Special Issue "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)

Special Issue Editor

Guest Editor
Prof. Dr. Charles Xu

Institute for Chemicals and Fuels from Alternative Resources (ICFAR), Department of Chemical and Biochemical Engineering, Western University, Ontario, Canada
Website | E-Mail
Phone: 519-661-2111 ext. 86414
Fax: 519-661-4016
Interests: Biorefining technologies; Bio-fuels; Bio-based chemicals; Bio-based materials; Thermochemical conversion; Hydrothermal liquefaction; Pyrolysis; Combustion; Gasification; Lignocellulosic biomass; Forestry residues; Agricultural residues; Sugars; Starch; Cellulose; Lignin; Municipal solid wastes; Wastewater sludge; Catalysis; Catalysts; Chemical reaction engineering; Green process engineering

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

Manuscript Submission Information

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Published Papers (7 papers)

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Research

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Open AccessFeature PaperArticle Exploring the Effect of Au/Pt Ratio on Glycerol Oxidation in Presence and Absence of a Base
Catalysts 2018, 8(2), 54; https://doi.org/10.3390/catal8020054
Received: 24 December 2017 / Revised: 26 January 2018 / Accepted: 29 January 2018 / Published: 31 January 2018
Cited by 1 | PDF Full-text (2739 KB) | HTML Full-text | XML Full-text | Supplementary Files
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
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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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Open AccessArticle Promoting Role of Bismuth on Hydrotalcite-Supported Platinum Catalysts in Aqueous Phase Oxidation of Glycerol to Dihydroxyacetone
Catalysts 2018, 8(1), 20; https://doi.org/10.3390/catal8010020
Received: 16 December 2017 / Revised: 7 January 2018 / Accepted: 9 January 2018 / Published: 11 January 2018
Cited by 2 | PDF Full-text (2600 KB) | HTML Full-text | XML Full-text | Supplementary Files
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
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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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Open AccessArticle Arenesulfonic Acid-Functionalized Bentonite as Catalyst in Glycerol Esterification with Acetic Acid
Catalysts 2017, 7(7), 211; https://doi.org/10.3390/catal7070211
Received: 13 May 2017 / Revised: 28 June 2017 / Accepted: 3 July 2017 / Published: 14 July 2017
Cited by 2 | PDF Full-text (2191 KB) | HTML Full-text | XML Full-text
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
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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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Open AccessArticle 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
Catalysts 2017, 7(7), 196; https://doi.org/10.3390/catal7070196
Received: 29 April 2017 / Revised: 19 June 2017 / Accepted: 23 June 2017 / Published: 25 June 2017
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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
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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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Open AccessArticle Catalytic Acetalization: An Efficient Strategy for High-Value Utilization of Biodiesel-Derived Glycerol
Catalysts 2017, 7(6), 184; https://doi.org/10.3390/catal7060184
Received: 27 March 2017 / Revised: 24 May 2017 / Accepted: 26 May 2017 / Published: 8 June 2017
Cited by 1 | PDF Full-text (6456 KB) | HTML Full-text | XML Full-text
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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Open AccessReview Navigating Glycerol Conversion Roadmap and Heterogeneous Catalyst Selection Aided by Density Functional Theory: A Review
Catalysts 2018, 8(2), 44; https://doi.org/10.3390/catal8020044
Received: 16 December 2017 / Revised: 5 January 2018 / Accepted: 6 January 2018 / Published: 24 January 2018
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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
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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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Open AccessReview Olefins from Biomass Intermediates: A Review
Catalysts 2018, 8(1), 2; https://doi.org/10.3390/catal8010002
Received: 16 November 2017 / Revised: 14 December 2017 / Accepted: 19 December 2017 / Published: 23 December 2017
PDF Full-text (3632 KB) | HTML Full-text | XML Full-text
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
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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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