Synthesis of New Acetals and Ketals of Glycerol as Diesel Additives (original) (raw)
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Fuel Processing Technology, 2013
Certain acetals can be produced from renewable resources (bioalcohols) and seem to be good candidates for different applications, such as oxygenated diesel additives. This paper addresses the production of acetals (5-hydroxy-2-methyl-1,3 dioxane and 4-hydroxymethyl-2-methyl-1,3 dioxolane) from glycerol and acetaldehyde using Amberlyst 47 acidic ion exchange resin. This ion exchange resin performed well, recording 100% selectivity toward acetal formation at a suitably high initial glycerol concentration. When the initial acetaldehyde concentration was significantly higher than the glycerol concentration, 2,4,6 trimethyl-1,3,5 trioxane was the main reaction product. Unlike other acetalization reactions, the one studied here does not have thermodynamic limitations, and 100% conversion is achieved under different reaction conditions. A kinetic study was performed in a batch stirred tank reactor to study the influence of different process parameters, such as temperature, feed composition and stirring speed. A pseudo-homogeneous kinetic model was developed to describe this reaction kinetics, proving that its rate is just first order on the acetaldehyde concentration under the conditions studied.
Heterogeneous catalytic reaction of glycerol with acetone for solketal production
MATEC Web of Conferences
The rapid growth of biodiesel industries has also increased the production of glycerol as side product. Without proper treatment, glycerol may cause serious problem for the environment. Glycerol can be reacted with acetone to produce solketal as a fuel additive. The aim of this research was to study the glycerol ketalization with acetone using Amberlyst-15 as catalyst. Experiments were undertaken in a batch reactor. A set of experiment was conducted at varying temperature (35 to 60oC), initial mole ratio of acetone to glycerol (2 – 6) and catalyst loading (1,3,5 and 7% w/w). Sample was analyzed every 30 minutes. The results showed that optimal condition was achieved at temperature of 60 °C, initial mole ratio of acetone to glycerol of 3, and the catalyst load of 3%. The highest glycerol conversion achieved was 87.41 % at 60oC for 3 hours reaction. The Pseudo Steady State Hypothesis (PSSH) has been developed as rnet =k4.CG.CAC/1+k5.CG. Parameter estimation of k4 and k5 were evaluated...
Glycerol (Byproduct of Biodiesel Production) as a Source for Fuels and Chemicals Mini Review
The Open Fuels & Energy Science Journal, 2010
Currently the large surplus of glycerol formed as a by-product during the production of biodiesel offered an abundant and low cost feedstock. Researchers showed a surge of interest in using glycerol as renewable feedstock to produce functional chemicals. This Minireview focuses on recent developments in the conversion of glycerol into valueadded products, including citric acid, lactic acid, 1,3-dihydroxyacetone (DHA), 1,3-propanediol (1,3-PD), dichloro-2- propanol (DCP), acrolein, hydrogen, and ethanol etc. The versatile new applications of glycerol in the everyday life and chemical industry will improve the economic viability of the biodiesel industry.
Glycerol ketals: Synthesis and profits in biodiesel blends
2012
a b s t r a c t Surplus of glycerol due to the increase of biodiesel production has become an economic drawback for the development of biofuel itself. In this work, we show that it is possible to take advantage of glycerol for the synthesis of derivatives such as ketals, which can be used in biodiesel blends. The synthesis of ketals has been successfully carried out in good yields by using a cheap and reusable catalyst, K10 montmorillonite. The analysis of biodiesel blends quality parameters revealed the improvement of their cold properties, but some parameters such as fatty acid methyl ester (FAME) content and oxidation stability do not reached EN14214 specifications. In order to overcome this issue, esterification of the free hydroxyl group has been carried out leading to products with improved and promising properties for biodiesel blends.
Biofuel additive production from glycerol and determination of its effect on some fuel properties
SN Applied Sciences
In this study, the effects of glycerol ethers as a biobased additive on some important fuel properties of the diesel-biodiesel blend are investigated. For this, firstly, glycerol ethers are synthesized by the etherification reaction of glycerol with tert-butyl alcohol with the presence of Amberlyst-15 as an acidic catalyst. The process of synthesis is followed by analyzing product composition through Fourier-transform infrared spectroscopy and gas chromatography-mass spectroscopy. Lastly, synthesized glycerol tert-butyl ethers are mixed with a diesel-biodiesel blend, and the effects of glycerol ethers on the fuel properties are determined. The analysis results show that glycerol tert-butyl ether mixture consists of mono-and di-ethers of glycerol. Due to the dehydration reaction and hindrance effect, the tri-ether of glycerol is not generated. The outcomes of determination of fuel properties reveal that glycerol ethers can be blended with a biodiesel-diesel mixture without any significant change in the fuel properties by fully meeting the ASTM D7467 standard, indicating glycerol ethers could serve as a biobased additive to diesel-biodiesel blend.
Environmental Technology, 2017
Synthesis of bioadditives of fuels from biodiesel-derived glycerol by esterification with acetic acid on solid catalysts In this paper, glycerol esterification with acetic acid was studied on several solid acid catalysts: Al 2 O 3 , Al-MCM-41, HPA/SiO 2 , HBEA, Amberlyst-15 and Amberlyst-36 with the aim of determining the reaction conditions and the nature of the surface acid sites required to produce selectively triacetylglycerol (triacetin). The acidity of the catalysts (nature, density and strength of acid sites) was characterized by temperature programmed desorption of NH 3 and FTIR of adsorbed pyridine. Al 2 O 3 (Lewis acidity) did not show any activity in the reaction. In contrast, highest activity and selectivity to the triacetylated product (triacetin) were obtained on catalysts with Brønsted acidity: Amberlyst 15 and Amberlyst 36. The effect of temperature and molar ratio of acetic acid to glycerol was studied, finding that both parameters have a significant impact on the obtention of the desired product. Glycerol conversion rate and selectivity to triacetin increased when temperature or acetic acid to glycerol molar ratio were increased reaching a triacetin yield on Amberlyst 36 of 44% at 393 K and acetic acid to glycerol molar ratio of 6. Deactivation and reusability of Amberlyst 36 were evaluated by performing consecutive catalytic tests. The presence of some irreversible deactivation due to sulphur loss was observed. In addition, the feasibility of using crude glycerol from biodiesel production as reactant was also investigated. Conversion of crude pre-treated glycerol yielded values of triacetin and diacetin similar to those obtained with the commercial pure glycerol although at a lower rate.
Catalytic conversion of biodiesel derived raw glycerol to value added products
The huge amount of glycerol obtained during the production of biofuels has led to the search of alternatives for the use of this by-product. New applications for this polyol as a low-cost raw material need to be developed and existing ones need to be expanded. To address this problem, production of value-added molecules from crude glycerol is an effective alternative method for its disposal by incineration. Thus, the ready bioavailability, renewability and unique structure of glycerol make it a particularly attractive starting point for the production of a large number of specialty chemicals. The main purpose of this review is to focus on the catalytic reactivity of different kinds of catalysts in oxidation, dehydration, acetylation, etherification, esterification, acetalization, and ammoxidation process of glycerol conversion. Typical products are citric acid, lactic acid, 1,3-dihydroxyacetone, 1,3propanediol, dichloro-2-propanol, acrolein, hydrogen, and ethanol. Recent studies on the catalysts, reaction conditions and possible pathways are primarily discussed.
Heterogeneous Catalysts for Conversion of Biodiesel-Waste Glycerol into High-Added-Value Chemicals
Catalysts
The valuable products produced from glycerol transformation have become a research route that attracted considerable benefits owing to their huge volumes in recent decades (as a result of biodiesel production as a byproduct) as well as a myriad of chemical and biological techniques for transforming glycerol into high-value compounds, such as fuel additives, biofuels, precursors and other useful chemicals, etc. Biodiesel has presented another challenge in the considerable increase in its byproduct (glycerol). This review provides a recent update on the transformation of glycerol with an exclusive focus on the various catalysts’ performance in designing reaction operation conditions. The different products observed and cataloged in this review involved hydrogen, acetol, acrolein, ethylene glycol, and propylene glycol (1,3-propanediol and 1,2-propanediol) from reforming and dehydration and hydrogenolysis reactions of glycerol conversions. The future prospects and critical challenges ar...
Biodiesel (BD) is an alternative energy source to conventional diesel derived from fossil materials, which are unsustainable and non-renewable and contribute to global warming. BD production via transesterification with methanol leads to the synthesis of glycerol; this process accounts for 10% (w/w) of the total BD produced worldwide. The increasing demand for environmentally harmless BD has created a glycerol glut, which must be utilized to increase BD profitability. Glycerol is a stable and multifunctional compound used as a building block in fine chemical synthesis. Acetylation and carboxylation pathways have been studied to utilize and/or upgrade glycerol into fine chemicals. The use of catalysts, especially heterogeneous catalysts, remains the green approach for tailoring carboxylation and acetylation routes to achieve the desired products, namely, glycerol carbonate and glycerol acetyl esters, respectively. However, side-product formation, poorly structured channels of some catalysts, and catalyst deactivation or reusability hinder the effective utilization of heterogeneous catalysts and must be further studied. Moreover, introduction of variations to optimize reaction-influencing parameters is a potential green method that must be explored.
Renewable and Sustainable Energy Reviews, 2015
Biodiesel is a biofuel obtained from vegetable oils or animal fats by transesterification with methanol, so that it offers a very promising alternative respect to diesel fuel, since it is able to provide a suitable substitute for the fossil diesel in unmodified internal combustion engines, pure or in blends. However, a major barrier exists to consolidate this conventional biodiesel, as the more suitable biofuel for the replacement of fossil fuel. This drawback is related to the significant amount of glycerol obtained as a byproduct in the transesterification process, which exceeds at least 10% by weight of oil used as raw material. Thus, future widespread use of biofuels depends on developing new process technologies to produce high quality transportation fuels from biologically derived feedstocks, which avoid this key handicap. These new biofuels, like the biodiesel, need to be also compatible with the fossil fuel as well as with existing transportation infrastructures to be economically feasible. In this respect, various alternative methods are currently under development to convert vegetable oils into a high quality diesel fuel, fully compatible with petroleum derived diesel fuel but avoiding the existing glycerol glut. The present review aims to explore the current state of available technologies and recent information in research, production practices and engineering developed to produce alternative high-quality diesel fuel from vegetable oils, by hydrotreating of triglycerides in conventional oil refineries (green diesel) as well as those novel biofuels that integrate glycerol into their composition (Gliperol s , DMC-Biod s and Ecodiesel s) and the respective technologies for their productions. These very recent biofuels obtained from oils and fats, seek to achieve greater atom efficiency (ideally 100%) because nor glycerol neither other byproduct is generated, avoiding any purification treatment, so that the overall production process of the biofuel is in large extension simplified.