Bio-Glycerol as Sustainable Raw Material for Biorefinery - Biocatalytic Synthesis of Glycerol Carbonate (original) (raw)
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Environmental-friendly strategy for biocatalytic conversion of waste glycerol to glycerol carbonate
2014
In this work, the conversion of waste glycerol from biodiesel production to glycerol carbonate (GlyC) as added-value product has been investigated. The transformation of waste glycerol to GlyC has been achieved taking the advantage of dimethyl carbonate (DMC) reaction with glycerol catalyzed by heterogeneous lipase biocatalyst under solvent-free conditions. The biocatalyst design was the lipase enzyme anchored on magnetic nano-particle surface via covalent binding. Waste glycerol with different matrixes according to the feedstock patterns (e.g. soybean, sunflower, rape, corn, olive, palm, and residual oil) has been tested for GlyC bio-synthesis. Content of MeOH, H 2 O, metals and salts from sample matrix (e.g. waste glycerol) was characterized using gravimetric and energy dispersive X-ray fluorescence (EDXRF) spectrometry techniques. Impurities effects of the waste glycerol on the performance of the biocatalytic process and also different strategies to avoid them were investigated.
Central European Journal of Chemistry, 2014
Bio-glycerol (B-Gly) was converted to glycerol carbonate (GlyC) as an important added-value product using an advanced biocatalytic process involving the glycerol (Gly) carbonylation with dimethyl carbonate (DMC) assisted by a heterogeneous enzyme biocatalyst (lipase covalently attached on magnetic nano-particles surface). The biocatalytic process was set up optimizing the experimental parameters (e.g. molar ratio of the reagents, temperature, incubation time and catalyst content). In addition, the efficiency of DMC as carbonylation agent was evaluated against diethyl carbonate (DEC) and dibenzyl carbonate (DBC). B-Gly was tested as a raw material for GlyC synthesis in the set up biocatalytic process using commercial pure Gly (S-Gly) as reference. B-Gly was produced based on a conventional transesterification process applied to both crude and residual sun-flower oil. Crude sun-flower oil was the typical commercial one and residual sun-flower oil was that recovered from the cooking process. Comparable performances were obtained using B-Gly from residual oil and S-Gly (e.g. conversion of Gly of 36% and 45% for selectivity in GlyC of 90% and 92%, respectively), while the use of B-Gly from crude residual oil led to a Gly conversion of only 27% with selectivity in GlyC of 95%.
Recent Advances in Conversion of Glycerol: A Byproduct of Biodiesel Production to Glycerol Carbonate
Journal of Chemistry
Owing to erupted ecological concerns and escalated energy consumption, biodiesel produced by transesterifying nonedible and used cooking oils has been acknowledged as a viable source of clean and sustainable energy, alternative to fossil fuels. This transesterification process led to an excessive supply of glycerol as the primary byproduct which can then be transformed into value-added derivatives, primarily glycerol carbonate (GC), thereby drawing attention to its potential use in industrial applications. Although several methods for synthesis of GC utilize glycerol as building block, the transesterification approach using dimethyl carbonate (DMC) is the most effective route implementing safer and greener reaction conditions. This review is focused on different types of heterogeneous catalysts and characterization techniques used for identifying and deactivating those catalysts, covering the literature from the last decade to till date on this topic. Potent applications of GC as a ...
Energy Conversion and Management, 2014
Driven by high energy demand and environmental concerns, biodiesel as a substitute for fossil fuels is recognized to be promising renewable and clean energy. The increase in the biodiesel plant dramatically leads to the oversupply of its by-product glycerol in the biodiesel industries. Developing new industrial uses for glycerol is essential to increase the net energy and sustainability of biodiesel. Moreover, glycerol has great potential to be converted into marketable and valuable chemicals. The conversion of glycerol to glycerol carbonate (GC) has been extensively studied and transesterification of glycerol to GC has been proven to be the most promising route. Aimed to reveal the underlying mechanism of this successful conversion path, this paper reviews the chemo-and biocatalytic transesterification of glycerol with different carbonates sources. Also, a detail elucidation of the influence of the catalysts and operating conditions on the GC yield is included to provide an insight into the process. In addition, the future direction of glycerol carbonate production via catalytic transesterification is provided in this review.
Waste and Biomass Valorization, 2016
Synthesis of organic carbonates specifically glycerol carbonate has become a major concern among researchers due to its interesting chemical properties. In this study, we report the direct utilization of two different sources of crude glycerol in glycerolysis reaction with urea for the synthesis of glycerol carbonate using potassium silicate containing boiler ash as a catalyst. The level of interference of moisture and methanol content in crude glycerol was studied by mimicking conditions in pure glycerol and it was found that moisture at 10 wt% significantly effects the conversion of glycerol while methanol at 5 wt% affects the selectivity towards glycerol carbonate. However, due to the low moisture and methanol content in crude glycerol, comparable yield % of glycerol carbonate with commercial pure glycerol as starting feedstock was noted. Besides, the study also found that the potassium methylate and sodium methylate used as catalysts for the commercial production of biodiesel can be also used as an effective catalyst for the synthesis of glycerol carbonate. The current approach is a near approach for a greener environment which proposes use of both catalyst and glycerol derived from waste sources.
Resource-Efficient Technologies, 2017
Crude glycerol is produced as a by-product from biodiesel production via trans-esterification with methanol and this process accounts for 10% (w/w) of the total biodiesel produced worldwide. The glycerol glut created can be utilized to increase biodiesel profitability since disposal can pose a threat to the environment. The need is to transform this surplus crude glycerol into added-value products. Biological based conversions are efficient in providing products that are drop-in replacements for petrochemicals and offer functionality advantage, commanding higher price with the potential to increase bio-refinery revenue. Glycerol is a stable and multifunctional compound used as a building block in fine chemical synthesis like bio-polymers, polyunsaturated fatty acids, ethanol, hydrogen, n-butanol, glycerol carbonate, glycerol acetyl esters etc. Bio-catalysts add higher value to bio based products by catalyzing not only their selective modification, but also their synthesis under controlled and mild conditions. This article focuses on different bioconversion technologies of crude-glycerol to value added industrial products-obtained as waste from current bio-diesel production. We abridge the recent relevant approach for the production of various platform chemicals from bio-glycerol over enzyme and chemical catalysts.
Energies
As a promising alternative renewable liquid fuel, biodiesel production has increased and eventually led to an increase in the production of its by-product, crude glycerol. The vast generation of glycerol has surpassed the market demand. Hence, the crude glycerol produced should be utilized effectively to increase the viability of biodiesel production. One of them is through crude glycerol upgrading, which is not economical. A good deal of attention has been dedicated to research for alternative material and chemicals derived from sustainable biomass resources. It will be more valuable if the crude glycerol is converted into glycerol derivatives, and so, increase the economic possibility of the biodiesel production. Studies showed that glycerol carbonate plays an important role, as a building block, in synthesizing the glycerol oligomers at milder conditions under microwave irradiation. This review presents a brief outline of the physio-chemical, thermodynamic, toxicological, product...
Catalytic transesterification of glycerol: Optimization for production of glycerol carbonate
Malaysian Journal of Fundamental and Applied Sciences, 2019
The purpose of this research was to study the effect of reaction temperature, reaction time and dimethyl carbonate:glycerol (DMC:Gly) molar ratio on the conversion of glycerol and yield of glycerol carbonate. The reaction was further optimized with central composite design (CCD), 15 runs of transesterification reaction were conducted. Meanwhile, the calcined calcium oxide catalyst was fixed at catalyst/glycerol molar ratio at 0.06 while the stirring rate was maintained at 1000 rpm for every runs. ANOVA results indicated that reaction temperature and reactants ratio (DMC:Gly) influenced the yield significantly. Synergy effect of reaction temperature with reaction time and reaction temperature with DMC:Gly molar ratio seem to have greater significance on the conversion instead of a single parameter. Under optimization studies, the maximum possible conversion and yield were 100% and 96.36% respectively which could be accomplished at 60.16 °C reaction temperature with 1.19 hour reaction...
Fermentation
Glycerol carbonate (GC) is a value-added product originating from the valorization of widely available glycerol (Gly), a side stream from the production of biodiesel. Here we approach the production of this chemical comparing two reactions based on the transesterification of Gly with dimethyl carbonate (DMC) and ethylene carbonate (EC). When using DMC, it was observed that the free enzyme CALB (lipase B from Candida antarctica) gave the best results, whereas Eversa Transform (a genetic modification of Thermomyces lanuginosus lipase) performed better than the rest if EC was the reagent. With the selected catalysts, their immobilized analogous enzymes Novozym 435 and Lypozyme TL IM, respectively, were also tested. Observing that the yields for the reaction with EC were significantly faster, other operating variables were evaluated, resulting the best performance using a closed system, tert-butanol as solvent, a concentration of enzyme Eversa Transform of 3% w/w, a molar excess of EC:G...