a high selectivity to C3 products (63–72%) whereas Pt-rich catalysts promote the formation of formic and glycolic acids. The opposite trend was observed in absence of a base with Pt-rich catalysts showing higher selectivity to C3 products (83–88%). Full article
(This article belongs to the Special Issue Glycerol Conversion by Heterogeneous Catalysis)
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12 pages, 2600 KiB  
Article
Promoting Role of Bismuth on Hydrotalcite-Supported Platinum Catalysts in Aqueous Phase Oxidation of Glycerol to Dihydroxyacetone
by Wenjie Xue, Zenglong Wang, Yu Liang, Hong Xu, Lei Liu and Jinxiang Dong
Catalysts 2018, 8(1), 20; https://doi.org/10.3390/catal8010020 - 11 Jan 2018
Cited by 25 | Viewed by 6719
Abstract
Bismuth plays important roles in promoting the oxidation of alcohols towards high-value-added chemicals over a noble metal loading catalyst. Herein, Mg–Al hydrotalcite-supported platinum–bismuth nanoparticles (Pt–Bi/HT) were prepared by the co-impregnation method and used in the selective oxidation of glycerol towards dihydroxyacetone (DHA). The [...] Read more.
Bismuth plays important roles in promoting the oxidation of alcohols towards high-value-added chemicals over a noble metal loading catalyst. Herein, Mg–Al hydrotalcite-supported platinum–bismuth nanoparticles (Pt–Bi/HT) were prepared by the co-impregnation method and used in the selective oxidation of glycerol towards dihydroxyacetone (DHA). The incorporation of Bi species into Pt/HT significantly enhances the conversion of glycerol and the selectivity of DHA. The high selectivity of DHA with 80.6% could be achieved at 25.1% conversion of glycerol. The Bi species of the Pt–Bi/HT catalyst mainly exist in the form of BiOCl and Bi metal, which is different from the previous Pt–Bi based catalyst, confirmed by a combination of powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HR-TEM). A plausible mechanism is proposed to elucidate the promoting role of Bi species on the Pt/HT catalyst in the selective oxidation of glycerol towards DHA. Full article
(This article belongs to the Special Issue Glycerol Conversion by Heterogeneous Catalysis)
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2191 KiB  
Article
Arenesulfonic Acid-Functionalized Bentonite as Catalyst in Glycerol Esterification with Acetic Acid
by Maryam Tangestanifard and Hassan S. Ghaziaskar
Catalysts 2017, 7(7), 211; https://doi.org/10.3390/catal7070211 - 14 Jul 2017
Cited by 26 | Viewed by 5634
Abstract
The present study is focused on the synthesis of arenesulfonic acid-functionalized bentonite as a catalyst to produce monoacetin, diacetin, and triacetin from glycerol and acetic acid using toluene as solvent and a water removing agent. The best conditions for the present reaction with [...] Read more.
The present study is focused on the synthesis of arenesulfonic acid-functionalized bentonite as a catalyst to produce monoacetin, diacetin, and triacetin from glycerol and acetic acid using toluene as solvent and a water removing agent. The best conditions for the present reaction with acetic acid were an acetic acid:glycerol:toluene molar ratio of 7:1:1.4, 100 °C, and 0.074 wt % of catalyst (based on the total weight of glycerol). Under the reaction conditions, 96% glycerol conversion was achieved within 0.5 h from the start of the reaction. The maximum selectivity of 66% and 74% were achieved for diacetin and triacetin after 0.5 and 3 h of reaction, respectively, without formation of any byproduct. The arenesulfonic acid-functionalized bentonite was characterized by X-ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, N2 adsorption/desorption experiments (Brunauer, Emmett and Teller, BET, method), field emission scanning electron microscopy, and the surface acidity was determined by back titration. Without significant treatment, the catalyst was reusable for 5 consecutive runs. Full article
(This article belongs to the Special Issue Glycerol Conversion by Heterogeneous Catalysis)
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5319 KiB  
Article
Selective Hydrogenolysis of Glycerol and Crude Glycerol (a By-Product or Waste Stream from the Biodiesel Industry) to 1,2-Propanediol over B2O3 Promoted Cu/Al2O3 Catalysts
by Malaya R. Nanda, Zhongshun Yuan, Hengfu Shui and Chunbao (Charles) Xu
Catalysts 2017, 7(7), 196; https://doi.org/10.3390/catal7070196 - 25 Jun 2017
Cited by 21 | Viewed by 5395
Abstract
The performance of boron oxide (B2O3)-promoted Cu/Al2O3 catalyst in the selective hydrogenolysis of glycerol and crude glycerol (a by-product or waste stream from the biodiesel industry) to produce 1,2-propanediol (1,2-PDO) was investigated. The catalysts were characterized [...] Read more.
The performance of boron oxide (B2O3)-promoted Cu/Al2O3 catalyst in the selective hydrogenolysis of glycerol and crude glycerol (a by-product or waste stream from the biodiesel industry) to produce 1,2-propanediol (1,2-PDO) was investigated. The catalysts were characterized using N2-adsorption-desorption isotherm, Inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray diffraction (XRD), ammonia temperature programmed desorption (NH3-TPD), thermogravimetric analysis (TGA), temperature programmed reduction (TPR), and transmission electron microscopy (TEM). Incorporation of B2O3 to Cu/Al2O3 was found to enhance the catalytic activity. At the optimum condition (250 °C, 6 MPa H2 pressure, 0.1 h−1 WHSV (weight hourly space velocity), and 5Cu-B/Al2O3 catalyst), 10 wt% aqueous solution of glycerol was converted into 1,2-PDO at 98 ± 2% glycerol conversion and 98 ± 2% selectivity. The effects of temperature, pressure, boron addition amount, and liquid hourly space velocity were studied. Different grades of glycerol (pharmaceutical, technical, or crude glycerol) were used in the process to investigate the stability and resistance to deactivation of the selected 5Cu-B/Al2O3 catalyst. Full article
(This article belongs to the Special Issue Glycerol Conversion by Heterogeneous Catalysis)
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6456 KiB  
Article
Catalytic Acetalization: An Efficient Strategy for High-Value Utilization of Biodiesel-Derived Glycerol
by Suqun Sun, Min He, Yuanwei Dai, Xin Li, Zhijun Liu and Li Yao
Catalysts 2017, 7(6), 184; https://doi.org/10.3390/catal7060184 - 8 Jun 2017
Cited by 11 | Viewed by 4314
Abstract
In this study, an efficient process for high value utilization of biodiesel-derived glycerol was proposed via a simple reaction of acetalization catalyzed by novel catalysts of ester sulfate-functionalized ionic liquids (ILs). The relationship between the IL structure and its catalytic activity was investigated. [...] Read more.
In this study, an efficient process for high value utilization of biodiesel-derived glycerol was proposed via a simple reaction of acetalization catalyzed by novel catalysts of ester sulfate-functionalized ionic liquids (ILs). The relationship between the IL structure and its catalytic activity was investigated. The effects of reaction conditions, and the substrate adaptability, were also carefully studied. The results demonstrate that ester sulfate-functionalized IL shows excellent catalytic activity on the acetalization of glycerol with aldehyde (ketone). Under the optimized condition, 87% glycerol conversion was obtained with 99% acetal selectivity when glycerol was condensed with cyclohexanone. In particular, 29% of product consists of six-membered compound, an important fine chemical and an excellent precursor in organic chemistry, because of the significant steric-hindrance effect of IL catalyst. Furthermore, the IL catalyst shows good recyclability where insignificant activity loss was exhibited even after six runs. Full article
(This article belongs to the Special Issue Glycerol Conversion by Heterogeneous Catalysis)
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Review

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27 pages, 4494 KiB  
Review
Navigating Glycerol Conversion Roadmap and Heterogeneous Catalyst Selection Aided by Density Functional Theory: A Review
by Bin Liu and Feng Gao
Catalysts 2018, 8(2), 44; https://doi.org/10.3390/catal8020044 - 24 Jan 2018
Cited by 29 | Viewed by 11497
Abstract
Glycerol has been utilized in an extremely diversified manner throughout human civilization—ranging from food, to various consumer products, to pharmaceuticals, and even explosives. Large surplus in glycerol supply thanks to biodiesel production and biomass processing has created a demand to further boost its [...] Read more.
Glycerol has been utilized in an extremely diversified manner throughout human civilization—ranging from food, to various consumer products, to pharmaceuticals, and even explosives. Large surplus in glycerol supply thanks to biodiesel production and biomass processing has created a demand to further boost its utility. One growing area is to expand the use of glycerol as an alternative feedstock to supplement fuels and chemicals production. Various catalytic processes have been developed. This review summarizes catalytic materials for glycerol reforming, hydrodeoxygenation, and oxidation. In particular, rationale for catalyst selection and new catalyst design will be discussed aided by the knowledge of reaction mechanisms. The role of theoretical density functional theory (DFT) in elucidating complex glycerol conversion chemistries is particularly emphasized. Full article
(This article belongs to the Special Issue Glycerol Conversion by Heterogeneous Catalysis)
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3632 KiB  
Review
Olefins from Biomass Intermediates: A Review
by Vasiliki Zacharopoulou and Angeliki A. Lemonidou
Catalysts 2018, 8(1), 2; https://doi.org/10.3390/catal8010002 - 23 Dec 2017
Cited by 102 | Viewed by 12824
Abstract
Over the last decade, increasing demand for olefins and their valuable products has prompted research on novel processes and technologies for their selective production. As olefins are predominately dependent on fossil resources, their production is limited by the finite reserves and the associated [...] Read more.
Over the last decade, increasing demand for olefins and their valuable products has prompted research on novel processes and technologies for their selective production. As olefins are predominately dependent on fossil resources, their production is limited by the finite reserves and the associated economic and environmental concerns. The need for alternative routes for olefin production is imperative in order to meet the exceedingly high demand, worldwide. Biomass is considered a promising alternative feedstock that can be converted into the valuable olefins, among other chemicals and fuels. Through processes such as fermentation, gasification, cracking and deoxygenation, biomass derivatives can be effectively converted into C2–C4 olefins. This short review focuses on the conversion of biomass-derived oxygenates into the most valuable olefins, e.g., ethylene, propylene, and butadiene. Full article
(This article belongs to the Special Issue Glycerol Conversion by Heterogeneous Catalysis)
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