Shiro Saka

Kinetics of transesterification in rapeseed oil to biodiesel fuel as treated in supercritical methanol

A kinetic study in free catalyst transesterification of rapeseed oil was made in subcritical and supercritical methanol under different reaction conditions of temperatures and reaction times. Runs were made in a bath-type reaction vessel ranging from 200°C in subcritical temperature to 500°C at supercritical state with different molar ratios of methanol to rapeseed oil to determine rate constants by employing a simple method. As a result, the conversion rate of rapeseed oil to its methyl esters was found to increase dramatically in the supercritical state, and reaction temperature of 350°C was considered as the best condition, with the molar ratio of methanol in rapeseed oil being 42.

Effects of water on biodiesel fuel production by supercritical methanol treatment

In the conventional transesterification of fats/vegetable oils for biodiesel production, free fatty acids and water always produce negative effects, since the presence of free fatty acids and water causes soap formation, consumes catalyst and reduces catalyst effectiveness, all of which result in a low conversion. The objective of this study was, therefore, to investigate the effect of water on the yield of methyl esters in transesterification of triglycerides and methyl esterification of fatty acids as treated by catalyst-free supercritical methanol. The presence of water did not have a significant effect on the yield, as complete conversions were always achieved regardless of the content of water. In fact, the present of water at a certain amount could enhance the methyl esters formation. For the vegetable oil containing water, three types of reaction took place; transesterification and hydrolysis of triglycerides and methyl esterification of fatty acids proceeded simultaneously during the treatment to produce a high yield. These results were compared with those of methyl esters prepared by acid- and alkaline-catalyzed methods. The finding demonstrated that, by a supercritical methanol approach, crude vegetable oil as well as its wastes could be readily used for biodiesel fuel production in a simple preparation.

Reactivity of triglycerides and fatty acids of rapeseed oil in supercritical alcohols

A catalyst-free biodiesel production method with supercritical methanol has been developed that allows a simple process and high yield because of simultaneous transesterification of triglycerides and methyl esterification of fatty acids. From these lines of evidence, we expected that similar results would be attained with the use of various alcohols by the supercritical treatment. However, it still remains unclear which type of reaction, transesterification or alkyl esterification, is faster. This parameter would be important in designing the optimum reaction conditions of the supercritical alcohol method. Therefore, we studied the effect of transesterification of triglycerides and esterification of fatty acids in rapeseed oil. Reaction temperature was set at 300 degrees C, and methanol, ethanol, 1-propanol, 1-butanol or 1-octanol was used as the reactant. The results showed that transesterification of triglycerides (rapeseed oil) was slower in reaction rates than alkyl esterification of fatty acids for any of the alcohols employed. Furthermore, saturated fatty acids such as palmitic and stearic acids had slightly lower reactivity than that of the unsaturated fatty acids; oleic, linoleic and linolenic.

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 rapessed 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°C and 20 min for hydrolysis and methyl esterification, respectively. Variables affecting the yields in hydrolysis and methyl esterification are discussed.

Pyrolysis behavior of levoglucosan as an intermediate in cellulose pyrolysis: polymerization into polysaccharide as a key reaction to carbonized product formation

Pyrolysis behavior of levoglucosan (1,6-anhydro-β-d-glucopyranose), the major anhydromonosaccharide formed during cellulose pyrolysis, was studied at 250°–400°C under nitrogen. The pyrolysis products were found to change stepwise: levoglucosan → MeOH-soluble fraction (lower-molecular-weight products and oligosaccharides) → water-soluble fraction (polysaccharides) → insoluble fraction (carbonized products). From the present experimental results, a pathway of cellulose pyrolysis via anhydromonosaccharide is proposed including polymerization to polysaccharides (a reversible reaction) as a key reaction to carbonized product formation.

A comparative study on chemical conversion of cellulose between the batch-type and flow-type systems in supercritical water

Microcrystalline cellulose (avicel) was treated in supercritical waterusing batch-type and flow-type systems. The flow-type system made it possibletoshorten the heating, treating and cooling times, compared with the batch-typesystem. As a result, the flow-type system was able to liquefy avicel withoutproducing any supercritical water-insoluble residue. Although hydrolyzedproducts such as glucose and fructose, and pyrolyzed products such aslevoglucosan, 5-hydroxymethyl furfural, erythrose, methylglyoxal,glycolaldehydeand dihydroxyacetone were found in common from the water-soluble portiontreatedby both systems, the flow-type system gave a water-soluble portion with morehydrolyzed and less pyrolyzed products, together with water-solubleoligosaccharides consisting of cellobiose to cellododecaose and theirdecomposedproducts at their reducing end of glucose, such as[β–glucopyranosyl]1–11 β–levoglucosan,[β–glucopyranosyl]1–11 β–erythrose and[β–glucopyranosyl]1–11 β–glycolaldehyde. Inaddition, the precipitates of polysaccharides were recovered after 12h setting of the water-soluble portion. These results indicatedthat the flow-type system can hydrolyze cellulose with minimizing pyrolyzedproducts. On the other hand, the batch-type system resulted in a higher yieldof the pyrolyzed products due to the longer treatment, but a higher yield ofglucose due possibly to the higher pressure and concomitantly higher ionicproduct of water. Based on these lines of evidence, the process to increase theyield of the sugar is discussed under supercritical water treatment.

Biodiesel production by heterogeneous catalysts and supercritical technologies

Intensive studies are underway to develop more efficient biodiesel conversion processes. Among the various new technologies, both solid catalyst and non-catalytic supercritical processes are recognized as those that can be turned to practical use in the near future. The current status and challenging issues for these two technologies are, therefore, reviewed in this work as innovative biodiesel production technologies.

Pyrolysis reactions of various lignin model dimers

Primary pyrolysis reactions and relative reactivities for depolymerization and condensation/carbonization were evaluated for various lignin model dimers with α-O-4, β-O-4, β-1, and biphenyl substructures by characterizing the tetrahydrofuran (THF)-soluble and THF-insoluble fractions obtained after pyrolysis at 400°C. Reactivity was quite different depending on the model structure: depolymerization: α-O-4 [phenolic (ph), nonphenolic (nonph)], β-O-4 (ph) > β-O-4 (nonph), β-1 (ph, nonph) > biphenyl (ph, nonph); condensation/carbonization: β-1 (ph) > β-O-4 (ph) > α-O-4 (ph) > β-O-4 (nonph), biphenyl (ph, nonph), α-O-4 (nonph), β-1 (nonph). Major degradation pathways were also identified for β-O-4 and β-1 model dimers: β-O-4 types: Cβ-O cleavage to form cinnamyl alcohols and phenols and Cγ-elimination yielding vinyl ethers; β-1 types: Cα-Cβ cleavage yielding benzaldehydes and styrenes and Cγ-elimination yielding stilbenes. Relative reactivities of these pathways were also quite different between phenolic and nonphenolic forms even in the same types; Cβ-O cleavage (β-O-4) and Cγ-elimination (β-1) were substantially enhanced in phenolic forms.

Chemical conversion of various celluloses to glucose and its derivatives in supercritical water

The supercritical water biomass conversion system was designed and developed in our laboratory. The reaction vessel with cellulose sample was treated with this system at supercritical state of water for a designated period (3–105 s) under the conditions of a tin bath temperature of 500°C and pressure of 35 MPa. The recovered products of hydrolysates were then analyzed by high performance liquid chromatography. The obtained results indicated that a high amount of glucose and levoglucosan can be achieved from both celluloses I and II for 5–10 s supercritical treatment, while that from starch for 3–5 s treatment. Although this difference could be due to a difference in the molecular structure between cellulose and starch, a difference between celluloses I and II was not significant. Instead, an accessibility of the water towards cellulose molecules seemed to be significant for their chemical conversion. With the longer treatment, amounts of these compounds observed were decreased due to decomposition. Therefore, it may be concluded that, compared with acid hydrolysis or enzymatic saccharification, cellulose may be hydrolyzed to glucose and its derivatives more or less to the same degree as in corn starch under supercritical state. This finding suggests that the supercritical treatment can overcome the difficulties in hydrolyzing cellulose to glucose, found in the acid hydrolysis or enzymatic saccharification techniques.

Decomposition behavior of cellulose in supercritical water, subcritical water, and their combined treatments

A comparative study on decomposition of cellulose between supercritical water (400°C, 40 MPa) and subcritical water (280°C, 40 MPa) treatments was made to elucidate the difference in their decomposition behavior. Consequently, the supercritical water treatment was found to be more suitable for obtaining high yields of hydrolyzed products. However, cellulose was found to be more liable to fragment under supercritical water treatment, resulting in a decrease in the yield of hydrolyzed products. On the contrary, cellulose was found to be liable to more dehydration in the subcritical water treatment. Based on these results, we have proposed the combined process of short supercritical water treatment followed by subcritical water treatment so as to inhibit fragmentation. Consequently, this combined treatment was able to effectively control the reaction condition, and to increase the yield of hydrolyzed products.