棕榈油制备润滑剂的研究
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摘要
本研究针对棕榈油脂肪酸中含有不饱和的C=C双键,其甘油分子中含有β-H,致使其氧化稳定性较差的问题,通过环氧化和开环反应消除棕榈油脂肪酸中的C=C双键,通过酯交换反应消除棕榈油甘油分子中的β-H,提高其氧化稳定性,制备环氧棕榈油、乙酸异构酯和三羟甲基丙烷三酯三种润滑剂基础油,并与添加剂复配制备三种不同粘度等级的绿色食品机械润滑剂。
以棕榈油为原料,采用过氧乙酸和过氧甲酸两种方法制备环氧棕榈油,通过单因素、正交和响应面设计,并对两种方法进行对比,得到过氧甲酸法制备的环氧棕榈油具有较高的环氧值,其最佳制备条件为:投料比m(棕榈油):m(甲酸):m(30%的双氧水):m(浓硫酸)=30:6:43:0.3,反应温度为65℃,反应时间为6h,在此条件下得到产品的环氧值为3.89%。环氧棕榈油的结构由红外光谱表征。
以过氧甲酸法制备的环氧棕榈油为原料,在无催化剂条件下使其与乙酸作用发生开环反应制备乙酸异构酯。通过实验设计和数据处理,得到环氧棕榈油在乙酸作用下的开环动力学模型,r=k[Ep][CH_3COOH]~(1.6),[Ep]为环氧键的摩尔浓度,[CH_3COOH]为乙酸的摩尔浓度,k为反应速率常数。由动力学研究还得出,k与反应温度T遵循阿仑尼乌斯方程,开环反应速率随着温度的升高而增大,开环反应的活化能Ea为40.28KJ·mol~(-1)。依据环氧棕榈油在乙酸作用下的开环动力学性质,选取乙酸和环氧键的摩尔比为5:1,反应温度90℃,反应时间3h,制得乙酸异构酯的剩余环氧值为0.09%,其结构由红外光谱表征。
本研究还以棕榈油为原料,先与甲醇反应制备棕榈油脂肪酸甲酯,再使棕榈油脂肪酸甲酯和三羟甲基丙烷酯交换制备不含β-H的三羟甲基丙烷三酯,并通过单因素和响应面设计,得到三羟甲基丙烷三酯的最佳制备条件为:棕榈油脂肪酸甲酯和三羟甲基丙烷的摩尔比为7.3:1,甲醇钠加入量为总量的0.86%,反应温度为168℃,反应时间为7h,在此条件下三酯生成率最高为88.75%。经分子蒸馏后,产品的纯度达98.6%,结构由红外光谱和质谱表征。
此外,以自制环氧棕榈油、乙酸异构酯和三羟甲基丙烷三酯为基础油,PB-1300(聚异丁烯)、T803B(聚α-烯烃)、BHT(2, 6-二叔丁基对甲酚)和司苯-80(山梨糖醇单甘油酯)为添加剂,复配制得68、220和150三种不同粘度等级的润滑剂。三种合成润滑剂均有很好的粘温性能、安全稳定性和生物降解性,其色泽、酸值、硫酸盐灰分、水分、机械杂质等指标也优于市售石油基润滑剂,是三种绿色食品机械润滑剂。
The C=C double bonds in the unsaturated fatty acid and theβ-H in the glycerol molecule make palm oil have poor oxidation stability. In this paper, through epoxidation and ring-opening reaction, the C=C was removed, and through transesterification, theβ-H was removed. After chemical modification, the oxidation stability of palm oil was greatly improved. Three kinds of lubricant base oils: epoxy palm oil, acetic acid isomer-ester and trimethylolpropane tri-ester were prepared in this paper. Then, the base oils were compounded with additives to prepare three different viscosity grades of green food machinery lubricants.
The epoxy palm oil was prepared using peracetic acid and peroxyformic acid. Adopting single-factor experiments, orthogonal experiments and response surface methodology, and comparing of the two preparation methods, the epoxy palm oil which was prepared using peroxyformic acid had a higher epoxy value. The optimum conditions were determined as follows: mass ratio of palm oil to formic acid to hydrogen peroxide (concentration 30%) to concentrated sulfuric acid 30:6:43:0.3, reaction time 6h, temperature 65℃, and in this condition, its epoxy value was 3.89%. The structural confirmation of the epoxy palm oil was done by FT-IR.
The epoxy palm oil prepared using peroxyformic acid was reacted with acetic acid to prepare acetic acid isomer-ester through ring opening reaction. By experimental design and data processing, the rate equation of oxirane cleavage was found to be satisfied with r= k[Ep][CH_3COOH]~(1.6), [Ep] was the molar concentration of oxiranes; [CH_3COOH] was the molar concentration of acetic acid and k was the rate constant. The study also showed that, k and the reaction temperature T followed the Arrhenius equation, and the higher the reaction temperature, the faster the oxirane cleavage reaction. The activation energy of oxirane cleavage was 40.28KJ·mol-1. According to the kinetic study, selecting the molar ratio of acetic acid to oxiranes 5:1, reaction temperature 90℃, reaction time 3h, in this condition, the residual epoxy value of the acetic acid isomer-ester was 0.09%, and the structural confirmation was done by FT-IR.
The palm oil was also reacted with methanol to prepare palm oil methyl ester, then the palm oil methyl ester was reacted with trimethylolpropane to synthesize trimethylolpropane tri-ester. Adopting the single-factor experiments and response surface methodology, the optimum conditions were determined as follows: the molar ratio of palm oil methyl ester and trimethylolpropane was 7.3:1, amount of sodium methoxide 0.86%, reaction for 7h at temperature of 168℃, and the production rate of tri-ester was up to 88.75%. After purification with molecular distillation, the purity of tri-ester was 98.6%. The structural confirmation was done by FT-IR and MS.
Then, the epoxy palm oil, acetic acid isomer-ester and trimethylolpropane tri-ester were compounded with PB-1300 (polyisobutylene), T803B (poly-α-olefin), BHT (2,6-Di-tert-butyl-4-methylphenol) and S-80(sorbitol monoglycerides) to prepare green food machinery lubricants of different viscosity grades of 68, 220 and 150. The three kinds of lubricants all had good viscosity-temperature performances, outstanding security stability and excellent biodegradability, and their color, acid value, sulfate ash, moisture, mechanical impurities and other properties were also better than commercial petroleum-based lubricants.
以棕榈油为原料,采用过氧乙酸和过氧甲酸两种方法制备环氧棕榈油,通过单因素、正交和响应面设计,并对两种方法进行对比,得到过氧甲酸法制备的环氧棕榈油具有较高的环氧值,其最佳制备条件为:投料比m(棕榈油):m(甲酸):m(30%的双氧水):m(浓硫酸)=30:6:43:0.3,反应温度为65℃,反应时间为6h,在此条件下得到产品的环氧值为3.89%。环氧棕榈油的结构由红外光谱表征。
以过氧甲酸法制备的环氧棕榈油为原料,在无催化剂条件下使其与乙酸作用发生开环反应制备乙酸异构酯。通过实验设计和数据处理,得到环氧棕榈油在乙酸作用下的开环动力学模型,r=k[Ep][CH_3COOH]~(1.6),[Ep]为环氧键的摩尔浓度,[CH_3COOH]为乙酸的摩尔浓度,k为反应速率常数。由动力学研究还得出,k与反应温度T遵循阿仑尼乌斯方程,开环反应速率随着温度的升高而增大,开环反应的活化能Ea为40.28KJ·mol~(-1)。依据环氧棕榈油在乙酸作用下的开环动力学性质,选取乙酸和环氧键的摩尔比为5:1,反应温度90℃,反应时间3h,制得乙酸异构酯的剩余环氧值为0.09%,其结构由红外光谱表征。
本研究还以棕榈油为原料,先与甲醇反应制备棕榈油脂肪酸甲酯,再使棕榈油脂肪酸甲酯和三羟甲基丙烷酯交换制备不含β-H的三羟甲基丙烷三酯,并通过单因素和响应面设计,得到三羟甲基丙烷三酯的最佳制备条件为:棕榈油脂肪酸甲酯和三羟甲基丙烷的摩尔比为7.3:1,甲醇钠加入量为总量的0.86%,反应温度为168℃,反应时间为7h,在此条件下三酯生成率最高为88.75%。经分子蒸馏后,产品的纯度达98.6%,结构由红外光谱和质谱表征。
此外,以自制环氧棕榈油、乙酸异构酯和三羟甲基丙烷三酯为基础油,PB-1300(聚异丁烯)、T803B(聚α-烯烃)、BHT(2, 6-二叔丁基对甲酚)和司苯-80(山梨糖醇单甘油酯)为添加剂,复配制得68、220和150三种不同粘度等级的润滑剂。三种合成润滑剂均有很好的粘温性能、安全稳定性和生物降解性,其色泽、酸值、硫酸盐灰分、水分、机械杂质等指标也优于市售石油基润滑剂,是三种绿色食品机械润滑剂。
The C=C double bonds in the unsaturated fatty acid and theβ-H in the glycerol molecule make palm oil have poor oxidation stability. In this paper, through epoxidation and ring-opening reaction, the C=C was removed, and through transesterification, theβ-H was removed. After chemical modification, the oxidation stability of palm oil was greatly improved. Three kinds of lubricant base oils: epoxy palm oil, acetic acid isomer-ester and trimethylolpropane tri-ester were prepared in this paper. Then, the base oils were compounded with additives to prepare three different viscosity grades of green food machinery lubricants.
The epoxy palm oil was prepared using peracetic acid and peroxyformic acid. Adopting single-factor experiments, orthogonal experiments and response surface methodology, and comparing of the two preparation methods, the epoxy palm oil which was prepared using peroxyformic acid had a higher epoxy value. The optimum conditions were determined as follows: mass ratio of palm oil to formic acid to hydrogen peroxide (concentration 30%) to concentrated sulfuric acid 30:6:43:0.3, reaction time 6h, temperature 65℃, and in this condition, its epoxy value was 3.89%. The structural confirmation of the epoxy palm oil was done by FT-IR.
The epoxy palm oil prepared using peroxyformic acid was reacted with acetic acid to prepare acetic acid isomer-ester through ring opening reaction. By experimental design and data processing, the rate equation of oxirane cleavage was found to be satisfied with r= k[Ep][CH_3COOH]~(1.6), [Ep] was the molar concentration of oxiranes; [CH_3COOH] was the molar concentration of acetic acid and k was the rate constant. The study also showed that, k and the reaction temperature T followed the Arrhenius equation, and the higher the reaction temperature, the faster the oxirane cleavage reaction. The activation energy of oxirane cleavage was 40.28KJ·mol-1. According to the kinetic study, selecting the molar ratio of acetic acid to oxiranes 5:1, reaction temperature 90℃, reaction time 3h, in this condition, the residual epoxy value of the acetic acid isomer-ester was 0.09%, and the structural confirmation was done by FT-IR.
The palm oil was also reacted with methanol to prepare palm oil methyl ester, then the palm oil methyl ester was reacted with trimethylolpropane to synthesize trimethylolpropane tri-ester. Adopting the single-factor experiments and response surface methodology, the optimum conditions were determined as follows: the molar ratio of palm oil methyl ester and trimethylolpropane was 7.3:1, amount of sodium methoxide 0.86%, reaction for 7h at temperature of 168℃, and the production rate of tri-ester was up to 88.75%. After purification with molecular distillation, the purity of tri-ester was 98.6%. The structural confirmation was done by FT-IR and MS.
Then, the epoxy palm oil, acetic acid isomer-ester and trimethylolpropane tri-ester were compounded with PB-1300 (polyisobutylene), T803B (poly-α-olefin), BHT (2,6-Di-tert-butyl-4-methylphenol) and S-80(sorbitol monoglycerides) to prepare green food machinery lubricants of different viscosity grades of 68, 220 and 150. The three kinds of lubricants all had good viscosity-temperature performances, outstanding security stability and excellent biodegradability, and their color, acid value, sulfate ash, moisture, mechanical impurities and other properties were also better than commercial petroleum-based lubricants.
引文
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