Continuous production of palm methyl esters

A system for continuous transesterification of palm oil was developed using a continuous stirred-tank reactor (CSTR) and pumps for continuous delivery of oil and catalyst and for continuous removal of product. Potassium hydroxide was used as the catalyst, the methanol-to-oil molar ratio was 6∶1, and reaction temperature was 60°C. The yield of methyl esters increased from 58.8% of theoretical yield at a residence time of 40 min to 97.3% at a residence time of 60 min. However, higher residence times decreased the production rate. During long-term continuous operation, the CSTR displayed steady state conditions in terms of product profile and methyl ester concentration. This process has good potential in the manufacture of biodiesel.     

A simple capillary column GC method for analysis of palm oil-based polyol esters

A reliable, simultaneous analysis of palm oil polyol esters using capillary column GC is described. The polyol esters were esterified from palm oil methyl esters (POME) and palm kernel oil methyl esters (PKOME) with trimethylolpropane [2-ethyl-2-(hydroxymethyl)-1,3-propanediol; TMP] to produce the biodegradable base oil for lubricant production. Analysis was performed using a high-temperature capillary column, SGE HT5 operated at a temperature gradient of 6°C/min starting from 80 to 340°C. Before injection, the sample was derivatized with N,O-bis (trimethylsilyl)trifluoroacetamide in ethyl acetate at 40°C for at least 10 min. This procedure provides a complete separation of reaction products: TMP, methyl esters, monoesters (ME), diesters (DE), and triesters (TE). As expected, the ME from palm kernel oil was resolved into five major peaks, DE into seven peaks, and TE into 10 peaks. Since no standard was available for this sample, the identities of the peaks were established by a secondary standard that was derived from pure methyl esters. This GC method has made possible the simultaneous determination of reaction product compositions in order to assess the extent of reaction.     

Lubrication properties of trimethylolpropane esters based on palm oil and palm kernel oils

Due to the global drive towards biodegradable products, trimethylolpropane [2‐ethyl‐2‐(hydroxymethyl)‐1, 3‐propanediol] (TMP) esters based on palm and palm kernel oils were synthesized, their lubrication properties evaluated, and their potential as base stock for biodegradable lubricants assessed. Two types of TMP esters were considered: palm kernel (PKOTE) and palm oil (PPOTE) TMP esters, derived from palm oil and palm kernel methyl esters, respectively. Lubrication properties such as viscosity, viscosity index (VI) and pour point (PP) were determined according to methods of the American Society for Testing and Materials. Wear and friction properties were evaluated using a four‐ball test machine, while oxidative stability was studied with the Penn State Micro‐oxidation thin‐film test. High VI ranges between 170 to 200 were recorded for these base stocks. PP were relatively high, between 4 to —1 °C, but were improved to at least —33 °C in high oleic palm oil TMP esters. The effects of chemical structure and impurities on wear properties and oxidative stability were also studied. The presence of methyl esters was found to improve wear, but hydroxyl groups in mono‐ and diesters had negative effects at high concentrations. Differences in chemical structures of PKOTE and PPOTE were shown to affect friction and wear results. Both base fluids exhibit oxidative stability comparable to other high oleic base fluids.     

Oxidative stability and storage behavior of fatty acid methyl esters derived from used palm oil

Fatty acid alkyl esters, especially FAME, are the most commonly used liquid biofuel. Because biofuels are expected to be important alternative renewable energy sources in the near future, more studies on their stability against oxidation need to be addressed. Biofuel derived from vegetable oils is well researched, currently with more attention focused on the reuse of waste oil sources than on pure vegetable oil for such production. A method to convert used palm oil, i.e., used frying oil, and residual oil of spent bleaching earths (SPE) to their respective methyl esters has been established by the Malaysian Palm Oil Board. These methyl esters can be used as diesel substitute. However, the methyl esters obtained from used frying oil have a low induction period (3.42 h). In Europe, any methyl esters must have an induction period of at least 6 h in Rancimat stability to be usable as biodiesel, as required by European Biodiesel Standard (EN 14214). To meet this requirement, the used frying oil methyl esters (UFOME) obtained can be treated with different types of antioxidants, either synthetic or natural, at different treatment levels, such as vitamin E, 3-ert-butyl-4-hydroxyanisole (BHA), 2,6-di-tert-butyl-4-methyl-phenol (BHT), 2,5-di-tert-butyl hydroquinone (TBHQ), and n-propyl gallate (PG), to investigate their oxidative stability and storage behavior. The order of increasing antioxidant effectiveness with respect to the oxidative stability of UFOME is: vitamin E<BHT<TBHQ<BHA<PG. Because methyl esters derived from residual oil of SBE have an induction period of 14.6 h, their treatment with antioxidants is unnecessary.     

Kinetics of transesterification of palm-based methyl esters with trimethylolpropane

Kinetics of transesterification of palm-based methyl esters (POME) with trimethylolpropane (TMP) to polyol esters was investigated. A kinetic model of reaction was obtained by assuming a series of irreversible elementary reactions at various temperatures. The reaction rate constants were determined under limited conditions. The optimal ratios for k ₂/k ₁ and k ₃/k ₁ were 0.70–0.80 and 0.21–0.25, respectively. Both palm oil methyl esters (PPOME) and palm-kernel oil methyl esters (PKOME) were reacted with TMP by using sodium methoxide as catalyst. The POME-to-TMP molar ratio and catalyst weight percentage were held constant at 10∶1 and 0.4%, respectively. The effects of temperature (70–110°C) and raw materials (PKOME and PPOME) were investigated and found to have a significant impact on the reaction kinetics. When using a large excess of POME and continual withdrawal of methanol via vacuum, the reaction reached completion in less than 20 min at 80°C. After removal of unreacted POME, the final product contained apprximately 98 wt% triesters.     

Production of hydrocarbons by pyrolysis of methyl esters from rapeseed oil

The pyrolysis of a mixture of methyl esters from rapeseed oil has been studied in a tubular reactor between 550 and 850°C and in dilution with nitrogen. A specific device for the condensation of cracking effluents was used for the fractionated recovery of liquid and gaseous effluents, which were analyzed on-line by an infrared analyzer and by gas chromatography. The cracking products in the liquid effluent were identified by gas chromatography/mass spectrometry coupling. The effects of temperature on the cracking reaction were studied for a constant residence time of 320 ms and a constant dilution rate of 13 moles of nitrogen/mole of feedstock. The principal products observed were linear 1-olefins,n-paraffins, and unsaturated methyl esters. The gas fraction also contained CO, CO₂, and H₂. The middle-chain olefins (C₁₀–C₁₄ cut) and short-chain unsaturated esters, produced with a high added value, had an optimum yield at a cracking temperature of 700°C.     

Separation of fatty acid methyl esters from tall oil by selective adsorption

Fatty acid methyl esters (FAME) and resin acids (RA) were separated from tall oil by selective adsorption. Commercial nonmodified molecular sieve 13X was used as adsorbent. The adsorption isotherms of fatty acids (FA), FAME, and RA on molecular sieve 13X at 25°C were determined using various solvents. The solvents were methanol, ethanol, isopropanol, acetone, benzene, hexane, isooctane, petroleum ether (40–60°C), and petroleum naphtha (80–180°C). With each solvent, FA and RA were adsorbed to a greater extent than FAME. Adsorption isotherms for RA and FAME in binary adsorption systems were also determined using petroleum ether, petroleum naphtha, benzene, and isopropanol. For each component in the binary adsorption, the equilibrium amounts are lower than the values for pure component adsorption. The adsorption of FAME decreased in the presence of RA markedly in petroleum ether and petroleum naphtha. This fact may be the indication of the phenomenon of selective adsorption. Separation was accomplished by adding a solution of esterified tall oil in solvents used in the binary adsorption systems, through a column packed with molecular sieve 13X. With petroleum naphtha, FAME and RA were recovered in yields of 93 and 94%, respectively, from esterified tall oil. Petroleum naphtha gave the best results. The effects of particle size of adsorbent and flow rate of solvent on the efficiency of the separation were also investigated in fixed-bed column studies. The particle size of adsorbent did not apparently alter the results. Changes in the particle size should not significantly change the number of available adsorption sites in a microporous molecular sieve.     

Kinetics of palm oil transesterification in a batch reactor

Methyl esters were produced by transesterification of palm oil with methanol in the presence of a catalyst (KOH). The rate of transesterification in a batch reactor increased with temperature up to 60°C. Higher temperatures did not reduce the time to reach maximal conversion. The conversion of triglycerides (TG), diglycerides (DG), and monoglycerides (MG) appeared to be second order up to 30 min of reaction time. Reaction rate constants for TG, DG, and MG hydrolysis reactions were 0.018–0.191 (wt%·min)⁻¹, and were higher at higher temperatures and higher for the MG reaction than for TG hydrolysis. Activation energies were 14.7, 14.2, and 6.4 kcal/mol for the TG, DG, and MG hydrolysis reactions, respectively. The optimal catalyst concentration was 1% KOH.     

Kinetic studies of epoxidation and oxirane cleavage of palm olein methyl esters

The kinetics for the epoxidation of methyl esters of palm olein (MEPOL) by peroxyformic acid and peroxyacetic acid generatedin situ were studied. The rate-determining step was found to be the formation of peroxy acid. Epoxidized MEPOL (EpMEPOL), with almost complete conversion of the unsaturated carbon and negligible ring-opening, can be synthesized by thein situ technique described. The kinetics of the oxirane cleavage of EpMEPOL by acetic acid were studied at various temperatures. The reaction was found to be first-order with respect to the epoxy concentration and second-order to the acetic acid concentration. The activation energy and the entropy of activation for the epoxidation of MEPOL were comparable to those for the oxirane cleavage of EpMEPOL by acetic acid, suggesting that the two reactions are competitive. The success of the epoxidation of MEPOL with only negligible oxirane cleavage is attributed to the heterogeneous nature of the system employed in thein situ technique.     

Enzymatic synthesis of wax esters from rapeseed fatty acid methyl esters and a fatty alcohol

Wax esters were transesterified from fatty acid methyl esters of rapeseed and a fatty alcohol (1-hexadecanol, 16:0). The amounts of both the substrates were fixed to 0.1 mmol and an immobilized enzyme, Lipozyme, was used as catalyst. The experiment was performed following a statistic central composite design with five variables. The enzyme/lipid ratio was varied between 0.3–0.9 of the substrate weight and the enzyme was equilibrated to different water activities varying from 0.11 to 0.44. A temperature range of 50–80°C was investigated and the reaction time lasted up to 40 min. A solvent, isooctane, constituted 0–30% of the substrate weight. The first experimental series was performed in small closed test tubes. In the second series the caps of the test tubes were off to evaporate the methanol produced during the reaction. The highest initial reaction rate was 9.6 g_{wax esters}/g_enzyme · h. It appeared when: the enzyme/lipid ratio was low, 0.3, the temperature was high, 80°C; no isooctane was present; and the water activity was below 0.11. The initial reaction rate was independent of the caps on the test tubes. With the large amount of enzyme the yield of wax esters was above 70% after 10 min in both experimental series. In the reaction with caps, the reaction reached equilibrium at 83% after 20 min at 80°C. However, without caps the continuous evaporation of methanol increased the equilibrium constantly, and after 40 min at 80°C a yield of 90% was reached.     

Palm oil methyl esters as lubricant additive in a small diesel engine

Malaysian crude palm oil has been successfully converted to methyl esters, also known as palm oil diesel (POD), which is readily combustible in diesel engines. This paper presents and discusses the results of current studies on the performance and the effects of POD on the wear characteristics of tribological components of a small, four-stroke diesel engine. Adding POD to commercial lubricating oil has enhanced the performance of such oils. Results obtained from this study show that the power output and brake specific fuel consumption of the engine, lubricated with commercial SAE 40 oil blended with POD, are comparable to those of 100% SAE 40 oil. Wear debris analysis shows that blends of POD and SAE 40 commercial lubricating oil increase the anti-wear characteristics of the engine when compared to 100% SAE 40 lubricating oil.     

Fast formation of high-purity methyl esters from vegetable oils

Experiments have confirmed that the base-catalyzed methanolysis of vegetable oils occurs much slower than butanolysis because of the two liquid phases initially present in the former reaction. For the same reason, second-order kinetics are not followed. The use of a cosolvent such as tetrahydrofuran or methyl tertiary butyl ether speeds up methanolysis considerably. However, like one-phase butanolysis, one-phase methanolysis initially exhibits a rapid formation of ester, but then slows drastically. Experiments show that the half-life of the hydroxide catalyst is too long to explain the sudden slowing of the reaction. Similarly, lower rate constants for the methylation of the mono- and diglycerides are not a reasonable explanation. Instead the cause has been identified as the fall in polarity which results from the mixing of the nonpolar oil with the methanol. This lowers the effectiveness of both hydroxide and alkoxide catalysts. Increasing the methanol/oil molar ratio to 27 in the one-phase system raises the polarity such that the methyl ester content of the ester product exceeds 99.4 wt% in 7 min. This has obvious implications for the size of new methyl ester plants as well as the capacity of existing facilities.     

Quality control of rapeseed oil methyl esters by determination of acyl conversion

A simple procedure for the evaluation of vegetable oil conversion to methyl esters of fatty acids has been developed. These methyl esters, prepared by the transesterification of vegetable oil with methanol, are used as alternative fuel for diesel engines. A method of gas-liquid chromatography (GLC) on packed columns is used to determine the conversion of acyls bound in acylglycerols to methyl esters. This procedure is based on comparison of the peak areas of methyl esters in fuel samples before and after reaction with an effective transesterification reagent, which will transform unreacted acylglycerols to methyl esters. A correlation between the bound glycerol content, determined by the thin-layer chromatography/flame-ionization detector method, and the acyl conversion, determined by GLC, is given. In acyl conversions to methyl esters over 96.0%, the bound glycerol content is less than 0.25% by weight.     

Fast formation of high-purity methyl esters from vegetable oils

Experiments have confirmed that the base-catalyzed methanolysis of vegetable oils occurs much slower than butanolysis because of the two liquid phases initially present in the former reaction. For the same reason, second-order kinetics are not followed. The use of a cosolvent such as tetrahydrofuran or methyl tertiary butyl ether speeds up methanolysis considerably. However, like one-phase butanolysis, one-phase methanolysis initially exhibits a rapid formation of ester, but then slows drastically. Experiments show that the half-life of the hydroxide catalyst is too long to explain the sudden slowing of the reaction. Similarly, lower rate constants for the methylation of the mono- and diglycerides are not a reasonable explanation. Instead the cause has been identified as the fall in polarity which results from the mixing of the nonpolar oil with the methanol. This lowers the effectiveness of both hydroxide and alkoxide catalysts. Increasing the methanol/oil molar ratio to 27 in the one-phase system raises the polarity such that the methyl ester content of the ester product exceeds 99.4 wt% in 7 min. This has obvious implications for the size of new methyl ester plants as well as the capacity of existing facilities.     

Evaluation of nonpolar methyl esters by column and gas chromatography for the assessment of used frying olive oils

The measurement of unaltered methyl esters separated from polar methyl esters by column chromatog-raphy was used to evaluate the alteration of an olive oil that had been used 15 times to fry potatoes. Unaltered methyl ester (the nonpolar fraction) decreased significantly (94.9 ± 0.8%vs 98.2 + 0.5%; p < 0.05), while the polar fraction increased significantly (4.0 ± 0.7%vs 2.1 ± 0.7%; p < 0.05) after 15 fryings. The unrecoverable fraction also increased. In order to avoid column contamination the gas Chromatographic analysis was only done on the nonpolar fractions. Linoleic and oleic acids showed a tendency to decrease while saturated fatty acid tended to increase. The unsaturated/saturated fatty acids ratio decreased from an initial value of 7.05 to 6.40 in the last frying. Quantitative gas Chromatographic analysis using both the percentage fatty acid composition and the relative amount of unaltered methyl esters showed a significant oleic acid decrease after 15 fryings (75.8 ± 0.6vs 78.9 ± 0.2 mg/100 mg oil; p < 0.05). To whom correspondence should be addressed     

芳香羧酸甲酯的硼氢化钠还原

采用NaBH_4-THF-甲醇体系将芳香羧酸甲酯进行还原反应2～5h得到相应的醇,收率为70%～90%。实验证明,NaBH_4-THF-甲醇体系对于芳香羧酸甲酯的还原具有很好的选择性。     

Polyaniline membranes for nanofiltration of solvent from dewaxed lube oil

Polyaniline nanofiltration membranes were synthesized to examine a potential candidate for application of solvent recovery from lube oil. An integrally skinned polyaniline membrane was cast on a woven polyester fabric and then was chemically crosslinked with glutaraldehyde in order to further increase the membranes resistant in a methyl ethyl ketone and toluene mixture. Subsequently, membrane performance was tested under different operational conditions. The operation pressure was fixed at 35 bar and was held constant for all of the tests. The membrane demonstrated a permeate flux of 10 l/(m² h) and oil rejection of 69%.

Abbreviations: PANi: Polyaniline; PI: polyimide; MEK: methyl ethyl ketone; GA: glutaraldehyde; NMP: N-methyl-2-pyrrolidone; 4MP: 4-methylpiperidine; SEM: Scanning Electron Microscope; OSN: organic solvent nanofiltration; MWCO: molecular weight cut-off.     

Electrolytic cleavage of 1,2,4-trioxolanes of sunflower oil methyl esters

Electrolytic cleavage of 1,2,4-trioxolanes produced from partial and complete ozonation of SFO methyl esters was presented. The electroreduction was conducted in an undivided cell using copper electrodes in the presence of alcohol and carboxylic acid as proton donor and either LiClO₄ or NaClO₄ as supporting electrolyte. The temperature of the system during electrolysis should be maintained below 100 °C to avoid possible thermolysis of 1,2,4-trioxolanes. FTIR and ¹H and ¹³C NMR analyses revealed that the reduction products include aldehyde, terminal alkene and acetal. Possible mechanisms explaining the formation of identified functional groups were discussed.     

Effects of epoxidation on the thermal oxidative stabilities of fatty acid esters derived from palm olein

A variety of esters from the reactions of monoalcohols with palm olein were prepared, epoxidized byin situ peroxyacid techniques, and some of their physical properties were compared. The thermal oxidative stabilities of these esters andbis(2-ethylhexyl) phthalate were studied. The esters were placed in an oven maintained at 120°C, and the loss of mass and acid, iodine, percent oxirane, hydroxyl, and peroxide values were monitored periodically. The epoxidized esters had higher densities and lower volatilities, and were more resistant toward oxidation than their unepoxidized counterparts. The stability of the oxirane was related to the initial acid value of the sample. Higher initial acid value resulted in a greater decrease in the oxirane content, indicating acid-catalyzed cleavage of the oxirane ring.     

聚酰亚胺膜的制备及对有机物系的纳滤分离

针对以均苯四甲酸二酐(PMDA)和4,4′-二氨基二苯醚(ODA)为原料合成聚酰亚胺的过程,研究了亚胺化方法、凝胶浴组成与温度等条件对膜的结构和分离性能的影响。实验结果表明,当聚酰胺酸铸膜液质量分数为15%、凝胶浴为30%乙醇(质量)的醇水溶液时,所制得的聚酰亚胺纳滤膜具有最佳的分离性能。操作压力为2MPa下稳态操作时,该膜对酮苯脱蜡工艺后的溶剂与润滑油基础油混合物的截留率达66%,通量为4.26L/(m2.h),为有机溶剂体系的纳滤膜分离技术的工业应用提供了基础。