离子液体中脂肪酶催化桐油合成生物柴油的研究
摘要
生物柴油以其可再生、环境友好等特性得到公众的认可。生物柴油可以通过物理法、化学法和生物法等方法制得,尤其是生物法,生物酶法合成生物柴油具有反应条件温和,零排放等优点,是最具发展前景的方法。本文采用脂肪酶催化酯交换制备生物柴油,生物酶法的关键是生物催化剂的催化活性和稳定性。
通过两步法制得的离子液体作为反应的溶剂,通过红外光谱和核磁共振对合成的离子液体进行了表征,结果表明合成的液体就是目标离子液体[BMIM]PF_6;在合成的离子液体中对脂肪酶的耐受性进行了测定,结果固定化脂肪酶在40℃的离子液体中培养24h,酶的活性仍能保持在70%以上。
本文主要研究了用桐油转化生物柴油,分析评价了桐油的理化性质,陕南桐油的磷脂含量49.65 mg/kg,酸值3.66 mgKOH/g,过氧化值4.43 mol/L,皂化值191.8 mgKOH/g,碘值166.7 g/100g,粘度(27℃)197.3 mpa.s。计算得到桐油平均分子量是894.55g/mol。通过对桐油的色谱分析得出桐油的主要成分为桐酸、亚油酸、油酸、其中桐酸相对含量为78.04%,其次是亚油酸和油酸分别为11.557%和4.167%。
原料油的预处理实验中,对桐油水化脱胶实验进行了优化,最终得到的优化条件为:水化时间21min,加水量3.9%,水化温度73℃,使桐油中磷脂的含量从最初的49.65mg/Kg到19.52 mg/kg,使得磷脂对反应的影响降到最低。
以离子液体[BMIM]PF_6为溶剂,在离子液体中合成生物柴油。通过正交实验对在离子液体中合成生物柴油的实验条件进行了优化,最优条件:醇油比为3:1,加酶量为油重的15%,反应温度为45℃,反应24小时。在此条件下,实际实验测得的实际甲酯转化率为76.3%。在反应体系中对脂肪酶的稳定性进行了研究,研究表明在以[BMIM]PF_6为溶剂的反应体系中,经过6次重复使用脂肪酸甲酯转化率仍能维持在50%以上。
People recognize biodiesel as it reproducible and environmental friendly.Biodiesel can be synthesized by physical method or chemical method or biological method.Especially the biological method,the biological enzyme synthesis biodiesel has the response condition to be temperate,merit and so on non-pollutant emission,was the recent years research hot spot.It is the most promising method in the various methods for biodiesel production.In this paper,the biological enzyme synthesis biodiesel has been chosen,and its key point is the activity and stability of the biological enzyme.
Ionic Liquid[BMIM]PF_6 was chosen as the solvent of the reaction,which was synthesized through a typical two-step way.The FT-IR and MRI were used to make sure that we get the[BMIM]PF_6.The stability of the lipase in[BMIM]PF_6 was investigated,after 24h suspended in[BMIM]PF_6 at 40℃,the lipase retained approximately above 70%of it original activity.
The aim of this research is to study the preparation method of biodiesel fules from Tung oil.The character of Tung oil were analyzed,the results show that phosphorous content was 49.65 mg/Kg,acid value was 3.66 mgKOH/g,peroxidate value was 4.43 mol/L, saponification value was 191.8 mgKOH/g,iodine value was 166.7 g/100g,viscosity value(27℃) was 197.3 mpa.s,the average molecular weight of Tung oil was 894.55g/mol. GC methods were used to analysis of Tung oil,the main compositions were elaeostearic acid(78.04%),octadecadienoic acid(11.557%),and octadecenoic acid(4.167%)
In the study of the pretreatment of raw oil,hydration degumming was accepted to optimize the condition of the experiment.The optimization of hydration degumming were: water 3.9%,temperature of 73℃,and the reaction time of 21min,leading to the decrease of phosphorous content from 49.65 mg/Kg to 19.52 mg/kg.After hydration degumming disadvantage of the phosphorus can reduce to minimum.
We Prepare biodiesel from Tung oil with ionic liquid[BMIM]PF_6,By the orthogonal test of the Tung oil transesterification reaction with[BMIM]PF_6,the optimum conditions for biodiesel preparation were:molar ratio of Tung oil to methanol 3:1,15%w/w(oil) of catalysts, reaction temperature 45℃,reaction time 24h,with the average yield of 76.3%.The stability of the lipase in the reaction was investigated,after 6 times use,the conversion of the fatty acid methyl retained approximately above 50%of it original rate.
通过两步法制得的离子液体作为反应的溶剂,通过红外光谱和核磁共振对合成的离子液体进行了表征,结果表明合成的液体就是目标离子液体[BMIM]PF_6;在合成的离子液体中对脂肪酶的耐受性进行了测定,结果固定化脂肪酶在40℃的离子液体中培养24h,酶的活性仍能保持在70%以上。
本文主要研究了用桐油转化生物柴油,分析评价了桐油的理化性质,陕南桐油的磷脂含量49.65 mg/kg,酸值3.66 mgKOH/g,过氧化值4.43 mol/L,皂化值191.8 mgKOH/g,碘值166.7 g/100g,粘度(27℃)197.3 mpa.s。计算得到桐油平均分子量是894.55g/mol。通过对桐油的色谱分析得出桐油的主要成分为桐酸、亚油酸、油酸、其中桐酸相对含量为78.04%,其次是亚油酸和油酸分别为11.557%和4.167%。
原料油的预处理实验中,对桐油水化脱胶实验进行了优化,最终得到的优化条件为:水化时间21min,加水量3.9%,水化温度73℃,使桐油中磷脂的含量从最初的49.65mg/Kg到19.52 mg/kg,使得磷脂对反应的影响降到最低。
以离子液体[BMIM]PF_6为溶剂,在离子液体中合成生物柴油。通过正交实验对在离子液体中合成生物柴油的实验条件进行了优化,最优条件:醇油比为3:1,加酶量为油重的15%,反应温度为45℃,反应24小时。在此条件下,实际实验测得的实际甲酯转化率为76.3%。在反应体系中对脂肪酶的稳定性进行了研究,研究表明在以[BMIM]PF_6为溶剂的反应体系中,经过6次重复使用脂肪酸甲酯转化率仍能维持在50%以上。
People recognize biodiesel as it reproducible and environmental friendly.Biodiesel can be synthesized by physical method or chemical method or biological method.Especially the biological method,the biological enzyme synthesis biodiesel has the response condition to be temperate,merit and so on non-pollutant emission,was the recent years research hot spot.It is the most promising method in the various methods for biodiesel production.In this paper,the biological enzyme synthesis biodiesel has been chosen,and its key point is the activity and stability of the biological enzyme.
Ionic Liquid[BMIM]PF_6 was chosen as the solvent of the reaction,which was synthesized through a typical two-step way.The FT-IR and MRI were used to make sure that we get the[BMIM]PF_6.The stability of the lipase in[BMIM]PF_6 was investigated,after 24h suspended in[BMIM]PF_6 at 40℃,the lipase retained approximately above 70%of it original activity.
The aim of this research is to study the preparation method of biodiesel fules from Tung oil.The character of Tung oil were analyzed,the results show that phosphorous content was 49.65 mg/Kg,acid value was 3.66 mgKOH/g,peroxidate value was 4.43 mol/L, saponification value was 191.8 mgKOH/g,iodine value was 166.7 g/100g,viscosity value(27℃) was 197.3 mpa.s,the average molecular weight of Tung oil was 894.55g/mol. GC methods were used to analysis of Tung oil,the main compositions were elaeostearic acid(78.04%),octadecadienoic acid(11.557%),and octadecenoic acid(4.167%)
In the study of the pretreatment of raw oil,hydration degumming was accepted to optimize the condition of the experiment.The optimization of hydration degumming were: water 3.9%,temperature of 73℃,and the reaction time of 21min,leading to the decrease of phosphorous content from 49.65 mg/Kg to 19.52 mg/kg.After hydration degumming disadvantage of the phosphorus can reduce to minimum.
We Prepare biodiesel from Tung oil with ionic liquid[BMIM]PF_6,By the orthogonal test of the Tung oil transesterification reaction with[BMIM]PF_6,the optimum conditions for biodiesel preparation were:molar ratio of Tung oil to methanol 3:1,15%w/w(oil) of catalysts, reaction temperature 45℃,reaction time 24h,with the average yield of 76.3%.The stability of the lipase in the reaction was investigated,after 6 times use,the conversion of the fatty acid methyl retained approximately above 50%of it original rate.
引文
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