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Catalytic Valorization of Glycerol: Strategies and Perspectives

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

Deadline for manuscript submissions: closed (10 January 2022) | Viewed by 34211

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Prof. Dr. Francesco Ruffo

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Department of Chemical Science, University of Naples Federico II, 80138 Naples, Italy
Interests: transition metals; homogeneous catalysis; supported homogeneous catalysis; ligand design; bio-active platinum compounds

Dr. Roberto Esposito

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Department of Science Chemistry, Monte S. Angelo University Federico II, via Cintia 21, 80126 Napoli, Italy
Interests: transition metals; homogeneous catalysis; supported homogeneous catalysis; ligand design; bio-active platinum compounds
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Dear Colleagues,

In recent years, there has been a significant increase in biodiesel production, which involves the mixture of fatty acid methyl esters obtained through the trans-esterification of vegetable oils with methanol. Consequently, today, close to two million tons per year of glycerol, the by-product of the reaction, is available. The generous availability, along with the beneficial eco-toxicologic profile of this functionalized C3 molecule, has motivated the scientific community to convert glycerol into high added-value chemicals through selective oxidation, oligomerization, hydrogenation, acetylation, dehydration, chlorination, pyrolysis, and esterification. The result is a wide range of products with applications such as surfactants, additives, solvents, and monomers.

The methodology of choice for these transformations is catalysis, and recent literature demonstrates great effort to develop catalytic systems, both homogeneous and heterogeneous, that are capable of meeting strict sustainability requirements.

This Special Issue of Catalysts aims to present a collection of the most recent progress and trends in improving already known glycerol transformations. This will include proposed useful conversions of glycerol along with theoretical understanding of the catalytic processes.

Prof. Dr. Francesco Ruffo
Dr. Roberto Esposito
Guest Editors

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Keywords

glycerol
biodiesel
catalytic glycerol valorization
catalytic glycerol acetylation
catalytic glycerol chlorination
catalytic glycerol dehydration
catalytic glycerol esterification
catalytic glycerol hydrogenation
catalytic glycerol ketalation
catalytic glycerol oligomerization
catalytic glycerol oxidation
catalytic glycerol pyrolysis.

Published Papers (11 papers)

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Editorial

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1 pages, 146 KiB

Open AccessEditorial

Editorial to the Special Issue “Catalytic Valorisation of Glycerol: Strategies and Perspectives”

by Francesco Ruffo and Roberto Esposito

Catalysts 2023, 13(1), 64; https://doi.org/10.3390/catal13010064 - 29 Dec 2022

Cited by 1 | Viewed by 766

Abstract

Chemical manufacturing has undergone profound changes over the past twenty years [...] Full article

(This article belongs to the Special Issue Catalytic Valorization of Glycerol: Strategies and Perspectives)

Research

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23 pages, 28630 KiB

Open AccessArticle

Valorization of Solketal Synthesis from Sustainable Biodiesel Derived Glycerol Using Response Surface Methodology

by Gayathri Arun, Muhammad Ayoub, Zulqarnain, Umesh Deshannavar, Mohd Hizami Mohd Yusoff, Sarah Farrukh and Farooq Sher

Catalysts 2021, 11(12), 1537; https://doi.org/10.3390/catal11121537 - 16 Dec 2021

Cited by 17 | Viewed by 2953

Abstract

Biodiesel production has gained considerable importance over the last few decades due to the increase in fossil fuel prices as well as toxic emissions of oxygen and nitrogen. The production of biodiesel via catalytic transesterification produces crude glycerol as a co-product along with biodiesel, amounting to 10% of the total biodiesel produced. Glycerol has a low value in its impure form, and the purification of glycerol requires sophisticated technologies and is an expensive process. The conversion of crude glycerol into value-added chemicals such as solketal is the best way to improve the sustainability of biodiesel synthesis using the transesterification reaction. Therefore, the conversion of crude glycerol into the solketal was investigated in a batch reactor simulation model developed by the Aspen Plus V11.0. The non-random two liquid theory (NRTL) method was used as a thermodynamic property package to study the effect of four input ketalization parameters. The model was validated with the findings of previous experimental studies of solketal synthesis using sulfuric acid as a catalyst. The influence of the following operating parameters was investigated: reaction time of 10,000 to 60,000 s, reaction temperature of 303 to 323 K, acetone to glycerol molar ratio of 2:1 to 10:1, and catalyst concentration of 0.005 to 0.03 wt %. The optimum solketal yield of 81.36% was obtained at the optimized conditions of 313 K, 9:1, 0.03 wt %, and 40,000 s. The effect of each input parameter on the ketalization process and interaction between input and output parameters was investigated by using the response surface methodology (RSM) optimizer. The relationship between independent and response variables developed by RSM fit most of the simulation data, which showed the accuracy of the model. A second-order differential equation fit the simulation data well and showed an R² value of 0.99. According to the findings of RSM, the influence of catalyst amount, acetone to glycerol molar ratio, and reaction time were more significant on solketal yield. The effect of temperature on the performance of the reaction was not found to be significant because of the exothermic nature of the process. The findings of this study showed that biodiesel-derived glycerol can be effectively utilized to produce solketal, which can be used for a wider range of applications such as a fuel additive. However, further work is required to enhance the solketal yield by developing new heterogeneous catalysts so that the industrial implementation of its production can be made possible. Full article

(This article belongs to the Special Issue Catalytic Valorization of Glycerol: Strategies and Perspectives)

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17 pages, 4509 KiB

Open AccessFeature PaperArticle

Calcium Hydroxyapatite: A Highly Stable and Selective Solid Catalyst for Glycerol Polymerization

by Negisa Ebadipour, Sébastien Paul, Benjamin Katryniok and Franck Dumeignil

Catalysts 2021, 11(10), 1247; https://doi.org/10.3390/catal11101247 - 17 Oct 2021

Cited by 11 | Viewed by 1848

Abstract

Calcium-based catalysts are of high interest for glycerol polymerization due to their high catalytic activity and large availability. However, their poor stability under reaction conditions is an issue. In the present study, we investigated the stability and catalytic activity of Ca-hydroxyapatites (HAps) as one of the most abundant Ca-source in nature. A stochiometric, Ca-deficient and Ca-rich HAps were synthesized and tested as catalysts in the glycerol polymerization reaction. Deficient and stochiometric HAps exhibited a remarkable 100% selectivity to triglycerol at 15% of glycerol conversion at 245 °C after 8 h of reaction in the presence of 0.5 mol.% of catalyst. Moreover, under the same reaction conditions, Ca-rich HAp showed a high selectivity (88%) to di- and triglycerol at a glycerol conversion of 27%. Most importantly, these catalysts were unexpectedly stable towards leaching under the reaction conditions based on the ICP-OES results. However, based on the catalytic tests and characterization analysis performed by XRD, XPS, IR, TGA-DSC and ICP-OES, we found that HAps can be deactivated by the presence of the reaction products themselves, i.e., water and polymers. Full article

(This article belongs to the Special Issue Catalytic Valorization of Glycerol: Strategies and Perspectives)

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15 pages, 7510 KiB

Open AccessArticle

Non-Porous Sulfonic Acid Catalysts Derived from Vacuum Residue Asphaltenes for Glycerol Valorization via Ketalization with Acetone

by Vadim Samoilov, Mariia Kniazeva, Tatyana Kuchinskaya, Lev Foss, Dmitry Borisov, Makhmut Yakubov and Anton Maximov

Catalysts 2021, 11(7), 776; https://doi.org/10.3390/catal11070776 - 26 Jun 2021

Cited by 4 | Viewed by 1643

Abstract

In this study, an approach for the preparation of heterogeneous acid catalysts based on asphaltenes isolated from vacuum residue is proposed. Varying the conditions for the sulfonation of asphaltenes made it possible to obtain materials with an acid value of 1.16 to 2.76 meq g⁻¹ and a total sulfur content of 6.4 to 12.3 wt%. The samples obtained were characterized by acid-base titration, nitrogen adsorption, sulfur elemental analysis and transmission electron microscopy techniques, and were studied as potential acid catalysts in the ketalization reaction between glycerol and acetone. Sulfonated asphaltenes (SA) were characterized by a homogeneous distribution of sulfonic groups over the granule surface and an almost complete absence of a porous structure. The ketalization reaction in the presence of SA proceeded without intradiffusion restrictions; as a result of which, their activity was higher than for known heterogeneous catalysts. The most active SA sample (total acid value, 1.16 meq g⁻¹) had an apparent activation energy of 18.0 kJ mol⁻¹, which was lower than the value obtained for the zeolite BEA-40 (29–53 kJ mol⁻¹) and the Amberlyst 36 resin (27 kJ mol⁻¹), and was close to the value for the homogeneous p-TSA catalyst (14.5 kJ mol⁻¹). The SA heterogeneous catalysts did not show any acid leaching and had no loss of activity after five catalytic cycles, with the total turnover number TON = 7247. Full article

(This article belongs to the Special Issue Catalytic Valorization of Glycerol: Strategies and Perspectives)

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19 pages, 6934 KiB

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Self-Assembled Hybrid ZnO Nanostructures as Supports for Copper-Based Catalysts in the Hydrogenolysis of Glycerol

by Lama Omar, Noémie Perret and Stephane Daniele

Catalysts 2021, 11(4), 516; https://doi.org/10.3390/catal11040516 - 20 Apr 2021

Cited by 11 | Viewed by 2196

Abstract

This study describes the use of new ZnO/PAAH hybrid nanomaterials (PAAH = polyacrylic acid) as copper catalyst supports for the hydrogenolysis of glycerol. A study of the synthesis parameters (washing process, temperatures of synthesis and calcination) of these hybrid supports has allowed us to vary their morphology and specific surface area and ultimately the sizes and dispersion of the copper nanoparticles, and to perform a general analysis of their effects on the catalytic performance of the materials. All catalysts were synthesized by the urea deposition-precipitation method (DPU) and were fully characterized to establish a structure–activity relationship. Optimization of the synthesis and catalytic conditions allowed remarkable yields/conversions of the order of 70% for selectivities in 1,2 propanediol of 90%. Full article

(This article belongs to the Special Issue Catalytic Valorization of Glycerol: Strategies and Perspectives)

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14 pages, 2141 KiB

Open AccessArticle

Improving Product Yield in the Direct Carboxylation of Glycerol with CO₂ through the Tailored Selection of Dehydrating Agents

by Nurul Razali and James McGregor

Catalysts 2021, 11(1), 138; https://doi.org/10.3390/catal11010138 - 18 Jan 2021

Cited by 10 | Viewed by 2980

Abstract

Improved yields of, and selectivities to, value-added products synthesised from glycerol are shown to be achieved through the judicious selection of dehydrating agents and through the development of improved catalysts. The direct carboxylation of glycerol with CO₂ over lanthanum-based catalysts can yield glycerol carbonate in the presence of basic species, or acetins in the presence of acidic molecules. The formation of glycerol carbonate is thermodynamically limited; removal of produced water shifts the chemical equilibrium to the product side. Acetonitrile, benzonitrile and adiponitrile have been investigated as basic dehydrating agents to promote glycerol carbonate synthesis. In parallel, acetic anhydride has been studied as an acidic dehydrating agent to promote acetin formation. Alongside this, the influence of the catalyst synthesis method has been investigated allowing links between the physicochemical properties of the catalyst and catalytic performance to be determined. The use of acetonitrile and La catalysts allows the results for the novel dehydrating agents to be benchmarked against literature data. Notably, adiponitrile exhibits significantly enhanced performance over other dehydrating agents, e.g., achieving a 5-fold increase in glycerol carbonate yield with respect to acetonitrile. This is in part ascribed to the fact that each molecule of adiponitrile has two nitrile functionalities to promote the reactive removal of water. In addition, mechanistic insights show that adiponitrile results in reduced by-product formation. Considering by-product formation, 4-hydroxymethyl(oxazolidin)-2-one (4-HMO) has, for the first time, been observed in all reaction systems using cyanated species. Studies investigating the influence of the catalyst synthesis route show a complex relationship between surface basicity, surface area, crystallite phase and reactivity. These results suggest alternative strategies to maximise the yield of desirable products from glycerol through tailoring the reaction chemistry and by-product formation via an appropriate choice of dehydrating agents and co-reagents. Full article

(This article belongs to the Special Issue Catalytic Valorization of Glycerol: Strategies and Perspectives)

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12 pages, 2084 KiB

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Kinetic Modeling of Solketal Synthesis from Glycerol and Acetone Catalyzed by an Iron(III) Complex

by Francesco Taddeo, Roberto Esposito, Vincenzo Russo and Martino Di Serio

Catalysts 2021, 11(1), 83; https://doi.org/10.3390/catal11010083 - 09 Jan 2021

Cited by 14 | Viewed by 3223

Abstract

In the last few years, the depletion of the fossil sources and their negative effect on the environment has led to find new alternatives; among these, biodiesel is considered one of the most promising for this purpose. Biodiesel can be produced from the transesterification of vegetable oils or animal fats, obtaining glycerol as a by-product. Glycerol can be used in different processes and one of the most interesting is the condensation with acetone to produce solketal. Among its applications, plasticizers, solvents, and pharmaceutical formulations are the most common. In this work, the attention was focused on the reaction between glycerol and acetone to give solketal promoted by an iron(III) complex. The reaction mechanism was hypothesized, and the kinetics was studied in a batch reactor. Finally, the thermodynamic and kinetic parameters were determined with a reliable model investigating the phenomena that occurred in the reaction network. Full article

(This article belongs to the Special Issue Catalytic Valorization of Glycerol: Strategies and Perspectives)

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17 pages, 6403 KiB

Open AccessArticle

Deep Control of Linear Oligomerization of Glycerol Using Lanthanum Catalyst on Mesoporous Silica Gel

by Daniela Caputo, Michele Casiello, Antonella Milella, Werner Oberhauser, Alfonso Maffezzoli, Angelo Nacci, Caterina Fusco and Lucia D’Accolti

Catalysts 2020, 10(10), 1170; https://doi.org/10.3390/catal10101170 - 12 Oct 2020

Cited by 7 | Viewed by 2125

Abstract

The valorization of glycerol (1), a waste of biodiesel production of Fatty Acid Methyl Esters (FAMEs), adopting a “green” approach, represents an important goal of sustainable chemistry. While the polymerization of 1 to hyperbranched oligomers is a well-established process, the linear analogues are difficult to obtain. In this context, we explore the reaction without the solvent of heterogeneous hybrid La(III)O-KIT-6 catalyst (2), which is based on lanthanum oxide on mesoporous silica gel, showing a superior linear selectivity compared to most of the analogous catalysts recently reported. Full article

(This article belongs to the Special Issue Catalytic Valorization of Glycerol: Strategies and Perspectives)

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Review

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15 pages, 2069 KiB

Open AccessFeature PaperReview

Glycerol and Catalysis by Waste/Low-Cost Materials—A Review

by Ana Alice Farias da Costa, Alex de Nazaré de Oliveira, Roberto Esposito, Christophe Len, Rafael Luque, Renata Coelho Rodrigues Noronha, Geraldo Narciso da Rocha Filho and Luís Adriano Santos do Nascimento

Catalysts 2022, 12(5), 570; https://doi.org/10.3390/catal12050570 - 23 May 2022

Cited by 16 | Viewed by 3170 | Correction

Abstract

The growing global demand for renewable energy sources can be reached using biofuels such as biodiesel, for example. The most used route to produce biodiesel is the transesterification reaction of oils or fats with short-chain alcohols, generating fatty acid esters (biodiesel) and a very important by-product, glycerol (Gly). Gly is widely used in different sectors of the industry, and in order to add value to this by-product, heterogeneous catalysis becomes a relevant tool, whether to transform glycerol into other chemical products of interest or even use it in the production of catalysts. Among the several studies found in the literature, the use of low-cost materials and/or wastes from the most diverse activities to prepare active catalytic materials for the transformation of Gly has been increasingly reported due to its valuable advantages, especially related to the cost of raw materials and environmental aspects. Thus, this brief review article presents the relationship between catalysis, low-cost materials, waste, and glycerol, through different studies that show glycerol being transformed through reactions catalyzed by materials produced from low-cost sources/waste or with the glycerol itself used as a catalyst. Full article

(This article belongs to the Special Issue Catalytic Valorization of Glycerol: Strategies and Perspectives)

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23 pages, 4973 KiB

Open AccessReview

An Overview of the Latest Advances in the Catalytic Synthesis of Glycerol Carbonate

by Debora Procopio and Maria Luisa Di Gioia

Catalysts 2022, 12(1), 50; https://doi.org/10.3390/catal12010050 - 02 Jan 2022

Cited by 26 | Viewed by 4040

Abstract

In recent years, the development of renewable energy alternatives to traditional fossil fuels has become one of the major challenges all over the world, due to the decline of fossil fuel reserves and their effect on global warming. Biodiesel has become a popular alternative energy source to reduce gas emissions compared to traditional fossil fuels. According to statistics, a nine-fold increase in global biofuel production between 2000 and 2020 was observed. However, its production generates a large amount of glycerol as a by-product, posing an environmental problem when disposed directly in landfills or by incineration. Therefore, low-value glycerol should be converted into high value-added derivatives. As glycerol carbonate is one of the most important derivatives of glycerol, this review aims to discuss the studies over the last ten years about glycerol carbonate synthetic methods, including the typical routes such as phosgene, esterification reaction, urea, oxidative and direct carbonylation as well as several rare synthetic procedures. At the same time, it summarizes the different catalytic reaction systems of each route comparing the advantages and disadvantages of various catalysts and evaluating their catalytic activity. Finally, the future development of glycerol carbonate synthesis is prospected from the point of view of development, technology research and industrialization. Full article

(This article belongs to the Special Issue Catalytic Valorization of Glycerol: Strategies and Perspectives)

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41 pages, 3338 KiB

Open AccessFeature PaperEditor’s ChoiceReview

Recent Advances in Glycerol Catalytic Valorization: A Review

by Manuel Checa, Sergio Nogales-Delgado, Vicente Montes and José María Encinar

Catalysts 2020, 10(11), 1279; https://doi.org/10.3390/catal10111279 - 03 Nov 2020

Cited by 98 | Viewed by 7701

Abstract

Once a biorefinery is ready to operate, the main processed materials need to be completely evaluated in terms of many different factors, including disposal regulations, technological limitations of installation, the market, and other societal considerations. In biorefinery, glycerol is the main by-product, representing around 10% of biodiesel production. In the last few decades, the large-scale production of biodiesel and glycerol has promoted research on a wide range of strategies in an attempt to valorize this by-product, with its transformation into added value chemicals being the strategy that exhibits the most promising route. Among them, C3 compounds obtained from routes such as hydrogenation, oxidation, esterification, etc. represent an alternative to petroleum-based routes for chemicals such as acrolein, propanediols, or carboxylic acids of interest for the polymer industry. Another widely studied and developed strategy includes processes such as reforming or pyrolysis for energy, clean fuels, and materials such as activated carbon. This review covers recent advances in catalysts used in the most promising strategies considering both chemicals and energy or fuel obtention. Due to the large variety in biorefinery industries, several potential emergent valorization routes are briefly summarized. Full article

(This article belongs to the Special Issue Catalytic Valorization of Glycerol: Strategies and Perspectives)

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