Biodiesel Fuel Production Research Articles

Noncatalytic Alcoholysis of Oils for Biodiesel Fuel Production by a Semi-batch Process

Noncatalytic Alcoholysis of Oils for Biodiesel Fuel Production by a Semi-batch Process

0730 バイオディーゼル燃料製造時の副生グリセリンのガス化(S44-1 燃料および潤滑技術(1),S44 燃料および潤滑技術)

0730 バイオディーゼル燃料製造時の副生グリセリンのガス化(S44-1 燃料および潤滑技術(1),S44 燃料および潤滑技術)

Biodiesel-fuel production in a packed-bed reactor using lipase-producing Rhizopus oryzae cells immobilized within biomass support particles

A packed-bed reactor (PBR) system using fungus whole-cell biocatalyst was developed for biodiesel fuel production by plant oil methanolysis. Lipase-producing Rhizopus oryzae cells were immobilized within 6 mm × 6 mm × 3 mm cuboidal polyurethane foam biomass support particles (BSPs) during batch cultivation in a 20-l air-lift bioreactor. Emulsification of the reaction mixture containing soybean oils and water improved the methanolysis reaction rate. Using a high flow rate for the reaction mixture in the PBR caused exfoliation of the immobilized cells from the BSPs, while the inefficient mixing of the reaction mixture at low flow rates allowed the BSPs to be covered with a hydrophilic layer of high methanol concentration, leading to a significant decrease in lipase activity. A high methyl ester content of over 90% was achieved at a flow rate of 25 l/h in the first cycle of repeated batch methanolysis and a high value of around 80% was maintained even after the tenth cycle. Comparison with methanolysis reaction in a shaken bottle suggested that the PBR enhances repeated batch methanolysis by protecting immobilized cells from physical damage and excess amounts of methanol. The process presented here is therefore considered to be promising for industrial biodiesel-fuel production.

Biocarbon production from Hungarian sunflower shells

The production of biodiesel and bioethanol fuels is often accompanied by the co-production of lignocellulosic “waste” byproducts. For example, the oil from sunflower seeds (that can be used to manufacture biodiesel fuel) has as “waste” co-products the sunflower shell and its stem. In this paper we examine the production of biocarbon (charcoal) from sunflower shells produced in Hungary. The conversion of these shells to biocarbon via the University of Hawaii's Flash Carbonization TM process is efficient and very quick. An increase in reaction pressure from 1.27 to 2.17 MPa causes a reduction in reaction time that results in a significant increase in charcoal production and profitability. These findings justify further study of the benefits of charcoal production at pressures above 2 MPa.

Use of Waste Fats of Animal and Vegetable Origin for the Production of Biodiesel Fuel: Quality, Motor Properties, and Emissions of Harmful Components

One of the ways to reduce the price of biodiesel fuel is to use waste fats of animal and vegetable origin. The objective of this work was to investigate the physical and chemical properties of the fatty acid methyl esters of animal and vegetable origin and their mixtures, to determine their motor characteristics, to choose the optimal composition of biofuel mixtures, and to perform comparative analyses of emissions of harmful components in exhaust gases. It was determined that pure fatty acid methyl esters of animal origin and linseed oil fatty acid methyl esters do not meet standard requirements and cannot be used directly in diesel engines. For diesel engines, three-component mixtures of rapeseed oil methyl esters (RME), pork lard methyl esters (PME) or beef tallow methyl esters (TME), and linseed oil methyl esters (LME) (where the proportion of LME and methyl esters of animal origin is 1:4) may be used as fuel. According to the comparative analyses of motor characteristics of three-component mixtures, ...

3-51.木質バイオマス由来粗メタノールを用い超臨界法によるバイオディーゼル製造((11)水熱・バイオディーゼル,Session 3 バイオマス等)

3-51.木質バイオマス由来粗メタノールを用い超臨界法によるバイオディーゼル製造((11)水熱・バイオディーゼル,Session 3 バイオマス等)

Biodiesel fuel production with solid amorphous-zirconia catalysis in fixed bed reactor

Abstract Amorphous zirconia catalysts, titanium-, aluminum-, and potassium-doped zirconias, were prepared and evaluated in the transesterification of soybean oil with methanol at 250 °C, and the esterification of n-octanoic acid with methanol at 175–200 °C. Titanium- and aluminum-doped zirconias are promising solid catalysts for the production of biodiesel fuels from soybean oil because of their high performance, with over 95% conversion in both of the esterifications.

Lipase localization in Rhizopus oryzae cells immobilized within biomass support particles for use as whole-cell biocatalysts in biodiesel-fuel production

To identify the lipase responsible for the methanolysis activity of fungus whole-cell biocatalysts, the lipase localization of Rhizopus oryzae cells was determined. Western blot analysis showed that R. oryzae cells produce two types of lipase with different molecular masses of 34 and 31 kDa; the former (ROL34) was bound to the cell wall, whereas the latter (ROL31) was mainly bound to the cell membrane. It was found that cell immobilization within reticulated polyurethane foam biomass support particles strongly inhibits the secretion of membrane-bound lipase into the culture medium. An investigation of the relationship between ROL34 and ROL31 suggested that ROL31 originates from the cleavage of a 28-amino-acid residue at the N-terminus of ROL34. The addition of olive oil to the culture medium led to the retention of increased amounts of lipase within the cell. This phenomenon was further confirmed by an immunofluorescence labeling of hyphal cells. When cells were cultivated with various substrate-related compounds, such as olive oil and oleic acid, the intracellular methanolysis activity strongly correlated with the relative amounts of the membrane-bound lipase, which suggests that ROL31 localized in the membrane plays a crucial role in the methanolysis activity of R. oryzae cells.

Batch (One- and Two-Stage) Production of Biodiesel Fuel From Rapeseed Oil

Biodiesel fuel is an alternative and renewable energy source, which may help to reduce air pollution, as well as our dependence on petroleum for energy. Several processes have already been developed for the production of biodiesel. Alkali-catalyzed transesterification with short-chain alcohols, for example, generates high yields of methyl esters in short reaction times. In this study, we have evaluated the efficacy of batch (one- and two-stage) transesterification of rapeseed oil in the production of rapeseed methyl ester. The conversion of rapeseed oil exhibited similar reaction patterns and yields in 30- and 1-L reaction systems. Approximately 98% of the rapeseed oil was converted at 400 rpm within 20 min, under the following conditions: 1% (w/w) KOH, 1ratio10 methanol molar ratio, and at 60 degrees C. In the 30-L, two-stage transesterification process, approx 98.5% of the rapeseed oil was converted at a 1ratio4.5 molar ratio and 1% (w/w) KOH at 60 degrees C for 30 min (first reaction condition), and at a 1ratio1 molar ratio and 0.2% (w/w) KOH at 60 degrees C for 30 min (second reaction condition).

Biological treatment of wastewater discharged from biodiesel fuel production plant with alkali-catalyzed transesterification

The biological treatment of wastewater discharged from a biodiesel fuel (BDF) production plant conducting alkali catalysis transesterification was investigated. BDF wastewater has a high pH and high hexane-extracted oil and low nitrogen concentrations, and inhibits the growth of microorganisms. The biological treatment of BDF wastewater is difficult because the composition of such wastewater is not suitable for microbial growth. To apply the microbiological treatment of BDF wastewater using an oil degradable yeast, Rhodotorula mucilaginosa, the pH was adjusted to 6.8 and several nutrients such as a nitrogen source (ammonium sulfate, ammonium chloride or urea), yeast extract, KH2PO4 and MgSO4.7H2O were added to the wastewater. The optimal initial concentration of yeast extract was 1 g/l and the optimal C/N ratio was between 17 and 68 when using urea as a nitrogen source. A growth inhibitor was also present in the BDF wastewater, and this growth inhibitor could be detected by measuring the solid content in an aqueous phase after the hexane extraction of the wastewater. Microorganisms could not grow at solid contents higher than 2.14 g/l in the wastewater. To avoid the growth inhibition, the BDF wastewater was diluted with the same volume of water. Oil degradation in the diluted BDF wastewater was observed and the best result was obtained under the determined optimal conditions. This treatment system is simple because no controllers, except for a temperature, are necessary. These results suggest that the biological treatment system developed for BDF wastewater is useful for small-scale BDF production plants.

Facilitatory effect of immobilized lipase-producing Rhizopus oryzae cells on acyl migration in biodiesel-fuel production

For biodiesel-fuel production by methanolysis of plant oils, Rhizopus oryzae cells producing a 1,3-positional specificity lipase were cultured with polyurethane foam biomass support particles (BSPs) in a 20 l air-lift bioreactor, and the cells immobilized within BSPs were used as whole-cell biocatalyst in repeated batch-cycle methanolysis reaction of soybean oil. The whole-cell biocatalyst had a higher durability in the methanolysis reaction when obtained from air-lift bioreactor cultivation than from shake-flask cultivation. Following repeated methanolysis reaction using the whole-cell biocatalyst, analysis of the reaction mixture composition indicated that monoglycerides (MGs) decreased and free fatty acids (FFAs) increased with increasing water content in the reaction mixture, and that MGs, diglycerides (DGs), and triglycerides (TGs) increased with increasing number of reaction cycles. The isomers of MGs and DGs generated during the 20th methanolysis reaction cycle consisted of 2-MGs and 1,2(2,3)-DGs, respectively. The hydrolytic activity of the whole-cell biocatalyst, on the other hand, was stable regardless of the number of reaction cycles. It was demonstrated thus that the whole cell biocatalyst promotes acyl migration of partial glycerides, and that the facilitatory effect is increased by increase in the water content of the reaction mixture but it is lost gradually with increasing number of reaction cycles.

Biodiesel fuel production with solid superacid catalysis in fixed bed reactor under atmospheric pressure

Solid superacid catalysts of sulfated tin and zirconium oxides and tungstated zirconia are prepared and evaluated in the trans-esterification of soybean oil with methanol at 200–300 °C and the esterification of n-octanoic acid with methanol at 175–200 °C. Tungstated zirconia–alumina is a promising solid acid catalyst for the production of biodiesel fuels from soybean oil because of its high performance in the conversions over 90% for both of the esterifications.

Effect of fatty acid membrane composition on whole-cell biocatalysts for biodiesel-fuel production

To stabilize the lipase activity of Rhizopus oryzae cells as whole-cell biocatalysts, the effect of cell membrane fatty acid composition on biodiesel-fuel production was investigated. The fatty acid composition of the cell membrane was easily controllable by addition of various fatty acids to the culture medium. Oleic or linoleic acid-enriched cells showed higher initial methanolysis activity than saturated fatty acid-enriched cells, among which palmitic acid-enriched cells exhibited significantly greater enzymatic stability than unsaturated fatty acid-enriched cells. It was assumed that fatty acids significantly affect the permeability and rigidity of the cell membrane, and that higher permeability and rigidity lead to increases in methanolysis activity and enzymatic stability, respectively. When the optimal fatty acid ratio of 0.67, indicated by R f [=oleic acid/(oleic acid + palmitic acid)], was adopted for repeated methanolysis reactions, both methanolysis activity and enzymatic stability were maintained at significantly elevated levels, with methyl ester content of around 55% even in the 10th batch cycles.

Production of Biodiesel Fuel by Transesterification of Rapeseed Oil

Fatty acid methyl esters (FAMEs) show large potential applications as diesel substitutes, also known as biodiesel fuel. Biodiesel fuel as renewable energy is an alternative that can reduce energy dependence on petroleum as well as air pollution. Several processes for the production of biodiesel fuel have been developed. Transesterification processes under alkali catalysis with short-chain alcohols give high yields of methyl esters in short reaction times. We investigated transesterification of rapeseed oil to produce the FAMEs. Experimental reaction conditions were molar ratio of oil to alcohol, concentration of catalyst, type of catalyst, reaction time, and temperature. The conversion ratio of rapeseed oil was enhanced by the alcohol:oil mixing ratio and the reaction temperature.

322 ディーゼル機関用植物油エチルエステル燃料の製造と機関性能 : 第二報 コモンレール直噴式機関における性能および排気(OS-2 バイオ燃料ディーゼル機関・排気後処理)

322 ディーゼル機関用植物油エチルエステル燃料の製造と機関性能 : 第二報 コモンレール直噴式機関における性能および排気(OS-2 バイオ燃料ディーゼル機関・排気後処理)

Two-step preparation for catalyst-free biodiesel fuel production: hydrolysis and methyl esterification.

Biodiesel fuel was prepared by a two-step reaction: hydrolysis and methyl esterification. Hydrolysis was carried out at a subcritical state of water to obtain fatty acids from triglycerides of rapeseed oil, while the methyl esterification of the hydrolyzed products of triglycerides was treated near the supercritical methanol condition to achieve fatty acid methyl esters. Consequently, the two-step preparation was found to convert rapeseed oil to fatty acid methyl esters in considerably shorter reaction time and milder reaction condition than the direct supercritical methanol treatment. The optimum reaction condition in this two-step preparation was 270 degrees C and 20 min for hydrolysis and methyl esterification, respectively. Variables affecting the yields in hydrolysis and methyl esterification are discussed.

628 バイオディーゼル燃料の精製純度がディーゼル機関の性能および排気特性に及ぼす影響

628 バイオディーゼル燃料の精製純度がディーゼル機関の性能および排気特性に及ぼす影響

Effect of Methanol and Water Contents on Production of Biodiesel Fuel from Plant Oil Catalyzed by Various Lipases in a Solvent-Free System.

Methyl esters synthesized from plant oil and methanol by the methanolysis reaction are potentially important as a biodiesel fuel. The methanolysis of soybean oil by lipases from various microorganisms was investigated. Several of the lipases were found to catalyze methanolysis in a water-containing system without an organic solvent. The lipases from Candida rugosa, Pseudomonas cepacia, and Pseudomonas fluorescens displayed particularly high catalytic ability. The reaction rates of methanolysis catalyzed by the C. rugosa and P. fluorescens lipases decreased significantly when the water content was low, showing that water prevents the inactivation of these lipases by methanol. On the other hand, the methanolysis reaction rate catalyzed by the P. cepacia lipase remained high even under a low water content. In addition, the P. cepacia lipase gave high methyl ester contents in the reaction mixture up to 2 or 3 molar equivalents of methanol to oil, which is attributed to the P. cepacia lipase having substantial methanol resistance. For the same methanol content, the reaction rates of methanolysis catalyzed by the P. cepacia lipase increased with decreasing water content, and hence lipases strongly resistant to high methanol, such as that from P. cepacia, are desirable for use in methanolysis reaction processes.

Biodiesel Fuel Production by Transesterification of Oils.

Biodiesel (fatty acid methyl esters), which is derived from triglycerides by transesterification with methanol, has attracted considerable attention during the past decade as a renewable, biodegradable, and nontoxic fuel. Several processes for biodiesel fuel production have been developed, among which transesterification using alkali-catalysis gives high levels of conversion of triglycerides to their corresponding methyl esters in short reaction times. This process has therefore been widely utilized for biodiesel fuel production in a number of countries. Recently, enzymatic transesterification using lipase has become more attractive for biodiesel fuel production, since the glycerol produced as a by-product can easily be recovered and the purification of fatty methyl esters is simple to accomplish. The main hurdle to the commercialization of this system is the cost of lipase production. As a means of reducing the cost, the use of whole cell biocatalysts immobilized within biomass support particles is significantly advantageous since immobilization can be achieved spontaneously during batch cultivation, and in addition, no purification is necessary. The lipase production cost can be further lowered using genetic engineering technology, such as by developing lipases with high levels of expression and/or stability towards methanol. Hence, whole cell biocatalysts appear to have great potential for industrial application.

Pretreatment of Immobilized Candida antarctica Lipase for Biodiesel Fuel Production from Plant Oil.

Pretreatment of Immobilized Candida antarctica Lipase for Biodiesel Fuel Production from Plant Oil.