New Glycerol Upgrading Processes

A special issue of Catalysts (ISSN 2073-4344).

Deadline for manuscript submissions: closed (30 April 2020) | Viewed by 38759

Special Issue Editor


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Guest Editor
Department of Chemical Engineering, College of Chemical Sciences, Complutense University of Madrid, 28040 Madrid, Spain
Interests: glycerol; biodiesel; valorization; catalysts; carbonates; ketals; monomers; ethers; esters; lactic acid; hydrogen; acrolein; acrilonitrile; acrylic acid; glycidol; diols; refining; oxidation; dehydration
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Special Issue Information

Dear Colleagues,

Among renewable energies, biofuels—particularly biodiesel and bioethanol—have seen their market share significantly increase throughout the past several decades, being the main products of the first biorefineries. These are now implemented in new processes and products to complement and/or substitute fossil fuels and materials derived from oil, gas, and coal, on one hand, and a plethora of chemicals produced in the petrochemical industry, on the other.

In the case of biodiesel, approximately 10% of glycerol is generated with respect to the mass of this biofuel as a by-product of the manufacture process, using both homogeneous and heterogeneous catalysis for the transesterification process. Glycerol has traditionally been produced from tallow and oil by acid hydrolysis, and it can also be produced by several microorganisms, the latter method being a promising biorefinery approach in the event that glycerol production needs to be enhanced. However, presently, most of the glycerol production comes from the biodiesel production process as a side stream, which has led to a saturation of the existing traditional glycerol market in the chemical, food, and pharmaceutical sectors. As a consequence, prices have remarkably dropped, thereby affecting the profitability of biodiesel production processes. Therefore, glycerol—either crude or pure—could be a waste to be disposed of or, on the other hand, it could become an opportunity by turning it into a platform chemical. A great number of compounds can be derived from glycerol by thermochemical, catalytic, and biochemical routes, including microbial bioprocesses, in which it is employed as a carbon source. For this purpose, there is an enormous amount of scientific and technical literature from the 1990s and the first decade of the 2000s describing new catalysts, biocatalysts, processes, and products that show the huge potential of glycerol as a building block and feedstock.

The aim of this Special Issue is to provide a general and up-to-date overview of the wide variety of processes and products that are now being devised, researched, and implemented using glycerol as a starting building block and carbon source for chemical synthesis, thermochemical transformations, and biochemical/microbial processes. In this sense, a part of the future biorefineries is being built on glycerol as the corner stone.

Dr. Miguel Ladero Galán
Guest Editor

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Keywords

  • glycerol 
  • catalysis 
  • biocatalysis 
  • microbial transformations 
  • reforming 
  • biorefinery
  • platform chemical

Published Papers (10 papers)

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Editorial

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5 pages, 2152 KiB  
Editorial
New Glycerol Upgrading Processes
by Miguel Ladero
Catalysts 2021, 11(1), 103; https://doi.org/10.3390/catal11010103 - 13 Jan 2021
Cited by 9 | Viewed by 1924
Abstract
Energy policies in the US and in the EU during the last decades have been focused on enhanced oil and gas recovery, including the so-called tertiary extraction or enhanced oil recovery (EOR), on one hand, and the development and implementation of renewable energy [...] Read more.
Energy policies in the US and in the EU during the last decades have been focused on enhanced oil and gas recovery, including the so-called tertiary extraction or enhanced oil recovery (EOR), on one hand, and the development and implementation of renewable energy vectors, on the other, including biofuels as bioethanol (mainly in US and Brazil) and biodiesel (mainly in the EU) [...] Full article
(This article belongs to the Special Issue New Glycerol Upgrading Processes)
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Research

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20 pages, 3871 KiB  
Article
VAlPOs as Efficient Catalysts for Glycerol Conversion to Methanol
by Gheorghița Mitran, Florentina Neațu, Ștefan Neațu, Mihaela M. Trandafir and Mihaela Florea
Catalysts 2020, 10(7), 728; https://doi.org/10.3390/catal10070728 - 1 Jul 2020
Cited by 10 | Viewed by 3194
Abstract
The catalytic activity of a series of vanadium aluminophosphates catalysts prepared by sol-gel method followed by combustion of the obtained gel was evaluated in glycerol conversion towards methanol. The materials were characterized by several techniques such as X-ray diffraction (XRD), UV-vis, Fourier-transform infrared [...] Read more.
The catalytic activity of a series of vanadium aluminophosphates catalysts prepared by sol-gel method followed by combustion of the obtained gel was evaluated in glycerol conversion towards methanol. The materials were characterized by several techniques such as X-ray diffraction (XRD), UV-vis, Fourier-transform infrared (FTIR), Raman and X-ray photoelectron (XPS) spectroscopies. The amount of vanadium incorporated in aluminophosphates framework played an important role in the catalytic activity, while in the products distribution the key role is played by the vanadium oxidation state on the surface. The sample that contains a large amount of V4+ has the highest selectivity towards methanol. On the sample with the lowest vanadium loading the oxidation path to dihydroxyacetone is predominant. The catalyst with higher content of tetrahedral isolated vanadium species, such V5APO, is less active in breaking the C–C bonds in the glycerol molecule than the one containing polymeric species. Full article
(This article belongs to the Special Issue New Glycerol Upgrading Processes)
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15 pages, 2418 KiB  
Article
High Yield to 1-Propanol from Crude Glycerol Using Two Reaction Steps with Ni Catalysts
by Martín N. Gatti, Julieta L. Cerioni, Francisco Pompeo, Gerardo F. Santori and Nora N. Nichio
Catalysts 2020, 10(6), 615; https://doi.org/10.3390/catal10060615 - 2 Jun 2020
Cited by 16 | Viewed by 2990
Abstract
The objective of the present work is to achieve high yield to 1-propanol (1-POH) by crude glycerol hydrogenolysis in liquid phase and find an alternative to the use of noble metals by employing Ni catalysts. Two Ni catalysts with different supports, alumina (γ-Al [...] Read more.
The objective of the present work is to achieve high yield to 1-propanol (1-POH) by crude glycerol hydrogenolysis in liquid phase and find an alternative to the use of noble metals by employing Ni catalysts. Two Ni catalysts with different supports, alumina (γ-Al2O3), and a phosphorous-impregnated carbon composite (CS-P) were studied and characterized in order to determine their acid properties and metallic phases. With the Ni/γ-Al2O3 catalyst, which presented small particles of metallic Ni interacting with the acid sites of the support, it was possible to obtain a complete conversion of crude glycerol with high selectivity towards 1,2-propylene glycol (1,2 PG) (87%) at 220 °C whereas with the Ni/CS-P catalyst, the presence of AlPOx species and the Ni2P metallic phase supplied acidity to the catalyst, which promoted the C-O bond cleavage reaction of the secondary carbon of 1,2 PG to obtain 1-POH with very high selectivity (71%) at 260 °C. It was found that the employment of two consecutive reaction stages (first with Ni/ γ-Al2O3 at 220 °C and then with Ni/CS-P at 260 °C) allows reaching levels of selectivity and a yield to 1-POH (79%) comparable to noble metal-based catalysts. Full article
(This article belongs to the Special Issue New Glycerol Upgrading Processes)
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12 pages, 747 KiB  
Article
High-Level Production of Succinic Acid from Crude Glycerol by a Wild Type Organism
by Anja Kuenz, Lisa Hoffmann, Katharina Goy, Sarah Bromann and Ulf Prüße
Catalysts 2020, 10(5), 470; https://doi.org/10.3390/catal10050470 - 25 Apr 2020
Cited by 21 | Viewed by 3573
Abstract
With the transition to the bio-based economy, it is becoming increasingly important for the chemical industry to obtain basic chemicals from renewable raw materials. Succinic acid, one of the most important bio-based building block chemicals, is used in the food and pharmaceutical industries, [...] Read more.
With the transition to the bio-based economy, it is becoming increasingly important for the chemical industry to obtain basic chemicals from renewable raw materials. Succinic acid, one of the most important bio-based building block chemicals, is used in the food and pharmaceutical industries, as well as in the field of bio-based plastics. An alternative process for the bio-based production of succinic acid was the main objective of this study, focusing on the biotechnological production of succinic acid using a newly isolated organism. Pure glycerol compared to crude glycerol, at the lowest purity, directly from a biodiesel plant side stream, was successfully converted. A maximum final titer of 117 g L−1 succinic acid and a yield of 1.3 g g−1 were achieved using pure glycerol and 86.9 g L−1 succinic acid and a yield of 0.9 g g−1 using crude glycerol. Finally, the succinic acid was crystallized, achieving maximum yield of 95% and a purity of up to 99%. Full article
(This article belongs to the Special Issue New Glycerol Upgrading Processes)
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24 pages, 4223 KiB  
Article
Valorization of Glycerol through the Enzymatic Synthesis of Acylglycerides with High Nutritional Value
by Daniel Alberto Sánchez, Gabriela Marta Tonetto and María Luján Ferreira
Catalysts 2020, 10(1), 116; https://doi.org/10.3390/catal10010116 - 14 Jan 2020
Cited by 9 | Viewed by 3059
Abstract
The production of specific acylglycerides from the selective esterification of glycerol is an attractive alternative for the valorization of this by-product of the biodiesel industry. In this way, products with high added value are generated, increasing the profitability of the overall process and [...] Read more.
The production of specific acylglycerides from the selective esterification of glycerol is an attractive alternative for the valorization of this by-product of the biodiesel industry. In this way, products with high added value are generated, increasing the profitability of the overall process and reducing an associated environmental threat. In this work, nutritional and medically interesting glycerides were obtained by enzymatic esterification through a two-stage process. In the first stage, 1,3-dicaprin was obtained by the regioselective esterification of glycerol and capric acid mediated by the commercial biocatalyst Lipozyme RM IM. Under optimal reaction conditions, 73% conversion of fatty acids and 76% selectivity to 1,3-dicaprin was achieved. A new model to explain the participation of lipase in the acyl migration reaction is presented. It evaluates the conditions in the microenvironment of the active site of the enzyme during the formation of the tetrahedral intermediate. In the second stage, the esterification of the sn-2 position of 1,3-dicaprin with palmitic acid was performed using the lipase from Burkholderia cepacia immobilized on chitosan as the biocatalyst. A biocatalyst containing 3 wt % of lipase showed good activity to esterify the sn-2 position of 1,3-dicaprin. A mixture of acylglycerides consisting mainly of capric acid esterified at sn-1 and sn-3, and of palmitic acid at the sn-2 position was obtained as the reaction product. The influence of the biocatalyst mass, the reaction temperature, and the molar ratio of substrates were evaluated for this reaction using a factorial design. Simple models were used to adjust the consumption of reagents and the generation of different products. The reaction product contained between 76% and 90% of acylglycerides with high nutritional value, depending on the reaction conditions. Full article
(This article belongs to the Special Issue New Glycerol Upgrading Processes)
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17 pages, 2567 KiB  
Article
Kinetic Modeling of Dihydroxyacetone Production from Glycerol by Gluconobacter oxydans ATCC 621 Resting Cells: Effect of Fluid Dynamics Conditions
by Susana de la Morena, Mateusz Wojtusik, Victoria E. Santos and Felix Garcia-Ochoa
Catalysts 2020, 10(1), 101; https://doi.org/10.3390/catal10010101 - 10 Jan 2020
Cited by 12 | Viewed by 2703
Abstract
Dihydroxyacetone production from glycerol has been studied. Cultures of Gluconobacter oxydans ATCC 621, a promising microorganism that is able to convert glycerol into dihydroxyacetone, has been employed. In this work, the influence of oxygen transport rate and the fluid dynamic conditions have been [...] Read more.
Dihydroxyacetone production from glycerol has been studied. Cultures of Gluconobacter oxydans ATCC 621, a promising microorganism that is able to convert glycerol into dihydroxyacetone, has been employed. In this work, the influence of oxygen transport rate and the fluid dynamic conditions have been studied working with resting cells cultures. Several experiments were carried out at two different scales: 250 mL Erlenmeyer flasks and a 2 L stirred tank bioreactor, varying the agitation speed. Product and substrate concentration were determined employing high-performance liquid chromatography. Additionally, oxygen concentration was measured in the runs carried out in stirred tank reactors. Taking into account the results obtained in these experiments, three different behaviors were observed, depending on the mass transfer and chemical reactions rates. For experiments with low stirring speed (below 200 rpm for shake flasks and 300 rpm for reactors), the oxygen transport rate is the controlling step, while at high stirring speed (over 300 rpm in shake flasks and 560 rpm in the bioreactor), the chemical reaction is controlling the overall process rate. In some runs conducted at medium agitation, a mix control was found. All the kinetic models were able to reproduce experimental data and fulfill thermodynamic and statistical criteria, highlighting the importance of the mass transfer rate upon this system. Full article
(This article belongs to the Special Issue New Glycerol Upgrading Processes)
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19 pages, 3991 KiB  
Article
Synthesis of Ibuprofen Monoglyceride in Solventless Medium with Novozym®435: Kinetic Analysis
by Marianela Ravelo, Mateusz Wojtusik, Miguel Ladero and Félix García-Ochoa
Catalysts 2020, 10(1), 76; https://doi.org/10.3390/catal10010076 - 4 Jan 2020
Cited by 8 | Viewed by 3835
Abstract
This study investigates the enzymatic esterification of glycerol and ibuprofen in a solventless medium catalyzed by immobilized lipase B from Candida antarctica (Novozym®435). Fixing the concentration of this enzymatic solid preparation at 30 g·L−1, and operating at a constant [...] Read more.
This study investigates the enzymatic esterification of glycerol and ibuprofen in a solventless medium catalyzed by immobilized lipase B from Candida antarctica (Novozym®435). Fixing the concentration of this enzymatic solid preparation at 30 g·L−1, and operating at a constant stirring speed of 720 rpm, the temperature was changed between 50 and 80 °C, while the initial concentration of ibuprofen was studied from 20 to 100 g·L−1. Under these conditions, the resistance of external mass transport can be neglected, as confirmed by the Mears criterion (Me < 0.15). However, the mass transfer limitation inside the pores of the support has been evidenced. The values of the effectiveness factor (η) vary between 0.08 and 0.16 for the particle size range considered according to the Weisz–Prater criteria. Preliminary runs permit us to conclude that the enzyme was deactivated at medium to high temperatures and initial concentration values of ibuprofen. Several phenomenological kinetic models were proposed and fitted to all data available, using physical and statistical criteria to select the most adequate model. The best kinetic model was a reversible sigmoidal model with pseudo-first order with respect to dissolved ibuprofen and order 2 with respect to monoester ibuprofen, assuming the total first-order one-step deactivation of the enzyme, with partial first order for ibuprofen and enzyme activity. Full article
(This article belongs to the Special Issue New Glycerol Upgrading Processes)
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18 pages, 1964 KiB  
Article
Optimization of Hydrogen Yield from the Anaerobic Digestion of Crude Glycerol and Swine Manure
by Aguilar-Aguilar F. A., Adriana Longoria, Juantorena A. U., Santos A. S., Pantoja L. A. and P. J. Sebastian
Catalysts 2019, 9(4), 316; https://doi.org/10.3390/catal9040316 - 31 Mar 2019
Cited by 7 | Viewed by 3374
Abstract
Crude glycerol and swine manure are residues with exponential production in Mexico, nonetheless, they have the potential to generate hydrogen from the fermentation process. For this reason, this study has evaluated the optimization of hydrogen yield from crude glycerol and swine manure, using [...] Read more.
Crude glycerol and swine manure are residues with exponential production in Mexico, nonetheless, they have the potential to generate hydrogen from the fermentation process. For this reason, this study has evaluated the optimization of hydrogen yield from crude glycerol and swine manure, using the response surface methodology. The response surface methodology helps in the compression of the mixture of crude glycerol/ swine manure, with the production of hydrogen as a result, which improves the yields of the process, reducing variability and time of development. A central composite design was employed with two factors, six axial points and four central points. The two factors evaluated were crude glycerol and swine manure concentrations, which were examined over a range of 4 to 10 g L−1 and 5 to 15 g L−1, respectively. This study demonstrated that the thermal pretreatment method is still the most suitable method to be applied, mainly in the preparation of hydrogen-producing inoculum. The maximum hydrogen yield was 142.46 mL per gram of volatile solid added. It used up 21.56% of the crude glycerol (2.75 g L−1) and 78.44% (10 g L−1) of the swine manure, maintaining a carbon/nitrogen ratio of 18.06, with a fermentation time of 21 days. The response surface methodology was employed to maximize the hydrogen production of crude glycerol/swine manure ratios by the optimization of factors with few assays and less operational cost. Full article
(This article belongs to the Special Issue New Glycerol Upgrading Processes)
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Review

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20 pages, 2032 KiB  
Review
Valorization of Biodiesel Byproduct Crude Glycerol for the Production of Bioenergy and Biochemicals
by Niravkumar Mahendrasinh Kosamia, Mahdieh Samavi, Bijaya Kumar Uprety and Sudip Kumar Rakshit
Catalysts 2020, 10(6), 609; https://doi.org/10.3390/catal10060609 - 1 Jun 2020
Cited by 52 | Viewed by 7271
Abstract
The rapid growth of global biodiesel production requires simultaneous effective utilization of glycerol obtained as a by-product of the transesterification process. Accumulation of the byproduct glycerol from biodiesel industries can lead to considerable environment issues. Hence, there is extensive research focus on the [...] Read more.
The rapid growth of global biodiesel production requires simultaneous effective utilization of glycerol obtained as a by-product of the transesterification process. Accumulation of the byproduct glycerol from biodiesel industries can lead to considerable environment issues. Hence, there is extensive research focus on the transformation of crude glycerol into value-added products. This paper makes an overview of the nature of crude glycerol and ongoing research on its conversion to value-added products. Both chemical and biological routes of glycerol valorization will be presented. Details of crude glycerol conversion into microbial lipid and subsequent products will also be highlighted. Full article
(This article belongs to the Special Issue New Glycerol Upgrading Processes)
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22 pages, 4651 KiB  
Review
Recent Development of Heterogeneous Catalysis in the Transesterification of Glycerol to Glycerol Carbonate
by Yue Ji
Catalysts 2019, 9(7), 581; https://doi.org/10.3390/catal9070581 - 30 Jun 2019
Cited by 36 | Viewed by 6197
Abstract
Glycerol is one of the most crucial by-products in the production of biodiesel, and owing to its oversaturation in the market, several synthetic strategies have been developed to transform it into other higher value-added products such as glycerol carbonate, epichlorohydrin, 1,3-propanediol, etc. Amongst [...] Read more.
Glycerol is one of the most crucial by-products in the production of biodiesel, and owing to its oversaturation in the market, several synthetic strategies have been developed to transform it into other higher value-added products such as glycerol carbonate, epichlorohydrin, 1,3-propanediol, etc. Amongst them, glycerol carbonate is considered to be the most valuable product. Considering the facile separation and reusability of catalyst, heterogeneous base catalysts have attracted considerable attention due to the obvious advantages over Brϕnsted acid and homogeneous base catalysts in the transesterification of glycerol. Herein, we will give a short overview on the recent development of the heterogeneous catalysis in the transesterification of glycerol with dialkyl carbonate. Focus will be concentrated on the heterogeneous base catalysts including alkaline-earth metal oxides (MgO, CaO, and mixed oxides), hydrotalcites, zeolites, clinoptilolites, organic bases, etc. Their catalytic mechanisms during the heterogeneous process will be elucidated in detail. Full article
(This article belongs to the Special Issue New Glycerol Upgrading Processes)
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