生物柴油的绿色制备工艺
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摘要
生物柴油是以生物质为原料生产的可再生的绿色能源,对解决当今世界面临的能源短缺和环境污染两大问题具有十分重要的意义。制取工艺中催化剂性能优劣直接影响工艺的可行性。本文主要研究了以离子液体和离子交换树脂为催化剂催化大豆油的酯交换反应制备生物柴油。
1.离子液体没有显著的蒸汽压,结构和酸性均可调,因此可作为酸性催化剂催化酯交换反应制备生物柴油。氯化胆碱·xZnCl_2离子液体具有制备简单,原料价格低廉,对水稳定等优点,可作为制备生物柴油的催化剂。本文研究了醇油比、催化剂用量、反应温度等因素对酯交换反应的影响,并首次给出了生物柴油与豆油的分离工艺。
2.以树脂为碱性催化剂,官能团基本为季铵盐,本文采用离子液体片段N-甲基咪唑可以提高树脂的耐高温性能。N-甲基咪唑功能化的阴离子交换树脂改变了树脂的极性,提高了生物柴油的产率。研究溶解在树脂上的NaOH对树脂的作用。以含有NaOH的N-甲基咪唑功能化的阴离子交换树脂为催化剂制备生物柴油,NaOH的用量仅为常规法的17%,NaOH与树脂的共催化作用提高了催化剂的整体催化效率,研究了影响酯交换反应的三个因素:醇油比、催化剂用量和搅拌速度。
离子液体和离子交换树脂均是环保,可回收的绿色催化剂,是目前制备生物柴油的理想催化剂。
Biodiesel, has been synthesized by transesterification of vegetable oil or animal oil and low carbon alcohol, the properties of which is similar to petroleum diesel. The traditional method is methanolysis of vegetable oils catalyzed by metal hydroxides (or alkoxides) and sulfuric acid. Nevertheless, technological problems, such as corrosion and emulsification, are usually associated with these acid/base methodologies. Therefore, applying environmental-friendly, recoverable catalyst for production of biodiesel has become the research hotspot. In this paper, we applied ionic liquids and anion-exchange resin for transesterification of soybean oil to biodesel.
Choline chloride·2ZnCl_2 possess easy production, high thermal stability with decomposition temperature of 322.82℃. The structure of choline chloride·xZnCl_2 were analyzed by IR, NMR 1H and NMR 13C which was in agreement with the theoretical structure. The acidity of choline chloride·xZnCl_2 was determined by using pyridine as infrared spectroscopic probe. The bands in ranges of 1445—1460 cm-1and 1602—1640 cm-1 are indicative of pyridine coordination to Lewis acid sites, that indicated choline chloride·xZnCl_2 were Lewis acid. The acidity of choline chloride·xZnCl_2 increased with increasing x. The acidity of choline chloride·3ZnCl_2 is the strongest, but the excess ZnCl_2 will partially hydrolyze with the adsorbed water. The yield fo biodiesel was slightly enhanced with increasing x from 1 to 3 because of the increasing acidity of choline chloride·xZnCl_2. Choline chloride·2ZnCl_2 was liquid at room temperature while choline chloride·ZnCl_2 and choline chloride·3ZnCl_2 were solid. The viscosity of choline chloride·2ZnCl_2 was determined to be 281 Pa?s at 298K. In this paper, the transesterification of soybean oil was catalyzed by choline chloride·2ZnCl_2 and the influences of reaction temperature, amount of ionic liquids and molar ratio of methanol to sobyean oil were investigated. The results showed that the influence of reaction temperature on the transesterification became smaller with an increase in temperature. The reaction temperature consumedly exceeded the boiling point of methanol such as 80℃and 90℃, and the methanol will quikly vaporize and form a large number of bubbles, which inhibited the reaction on the two-phase interface. The highest conversion is achieved at 10% choline chloride?2ZnCl_2. The production yield could be elevated by introducing excess amount of the reactant methanol. When methanol is further increased, the concentration of catalyst was diluted at a fixed amount of choline chloride?2ZnCl_2 and soybean oil, and the amount of methanol has a slight effect on the catalytic performance after 16:1. The yield of biodiesel using choline chloride?2ZnCl_2 as catalyst under molar ratio of methanol to oil of 16:1 with addition of 10% catalyst at 70°C for 72h was 54.52%. The effect of moisture on transesterification was also investigated. The research showed that choline chloride?2ZnCl_2 was moisture stable and the the yield was enhanced less than 2% without water. The yield of biodiesel was 54.52% at the optimal condition, therfore, biodiesel needed to be purified by solvent extraction using methanol as extractant, and the extraction rate could up to 86.76%.
Because of the non-ideal yield catalyzed by choline chloride?2ZnCl_2. N-methylimmidizolium functionalized anion exchange resin containing NaOH was synthesized and applied for production of biodiesel. The structure of PS-DVB and ROH (Na) were analyzed by IR, the results indicated that Cl in PS-DVB was substituted by zwitterinoic methylimidazolium chloride (mimCl) group. According to elementary analysis of RCl, the yield of RCl was calculated to be 92.02%. The yield of ROH was determined and calculated to be 84.8% by determination of the content of Cl- in methanol solution, therefore, the content of OH- in ROH was 2.91mmol/g. ROH (Na) provied with high thermal stability with 223.61℃, high content of OH- and homogenous microporous distribution, but transesterification was co-catalyzed by NaOH with ROH. Transesterification was catalyzed by 0.17% NaOH and the yield of biodiesel was 70.15% that did not reach to 97.25% catalyzed by ROH containing 3.95% Na. The introduction of N-methylimmidizolium modified the polarity of resin; enhanced the solubility of soybean oil and methanol; increased the co-catalytic activity of ROH (Na). The amount of NaOH was 17% compared with traditional method, greatly decreased the loss of NaOH. NaOH in ROH (Na) not only catalyzed the transesterification, but also activated the anion OH- of ROH. The influence of molar ratio to soybean oil, stirring rate and amount of catalyst were investigated. The molar ratio beyond 12:1, the yield of biodiesel was not enhanced obviously. When the amount of catalyst was 2.5% catalyst exhibited highest catalytic activity. Increasing the stirring rate would enhance the opotunity of reactant contacting with catalyst. The yield of biodiesel was not increased obviously after 570 rsp/min. The yield of biodiesel was up to 97.25% with molar ratio of methanol to soybean oil 16:1, the amount of catalyst 2.5%,reaction temperature 50℃, stirring rate 570 rsp/min and reaction time 10 h. The resin could be reused by regeneration.
1.离子液体没有显著的蒸汽压,结构和酸性均可调,因此可作为酸性催化剂催化酯交换反应制备生物柴油。氯化胆碱·xZnCl_2离子液体具有制备简单,原料价格低廉,对水稳定等优点,可作为制备生物柴油的催化剂。本文研究了醇油比、催化剂用量、反应温度等因素对酯交换反应的影响,并首次给出了生物柴油与豆油的分离工艺。
2.以树脂为碱性催化剂,官能团基本为季铵盐,本文采用离子液体片段N-甲基咪唑可以提高树脂的耐高温性能。N-甲基咪唑功能化的阴离子交换树脂改变了树脂的极性,提高了生物柴油的产率。研究溶解在树脂上的NaOH对树脂的作用。以含有NaOH的N-甲基咪唑功能化的阴离子交换树脂为催化剂制备生物柴油,NaOH的用量仅为常规法的17%,NaOH与树脂的共催化作用提高了催化剂的整体催化效率,研究了影响酯交换反应的三个因素:醇油比、催化剂用量和搅拌速度。
离子液体和离子交换树脂均是环保,可回收的绿色催化剂,是目前制备生物柴油的理想催化剂。
Biodiesel, has been synthesized by transesterification of vegetable oil or animal oil and low carbon alcohol, the properties of which is similar to petroleum diesel. The traditional method is methanolysis of vegetable oils catalyzed by metal hydroxides (or alkoxides) and sulfuric acid. Nevertheless, technological problems, such as corrosion and emulsification, are usually associated with these acid/base methodologies. Therefore, applying environmental-friendly, recoverable catalyst for production of biodiesel has become the research hotspot. In this paper, we applied ionic liquids and anion-exchange resin for transesterification of soybean oil to biodesel.
Choline chloride·2ZnCl_2 possess easy production, high thermal stability with decomposition temperature of 322.82℃. The structure of choline chloride·xZnCl_2 were analyzed by IR, NMR 1H and NMR 13C which was in agreement with the theoretical structure. The acidity of choline chloride·xZnCl_2 was determined by using pyridine as infrared spectroscopic probe. The bands in ranges of 1445—1460 cm-1and 1602—1640 cm-1 are indicative of pyridine coordination to Lewis acid sites, that indicated choline chloride·xZnCl_2 were Lewis acid. The acidity of choline chloride·xZnCl_2 increased with increasing x. The acidity of choline chloride·3ZnCl_2 is the strongest, but the excess ZnCl_2 will partially hydrolyze with the adsorbed water. The yield fo biodiesel was slightly enhanced with increasing x from 1 to 3 because of the increasing acidity of choline chloride·xZnCl_2. Choline chloride·2ZnCl_2 was liquid at room temperature while choline chloride·ZnCl_2 and choline chloride·3ZnCl_2 were solid. The viscosity of choline chloride·2ZnCl_2 was determined to be 281 Pa?s at 298K. In this paper, the transesterification of soybean oil was catalyzed by choline chloride·2ZnCl_2 and the influences of reaction temperature, amount of ionic liquids and molar ratio of methanol to sobyean oil were investigated. The results showed that the influence of reaction temperature on the transesterification became smaller with an increase in temperature. The reaction temperature consumedly exceeded the boiling point of methanol such as 80℃and 90℃, and the methanol will quikly vaporize and form a large number of bubbles, which inhibited the reaction on the two-phase interface. The highest conversion is achieved at 10% choline chloride?2ZnCl_2. The production yield could be elevated by introducing excess amount of the reactant methanol. When methanol is further increased, the concentration of catalyst was diluted at a fixed amount of choline chloride?2ZnCl_2 and soybean oil, and the amount of methanol has a slight effect on the catalytic performance after 16:1. The yield of biodiesel using choline chloride?2ZnCl_2 as catalyst under molar ratio of methanol to oil of 16:1 with addition of 10% catalyst at 70°C for 72h was 54.52%. The effect of moisture on transesterification was also investigated. The research showed that choline chloride?2ZnCl_2 was moisture stable and the the yield was enhanced less than 2% without water. The yield of biodiesel was 54.52% at the optimal condition, therfore, biodiesel needed to be purified by solvent extraction using methanol as extractant, and the extraction rate could up to 86.76%.
Because of the non-ideal yield catalyzed by choline chloride?2ZnCl_2. N-methylimmidizolium functionalized anion exchange resin containing NaOH was synthesized and applied for production of biodiesel. The structure of PS-DVB and ROH (Na) were analyzed by IR, the results indicated that Cl in PS-DVB was substituted by zwitterinoic methylimidazolium chloride (mimCl) group. According to elementary analysis of RCl, the yield of RCl was calculated to be 92.02%. The yield of ROH was determined and calculated to be 84.8% by determination of the content of Cl- in methanol solution, therefore, the content of OH- in ROH was 2.91mmol/g. ROH (Na) provied with high thermal stability with 223.61℃, high content of OH- and homogenous microporous distribution, but transesterification was co-catalyzed by NaOH with ROH. Transesterification was catalyzed by 0.17% NaOH and the yield of biodiesel was 70.15% that did not reach to 97.25% catalyzed by ROH containing 3.95% Na. The introduction of N-methylimmidizolium modified the polarity of resin; enhanced the solubility of soybean oil and methanol; increased the co-catalytic activity of ROH (Na). The amount of NaOH was 17% compared with traditional method, greatly decreased the loss of NaOH. NaOH in ROH (Na) not only catalyzed the transesterification, but also activated the anion OH- of ROH. The influence of molar ratio to soybean oil, stirring rate and amount of catalyst were investigated. The molar ratio beyond 12:1, the yield of biodiesel was not enhanced obviously. When the amount of catalyst was 2.5% catalyst exhibited highest catalytic activity. Increasing the stirring rate would enhance the opotunity of reactant contacting with catalyst. The yield of biodiesel was not increased obviously after 570 rsp/min. The yield of biodiesel was up to 97.25% with molar ratio of methanol to soybean oil 16:1, the amount of catalyst 2.5%,reaction temperature 50℃, stirring rate 570 rsp/min and reaction time 10 h. The resin could be reused by regeneration.
引文
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2.李昌珠,蒋丽娟,程树棋.生物柴油-绿色能源[M].北京:化学工业出版社, 2005.
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