阴离子型树脂催化制备生物柴油的研究
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摘要
脂肪酸甲酯又被称作生物柴油，作为石油的替代品，随着石油资源的日益短缺，越来越受到人们的关注。目前，生物柴油的主要生产方法是使用NaOH作为均相碱催化剂，催化脂肪酸甘油脂(动植物油脂的主成分)和甲醇进行酯交换反应制备脂肪酸甲酯。虽然该技术比较成熟，但还是存在反应产生皂化导致分离困难、需水洗除掉碱催化剂而产生大量碱性废水造成环境污染等缺点。采用非均相固体催化剂可以避免上述问题的产生，因此该类催化剂催化酯交换反应制备生物柴油对生物柴油的推广有着重要的意义。
本论文设计使用特种聚醚砜型树脂制备出的季铵盐型线型强碱型树脂与二氧化硅的共混物(QAPPES／SiO_2)和通用聚醚砜型树脂制备出的季铵盐型线型强碱型树脂与二氧化硅的共混物(QAPSF／SiO_2)为非均相催化剂，催化了大豆油和甲醇的酯交换反应，制备出脂肪酸甲酯。合成出的一系列的脂肪酸甲酯混合物可以通过气相色谱和质谱联用(GC／MS)的测试得到确定。通过气相色谱图，可以发现QAPPES／SiO_2和QAPSF／SiO_2催化大豆油和甲醇酯交换反应得到的产物和NaOH催化大豆油和甲醇酯交换反应得到的产物中各组分的气相色谱的保留时间和峰形基本一致。通过质谱图可以确定，最主要的三个组分具体的结构为C_(15)H_(31)COOCH_3、C_(17)H_(31)COOCH_3和C_(17)H_(35)COOCH_3。
影响QAPPES／SiO_2和QAPSF／SiO_2催化大豆油和甲醇酯交换反应的因素主要有甲醇和大豆油的体积比、催化剂加入量和大豆油的加入量的关系(质量／体积)、反应温度、反应时间和反应的搅拌速率。这些因素通过一系列的实验加以研究和优化。实验表明，较好的反应条件为：高速搅拌条件下，反应物醇油比(体积比)为3：1-4：1，催化剂加入量与豆油加入量数值上的关系为1：4-3：8(质量／体积)，反应温度为60℃。在此条件下反应8h，QAPPES／SiO_2催化大豆油和甲醇酯交换反应的转化率可达到76％，QAPSF／SiO_2催化大豆油和甲醇酯交换反应的转化率可达到74％。
本论文中同时对季铵盐阴离子型商用大孔交联型树脂D201和D202对大豆油和甲醇酯交换反应的催化效果进行了测试。产物的测试方法同QAPPES／SiO_2和QAPSF／SiO_2催化大豆油和甲醇酯交换反应产物的测试方法。结果表明，D201和D202同样可以催化大豆油和甲醇的酯交换反应，得到一系列的脂肪酸甲酯的产物。实验表明，较好的反应条件为：反应物醇油比(体积比)为1：1-2：1，反应温度为60℃，催化剂加入量与豆油加入量数值上的关系为1：4-1：2(质量／体积)。在此条件下反应6h，D201催化大豆油和甲醇酯交换反应的转化率可达到80％，D202可达到81％。
With the gradual shortage of petroleum resource, biodiesel has been paid much more attention as one of the alternative fuel. Presently, the transesterification reaction of triglyceride which are the leading components of vegetable oil or animal fat with methanol using NaOH or KOH as a homogeneous catalyst is conducted to produce methyl fatty acid ester as biodiesel. Although this process is a mature technology, there are some disadvantages including saponification during the reaction which leads to the difficulty in separation of the production and wastewater from the washing of the production to remove the base catalyst. These problems could be avoided by using the heterogeneous solid catalysts for the production of biodiesel.
In this work, we proposed to use a quaternary ammonium poly(phthalazinone ether sulfone)(QAPPES) anion exchange resin/SiO_2 and a quaternary ammonium polysulfone(QAPSF) anion exchange resin/SiO_2 to catalyse the transesterification of soybean oil with methanol to generate methyl fatty acid ester heterogeneously. A series of methyl fatty acid ester as the production could be determinated by gas chromatography/mass spectrometry(GC/MS). From the diagrams of GC/MS, we discovered that the components of the productions catalysed by QAPPES/SiO_2 and QAPSF/SiO_2 had the same retention time and the same form of peaks as the components of the production catalysed by NaOH. The cases had also occurred in simplex gas chromatography(GC) which was used to calculate the conversion rate of methyl fatty acid ester by peak areas. Through GC/MS, the precise components of the production could also be acquired. The three most important components were methyl palmitate(C_(15)H_(31)COOCH_3), methyl linoleate(C_(17)H_(31)COOCH_3) and methyl stearate(C_(17)H_(35)COOCH_3).
The influences of reaction included the volume ratio of methanol to oil, the catalyst amount to oil(weight/volume), temperature, reaction time and stirring rate of reaction which were studied and optimized. The best condition were that volume ratio of methanol to oil was 3:1 to 4:1; the catalyst amount to oil(weight/volume) was 1:4 to 3:8; and the temperature was 60℃; fast stirring during the reaction was necessary. After 8h the conversion rate could reach 76% by using QAPPES/SiO_2 and 74 by using QAPSF/SiO_2.
The commercial macroporous cross-link resins were also tested as heterogeneous catalysts to catalyze transesterification of soybean oil with methanol. A series of methyl fatty acid ester as the production could also be acquired. The analysis methods of the production catalyzed by D201 and D202 were as the same as the production catalyzed by QAPPES/SiO_2 and QAPSF/SiO_2. The best condition were that volume ratio of methanol to oil was 1:1 to 2:1; the catalyst amount to oil(weight/volume) was 1:4 to 1:2; and the temperature was 60℃. After 6h the conversion rate could reach 80% by using D201 and 81% by using D202.
本论文设计使用特种聚醚砜型树脂制备出的季铵盐型线型强碱型树脂与二氧化硅的共混物(QAPPES／SiO_2)和通用聚醚砜型树脂制备出的季铵盐型线型强碱型树脂与二氧化硅的共混物(QAPSF／SiO_2)为非均相催化剂，催化了大豆油和甲醇的酯交换反应，制备出脂肪酸甲酯。合成出的一系列的脂肪酸甲酯混合物可以通过气相色谱和质谱联用(GC／MS)的测试得到确定。通过气相色谱图，可以发现QAPPES／SiO_2和QAPSF／SiO_2催化大豆油和甲醇酯交换反应得到的产物和NaOH催化大豆油和甲醇酯交换反应得到的产物中各组分的气相色谱的保留时间和峰形基本一致。通过质谱图可以确定，最主要的三个组分具体的结构为C_(15)H_(31)COOCH_3、C_(17)H_(31)COOCH_3和C_(17)H_(35)COOCH_3。
影响QAPPES／SiO_2和QAPSF／SiO_2催化大豆油和甲醇酯交换反应的因素主要有甲醇和大豆油的体积比、催化剂加入量和大豆油的加入量的关系(质量／体积)、反应温度、反应时间和反应的搅拌速率。这些因素通过一系列的实验加以研究和优化。实验表明，较好的反应条件为：高速搅拌条件下，反应物醇油比(体积比)为3：1-4：1，催化剂加入量与豆油加入量数值上的关系为1：4-3：8(质量／体积)，反应温度为60℃。在此条件下反应8h，QAPPES／SiO_2催化大豆油和甲醇酯交换反应的转化率可达到76％，QAPSF／SiO_2催化大豆油和甲醇酯交换反应的转化率可达到74％。
本论文中同时对季铵盐阴离子型商用大孔交联型树脂D201和D202对大豆油和甲醇酯交换反应的催化效果进行了测试。产物的测试方法同QAPPES／SiO_2和QAPSF／SiO_2催化大豆油和甲醇酯交换反应产物的测试方法。结果表明，D201和D202同样可以催化大豆油和甲醇的酯交换反应，得到一系列的脂肪酸甲酯的产物。实验表明，较好的反应条件为：反应物醇油比(体积比)为1：1-2：1，反应温度为60℃，催化剂加入量与豆油加入量数值上的关系为1：4-1：2(质量／体积)。在此条件下反应6h，D201催化大豆油和甲醇酯交换反应的转化率可达到80％，D202可达到81％。
With the gradual shortage of petroleum resource, biodiesel has been paid much more attention as one of the alternative fuel. Presently, the transesterification reaction of triglyceride which are the leading components of vegetable oil or animal fat with methanol using NaOH or KOH as a homogeneous catalyst is conducted to produce methyl fatty acid ester as biodiesel. Although this process is a mature technology, there are some disadvantages including saponification during the reaction which leads to the difficulty in separation of the production and wastewater from the washing of the production to remove the base catalyst. These problems could be avoided by using the heterogeneous solid catalysts for the production of biodiesel.
In this work, we proposed to use a quaternary ammonium poly(phthalazinone ether sulfone)(QAPPES) anion exchange resin/SiO_2 and a quaternary ammonium polysulfone(QAPSF) anion exchange resin/SiO_2 to catalyse the transesterification of soybean oil with methanol to generate methyl fatty acid ester heterogeneously. A series of methyl fatty acid ester as the production could be determinated by gas chromatography/mass spectrometry(GC/MS). From the diagrams of GC/MS, we discovered that the components of the productions catalysed by QAPPES/SiO_2 and QAPSF/SiO_2 had the same retention time and the same form of peaks as the components of the production catalysed by NaOH. The cases had also occurred in simplex gas chromatography(GC) which was used to calculate the conversion rate of methyl fatty acid ester by peak areas. Through GC/MS, the precise components of the production could also be acquired. The three most important components were methyl palmitate(C_(15)H_(31)COOCH_3), methyl linoleate(C_(17)H_(31)COOCH_3) and methyl stearate(C_(17)H_(35)COOCH_3).
The influences of reaction included the volume ratio of methanol to oil, the catalyst amount to oil(weight/volume), temperature, reaction time and stirring rate of reaction which were studied and optimized. The best condition were that volume ratio of methanol to oil was 3:1 to 4:1; the catalyst amount to oil(weight/volume) was 1:4 to 3:8; and the temperature was 60℃; fast stirring during the reaction was necessary. After 8h the conversion rate could reach 76% by using QAPPES/SiO_2 and 74 by using QAPSF/SiO_2.
The commercial macroporous cross-link resins were also tested as heterogeneous catalysts to catalyze transesterification of soybean oil with methanol. A series of methyl fatty acid ester as the production could also be acquired. The analysis methods of the production catalyzed by D201 and D202 were as the same as the production catalyzed by QAPPES/SiO_2 and QAPSF/SiO_2. The best condition were that volume ratio of methanol to oil was 1:1 to 2:1; the catalyst amount to oil(weight/volume) was 1:4 to 1:2; and the temperature was 60℃. After 6h the conversion rate could reach 80% by using D201 and 81% by using D202.
引文
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