1.0. Introduction 4044 2.0. Biomass Chemistry and Growth Rates 4047 2.1. Lignocellulose and Starch-Based Plants 4047 2.2. Triglyceride-Producing Plants 4049 2.3. Algae 4050 2.4. Terpenes and Rubber-Producing Plants 4052 3.0. Biomass Gasification 4052 3.1. Gasification Chemistry 4052 3.2. Gasification Reactors 4054 3.3. Supercritical Gasification 4054 3.4. Solar Gasification 4055 3.5. Gas Conditioning 4055 4.0. Syn-Gas Utilization 4056 4.1. Hydrogen Production by Water−Gas Shift Reaction 4056

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Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering.

https://www.cti2000.it/Bionett/BioD-1999-101%20Biodiesel%20production%20review.pdf

Biodiesel production : a review

Biodiesel is gaining more and more importance as an attractive fuel due to the depleting fossil fuel resources. Chemically biodiesel is monoalkyl esters of long chain fatty acids derived from renewable feed stock like vegetable oils and animal fats. It is produced by transesterification in which, oil or fat is reacted with a monohydric alcohol in presence of a catalyst. The process of transesterification is affected by the mode of reaction condition, molar ratio of alcohol to oil, type of alcohol, type and amount of catalysts, reaction time and temperature and purity of reactants. In the present paper various methods of preparation of biodiesel with different combination of oil and catalysts have been described. The technical tools and processes for monitoring the transesterification reactions like TLC, GC, HPLC, GPC, 1H NMR and NIR have also been summarized. In addition, fuel properties and specifications provided by different countries are discussed.

Technical aspects of biodiesel production by transesterification—a review

A review on biodiesel production using catalyzed transesterification

Biodiesel fuel production by transesterification of oils.

Transesterification of soybean oil (SBO) and other triglycerides with alcohols, in the presence of a catalyst, yields fatty esters and glycerol. Di- and monoglycerides are intermediates. Reactions are consecutive and reversible. Rate constants have been determined for each reaction with a computerized kinetic program. The effects of the type of alcohol, 1-butanol or methanol (MeOH); molar ratio of alcohol to SBO; type and amount of catalyst; and reaction temperature on rate constants and kinetic order were examined. Forward reactions appear to be pseudo-first order or second order depending upon conditions used. Reverse reactions appear to be second order. At a molar ratio of MeOH/SBO of 6:1, a shunt reaction was observed. Energy of activation was determined for all forward and reverse reactions under a variety of experimental conditions from plots of log k vs 1/T. Values ranged from 8–20 kcal/mol.

Transesterification kinetics of soybean oil 1

Cetane numbers (C#) for the homologous series of straight-chain, saturated n-alcohols, C5−C12 and C14, were determined according to ASTM D 613. Measured C# ranged from 18.2–80.8 and increased linearly with carbon number (CN). Regression analyses developed equations that related various physical properties or molecular characteristics of these alcohols to calculated C#. The degree of relationship between measured and calculated C# was expressed as R2. The decreasing order of the precision with which these properties correlated with C# was: boiling point (bp)>melting point (mp)>CN>heat of combustion (HG)>refractive index (n20
 D)>density (d). This ranking was based upon R2 (0.99–0.96) and the Average % error (2.8–7.2%). C# were also determined for straight-chain homologs of saturated methyl esters with CN of 6, 10, 12, 14, 16 and 18. C# ranged from 18.0–75.6 and increased curvilinearly with CN. Equations were also developed that related physical properties of these esters to C#. The precision with which these properties correlated with C# was: bp>viscosity (V)>heat of vaporization (HV)>HG>CN>surface tension (ST)>mp>n20
 D>d. R2 ranged from 0.99 for bp to 0.98 for d. Equations for the alcohols were linear or quadratic, while equations for the esters were linear, quadratic or cubic based upon statistical considerations that included a Student’s t-test. With related physical properties and these equations, accurate predictions of C# can be made for saturated n-alcohols and methyl esters.

Predicting Cetane Numbers of n-Alcohols and Methyl Esters from their Physical Properties

A rapid quantitative capillary gas Chromatographic method has been developed for studying transesterification of soybean oil (SBO) to fatty esters. Standard solutions containing methyl linoleate, mono- , di- and trilinolein were analyzed with a 1.8 m X 0.32 mm SE- 30 fused silica column. The effect of carrier gas flow on reproducibility was determined. Prior to analysis, mono- (MG) and diglycerides (DG) were silylated with N,O- bis(trimethylsilyl) trifluoroacetamide.Tridecanoin was used as an internal standard. From plots of area and weight relationships, slopes and intercepts for all four compound classes were determined. Agreement between the measured and calculated compositions of the standard solutions was good; the overall standard deviation was 0.4. Slopes and intercepts also were determined for SBO and its methyl and butyl esters. Complete separation of ester, MG, DG and triglyceride was obtained in 12 min by temperature programming from 160 to 350 C. This method of analysis gave excellent results when used in a kinetic study of SBO transesterification.

Quantitation in the analysis of transesterified soybean oil by capillary gas chromatography 1

Cetane Numbers of Fatty Esters, Fatty Alcohols and Triglycerides Determined in a Constant Volume Combustion Bomb

Transformations of hydroxy to keto fatty esters have been monitored successfully by converting the hydroxy compounds to their trifluoroacetyl (TFA) or trimethylsilyl (TMS) derivatives followed by gas-liquid chromatography (GLC). The TFA derivatives have shorter retention times, are better separated from the keto esters, and permit more complete resolution of saturated and unsaturated hydroxy fatty esters than the TMS derivatives. Improved methods for derivative preparation which are rapid and convenient are described. Methyl dimorphecolate (methyl 9-hydroxy-trans,trans,10,12-octadecadienoate), which is thermally unstable and cannot be chromatographed as the trifluoroacetate or free hydroxy compound, was chromatographed satisfactorily as the trimethylsilyl ether.

Bernard Freedman

Papers

Transesterification kinetics of soybean oil 1

Predicting Cetane Numbers of n-Alcohols and Methyl Esters from their Physical Properties

Quantitation in the analysis of transesterified soybean oil by capillary gas chromatography 1

Cetane Numbers of Fatty Esters, Fatty Alcohols and Triglycerides Determined in a Constant Volume Combustion Bomb

Gas-liquid chromatography of hydroxy fatty esters: Comparison of trifluoroacetyl and trimethylsilyl derivatives