流化催化蒸馏合成乙酸乙酯/乙酸丁酯过程研究
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摘要
化学反应过程是化学转化技术的核心,如何提高化学反应过程效率,始终是科学家和工程技术人员重要研究任务。各类反应过程与分离过程耦合强化反应过程成为现代化学转化技术发展的一个重要方向。催化蒸馏技术是将非均相催化反应过程和蒸馏过程有机耦合强化反应过程,具有能耗低、操作简单、投资少等优点,是近30年发展起来的一种新的化学转化过程技术,在乙酸酯生产工业中具有良好应用前景。
从已商品化的四种强酸性离子交换树脂中筛选出了一种对合成乙酸乙酸和乙酸丁酯具有良好催化性能的凝胶型强酸性树脂A。通过对树脂酸性离子交换树脂的表征,认为其催化酯化反应的差异性主要是由—SO3H的含量和活性引起的。研究了粉碎、部分金属离子、温度预处理、重复使用及再生等因素对树脂A催化性能的影响。实验结果表明,树脂A催化剂经粉碎后对其催化性能影响不大,催化剂的选择好。树脂A与Fe2+、Ni+、Mn2+、Cr3+、Cu2+等金属离子结合后,催化活性都有不同程度的降低,其中与Fe2+和Ni+结合后,其催化活性降低较大；树脂A与Fe2+和Mn2+结合后经酸活化,催化活性恢复较好,但与Cr3+、Cu2+和Ni+结合后其催化活性恢复较差；与Fe3+结合后,其催化活性有所增加。树脂A重复使用15次后,其催化活性未见明显下降,在乙酸乙酸和乙酸丁酯体系的溶失率分别为0.35%和0.15%(wt%),树脂A可在180℃下使用。
在催化剂用量0.08g催化剂·g乙酸-1,反应2小时,反应温度为67.7℃,乙酸：乙醇的摩尔比为3：1,乙醇的转化率为90%以上。当乙酸：丁醇的摩尔比为3：1,催化剂用量为乙酸加入质量的0.08g催化剂·g乙酸-1,反应温度为80.5℃,反应2小时,丁醇的转化率为90%以上。在同时催化合成乙酸乙酯和乙酸丁酯的混合酯化反应时,在相同的实验条件下,乙醇和丁醇的转化率比单独进行的酯化反应要低一些。当乙酸：乙醇：丁醇的摩尔比为2：0.8：1,反应2小时,乙醇的转化率为72.73%,丁醇的转化率为64.4%；乙酸：乙醇：丁醇的摩尔比为2：1：0.8,反应2小时,乙醇的转化率为69.94%,丁醇的转化率为63.04%。
在间歇釜式反应器中研究了树脂A分别催化合成乙酸乙酯和乙酸丁酯的动力学模型。在消除内外扩散条件下,采用初始速率法,分别获得了树脂A催化合成乙酸乙酯和乙酸丁酯的拟均相动力学方程。在催化剂用量为0.01665～0.08333gcat·gA-1,反应温度为320.5K-340.7K,树脂A催化合成乙酸乙酯的拟均相动力学模型可描述为：
在催化剂用量为0.01665～0.08333gcat·gA-1,反应温度为336.3K～358.5K,树脂A催化合成乙酸丁酯的拟均相动力学模型可描述为：
合成乙酸乙酯动力学模型计算值与实验值的最大相对偏差为8.3%；合成乙酸丁酯动力学模型计算值与实验值的最大相对偏差为8.5%；两个模型的置信度为98%。
在Φ34mm的填料塔中,采用填装小型陶瓷拉西环的流化催化蒸馏塔,以空气-水和空气-水-催化剂细粉为研究体系,研究了液相中树脂细粉的加入对填料塔的流体力学性能和分离性能的影响。研究结果表明,液相中细粉催化剂的加入,对填料塔压降的影响不大。在相同的操作条件下,液相中树脂含量的增加,填料层中的持液量有增加,塔的分离能力有所提高。当液相中树脂细粉含量为4%时,塔的分离能力比无树脂细粉时提高约1/5。
在Φ34mm的流化催化蒸馏塔中连续合成了乙酸乙酯和乙酸丁酯。乙醇从塔下部的Y1o进料口进料,乙酸从塔上部的Y3进料口进料,乙酸中催化剂量为0.05g催化剂·g乙酸-1,进料乙酸与乙醇摩尔比为2.5,塔顶用99.5%的高浓度酯液以取出粗酯量的2.5倍“回流”,釜液循环,合成乙酸乙酯时塔顶有机相组成为乙酸乙酯95.71%,乙醇1.30%,水2.99%,几乎不含酸。乙醇的单程转化率为97.35%,乙酸乙酯的收率为98.27%。丁醇从塔的Y9进料口进料,乙酸从Y3进料口进料,乙酸中催化剂量为0.05g催化剂·g乙酸-1,乙酸和丁醇的进料总流量为3.0mol/h,进料乙酸与丁醇摩尔比为3：1,回流比为2时,合成乙酸丁酯时塔顶粗酯相的组成为乙酸丁酯97.46%,丁醇1.09%,水1.45%,几乎不含酸。丁醇的单程转化率为97.15%,乙酸丁酯的收率为97.88%。
Chemical reaction process is the core of the chemical conversion technology so that improving chemical reaction process efficiency is an important task for the scientists and the engineers. The development of the reaction and separation coupling techniques is a kind of trend for chemical conversion technology research. Catalytic distillation technology developed in the past30years is a strengthening the reaction process in which the heterogeneous catalyst reaction is coupled with the distillation process. Catalytic distillation has the advantages of low energy consumption, simplicity of operation and less investment, this technology has good practical prospects for the acetate production industry.
The best catalytic performance of gel-type strong acid resin A in synthesis of ethyl acetate and butyl acetate was picked from the four commercial strong acid ion exchange resins. Through the characterizations of acidic ion exchange resin, the catalytic esterification reaction differences were explained primarily by the content and the activity of group—SO3H. The effects of smashing, combined with some metal ions, temperature resistance, re-use and regeneration on the catalytical performance of the resin A were investigated. The results showed that the resin A catalyst had good selectivity and the smashing had little impact on its catalytical performance. The catalytic activity decreased to the respective degree after complex to the different metal ions such as Fe2+, Ni+, Mn2+, Cr3+, Cu2+et al. The catalytic activity of resin A interacted with ions of Fe2+and Ni+decreased to the most degree. The catalytic activity of resin combining with ions of Fe2+and Mn2+recovered well after acidactivation but did bad combining with ions of Cr3+, Cu2+and Ni+. The catalytic activity of resin A increased when it was combined with ion of Fe3+. The catalytic activity of resin A had no significant decline after reusing15times. The dissolved loss of resin A in the reaction systems synthesizing ethyl acetate and butyl acetate were0.35%and0.15%respectively. Resin A can be effectively used at180℃.
The effects of the resin A on the synthesis process of ethyl acetate and butyl acetate were studied respectively. The conversion of ethanol was above90%when catalyst amount was0.05gcat·gA-1, reaction temperature was67.7℃, the initial mole ratio of acetic acid to ethanol was3:1, reaction time was2hours. The conversion of butanol was above90%when catalyst amount was0.08gcat·gA-1, reaction temperature was80.5℃, the initial mole ratio of acetic acid to butanol was3:1, reaction time was2hours. The conversion of ethanol and butanol in the esterification of acetic acid with ethanol and butanol simultaneously were less than the conversion in the single reaction respectively at same conditions. When initial mole ratios of acetic acid, ethanol and butanol were2:0.8:1, the conversion rates of ethanol and butanol were72.73%and64.4%respectively after2hours. When the initial mole ratios were2:1:0.8, the conversion of ethanol and butanol were69.94%and63.04%respectively after2hours.
The kinetics of synthesizing ethyl acetate and butyl acetate with resin A catalyst were respectively investigated in batch reactor. The pseudo homogeneous kinetics model for two esterification reactions were obtained using the method of initial reaction rate by eliminating internal and external diffusion conditions. When the catalyst amount range was0.01665～0.08333gcat·gA-1and reaction temperature range was between320.5K～340.7K, the pseudo homogeneous kinetics model synthesizing ethyl acetate was following form:
When the catalyst amount range was0.01665～0.08333gcat·gA-1and the temperature range was between320.5K and340.7K, the pseudo homogeneous kinetics model synthesizing butyl acetate was following form:
In kinetic model for synthesis of ethyl acetate, the maximum relative deviation between the calculating value and the experimental value was8.3%. In kinetic model for synthesis of butyl acetate, the maximum relative deviation was8.5%. Both of confidence coefficients in two models were equal to98%.
The hydrodynamic performance and separation performance of the catalytic distillation column packed small size ceramic Rasching rings at the diameter of34mm with the fluidized resin powder in liquid phase were investigated by air-water system. The results showed that the resin powder had little effect on the pressure drop of the packed column. The increase of content resin powder in liquid phase increased, the liquid holdup of packing bed and increased the separation performance of the column at the same operating conditions. Compared with those without resin powder in the liquid phase, the separation performance of the pack column increased20percent with the resin powder content of4%.
The continuous synthesis processes of ethyl acetate and butyl acetate were investigated in a diameter of34mm fluidized catalytic distillation column. When ethanol fed in at Y10near tower bottom, acetic acid fed in at Y3near tower top, catalyst amount was0.05gcat·gA-1,mole ratios of acetic acid to ethanol was2.5:1, reflux ratio of99.5%ethyl acetate to taken out column top was2.5times, the proportion of ethyl acetate, acetic acid, ethanol and water in the organic phase from the column top were95.71%,0.028%,1.09%and2.95%respectively, almost did not contain acid. The conversion per pass of ethanol was97.35%and the yield of ethyl acetate was98.27%. When butanol fed in at Y9near tower bottom, acetic acid fed in at Y3near tower top, catalyst amount was0.05gcat·gA-1, mole ratios of acetic acid to ethanol was3:1, reflux ratio was2.0, the proportion of butyl acetate, butanol and water in the organic phase from the column top were97.46%,1.9%and1.45%respectively, almost did not contain acid. The conversion per pass of butanol was97.15%and the yield of butyl acetate was97.88%.
从已商品化的四种强酸性离子交换树脂中筛选出了一种对合成乙酸乙酸和乙酸丁酯具有良好催化性能的凝胶型强酸性树脂A。通过对树脂酸性离子交换树脂的表征,认为其催化酯化反应的差异性主要是由—SO3H的含量和活性引起的。研究了粉碎、部分金属离子、温度预处理、重复使用及再生等因素对树脂A催化性能的影响。实验结果表明,树脂A催化剂经粉碎后对其催化性能影响不大,催化剂的选择好。树脂A与Fe2+、Ni+、Mn2+、Cr3+、Cu2+等金属离子结合后,催化活性都有不同程度的降低,其中与Fe2+和Ni+结合后,其催化活性降低较大；树脂A与Fe2+和Mn2+结合后经酸活化,催化活性恢复较好,但与Cr3+、Cu2+和Ni+结合后其催化活性恢复较差；与Fe3+结合后,其催化活性有所增加。树脂A重复使用15次后,其催化活性未见明显下降,在乙酸乙酸和乙酸丁酯体系的溶失率分别为0.35%和0.15%(wt%),树脂A可在180℃下使用。
在催化剂用量0.08g催化剂·g乙酸-1,反应2小时,反应温度为67.7℃,乙酸：乙醇的摩尔比为3：1,乙醇的转化率为90%以上。当乙酸：丁醇的摩尔比为3：1,催化剂用量为乙酸加入质量的0.08g催化剂·g乙酸-1,反应温度为80.5℃,反应2小时,丁醇的转化率为90%以上。在同时催化合成乙酸乙酯和乙酸丁酯的混合酯化反应时,在相同的实验条件下,乙醇和丁醇的转化率比单独进行的酯化反应要低一些。当乙酸：乙醇：丁醇的摩尔比为2：0.8：1,反应2小时,乙醇的转化率为72.73%,丁醇的转化率为64.4%；乙酸：乙醇：丁醇的摩尔比为2：1：0.8,反应2小时,乙醇的转化率为69.94%,丁醇的转化率为63.04%。
在间歇釜式反应器中研究了树脂A分别催化合成乙酸乙酯和乙酸丁酯的动力学模型。在消除内外扩散条件下,采用初始速率法,分别获得了树脂A催化合成乙酸乙酯和乙酸丁酯的拟均相动力学方程。在催化剂用量为0.01665～0.08333gcat·gA-1,反应温度为320.5K-340.7K,树脂A催化合成乙酸乙酯的拟均相动力学模型可描述为：
在催化剂用量为0.01665～0.08333gcat·gA-1,反应温度为336.3K～358.5K,树脂A催化合成乙酸丁酯的拟均相动力学模型可描述为：
合成乙酸乙酯动力学模型计算值与实验值的最大相对偏差为8.3%；合成乙酸丁酯动力学模型计算值与实验值的最大相对偏差为8.5%；两个模型的置信度为98%。
在Φ34mm的填料塔中,采用填装小型陶瓷拉西环的流化催化蒸馏塔,以空气-水和空气-水-催化剂细粉为研究体系,研究了液相中树脂细粉的加入对填料塔的流体力学性能和分离性能的影响。研究结果表明,液相中细粉催化剂的加入,对填料塔压降的影响不大。在相同的操作条件下,液相中树脂含量的增加,填料层中的持液量有增加,塔的分离能力有所提高。当液相中树脂细粉含量为4%时,塔的分离能力比无树脂细粉时提高约1/5。
在Φ34mm的流化催化蒸馏塔中连续合成了乙酸乙酯和乙酸丁酯。乙醇从塔下部的Y1o进料口进料,乙酸从塔上部的Y3进料口进料,乙酸中催化剂量为0.05g催化剂·g乙酸-1,进料乙酸与乙醇摩尔比为2.5,塔顶用99.5%的高浓度酯液以取出粗酯量的2.5倍“回流”,釜液循环,合成乙酸乙酯时塔顶有机相组成为乙酸乙酯95.71%,乙醇1.30%,水2.99%,几乎不含酸。乙醇的单程转化率为97.35%,乙酸乙酯的收率为98.27%。丁醇从塔的Y9进料口进料,乙酸从Y3进料口进料,乙酸中催化剂量为0.05g催化剂·g乙酸-1,乙酸和丁醇的进料总流量为3.0mol/h,进料乙酸与丁醇摩尔比为3：1,回流比为2时,合成乙酸丁酯时塔顶粗酯相的组成为乙酸丁酯97.46%,丁醇1.09%,水1.45%,几乎不含酸。丁醇的单程转化率为97.15%,乙酸丁酯的收率为97.88%。
Chemical reaction process is the core of the chemical conversion technology so that improving chemical reaction process efficiency is an important task for the scientists and the engineers. The development of the reaction and separation coupling techniques is a kind of trend for chemical conversion technology research. Catalytic distillation technology developed in the past30years is a strengthening the reaction process in which the heterogeneous catalyst reaction is coupled with the distillation process. Catalytic distillation has the advantages of low energy consumption, simplicity of operation and less investment, this technology has good practical prospects for the acetate production industry.
The best catalytic performance of gel-type strong acid resin A in synthesis of ethyl acetate and butyl acetate was picked from the four commercial strong acid ion exchange resins. Through the characterizations of acidic ion exchange resin, the catalytic esterification reaction differences were explained primarily by the content and the activity of group—SO3H. The effects of smashing, combined with some metal ions, temperature resistance, re-use and regeneration on the catalytical performance of the resin A were investigated. The results showed that the resin A catalyst had good selectivity and the smashing had little impact on its catalytical performance. The catalytic activity decreased to the respective degree after complex to the different metal ions such as Fe2+, Ni+, Mn2+, Cr3+, Cu2+et al. The catalytic activity of resin A interacted with ions of Fe2+and Ni+decreased to the most degree. The catalytic activity of resin combining with ions of Fe2+and Mn2+recovered well after acidactivation but did bad combining with ions of Cr3+, Cu2+and Ni+. The catalytic activity of resin A increased when it was combined with ion of Fe3+. The catalytic activity of resin A had no significant decline after reusing15times. The dissolved loss of resin A in the reaction systems synthesizing ethyl acetate and butyl acetate were0.35%and0.15%respectively. Resin A can be effectively used at180℃.
The effects of the resin A on the synthesis process of ethyl acetate and butyl acetate were studied respectively. The conversion of ethanol was above90%when catalyst amount was0.05gcat·gA-1, reaction temperature was67.7℃, the initial mole ratio of acetic acid to ethanol was3:1, reaction time was2hours. The conversion of butanol was above90%when catalyst amount was0.08gcat·gA-1, reaction temperature was80.5℃, the initial mole ratio of acetic acid to butanol was3:1, reaction time was2hours. The conversion of ethanol and butanol in the esterification of acetic acid with ethanol and butanol simultaneously were less than the conversion in the single reaction respectively at same conditions. When initial mole ratios of acetic acid, ethanol and butanol were2:0.8:1, the conversion rates of ethanol and butanol were72.73%and64.4%respectively after2hours. When the initial mole ratios were2:1:0.8, the conversion of ethanol and butanol were69.94%and63.04%respectively after2hours.
The kinetics of synthesizing ethyl acetate and butyl acetate with resin A catalyst were respectively investigated in batch reactor. The pseudo homogeneous kinetics model for two esterification reactions were obtained using the method of initial reaction rate by eliminating internal and external diffusion conditions. When the catalyst amount range was0.01665～0.08333gcat·gA-1and reaction temperature range was between320.5K～340.7K, the pseudo homogeneous kinetics model synthesizing ethyl acetate was following form:
When the catalyst amount range was0.01665～0.08333gcat·gA-1and the temperature range was between320.5K and340.7K, the pseudo homogeneous kinetics model synthesizing butyl acetate was following form:
In kinetic model for synthesis of ethyl acetate, the maximum relative deviation between the calculating value and the experimental value was8.3%. In kinetic model for synthesis of butyl acetate, the maximum relative deviation was8.5%. Both of confidence coefficients in two models were equal to98%.
The hydrodynamic performance and separation performance of the catalytic distillation column packed small size ceramic Rasching rings at the diameter of34mm with the fluidized resin powder in liquid phase were investigated by air-water system. The results showed that the resin powder had little effect on the pressure drop of the packed column. The increase of content resin powder in liquid phase increased, the liquid holdup of packing bed and increased the separation performance of the column at the same operating conditions. Compared with those without resin powder in the liquid phase, the separation performance of the pack column increased20percent with the resin powder content of4%.
The continuous synthesis processes of ethyl acetate and butyl acetate were investigated in a diameter of34mm fluidized catalytic distillation column. When ethanol fed in at Y10near tower bottom, acetic acid fed in at Y3near tower top, catalyst amount was0.05gcat·gA-1,mole ratios of acetic acid to ethanol was2.5:1, reflux ratio of99.5%ethyl acetate to taken out column top was2.5times, the proportion of ethyl acetate, acetic acid, ethanol and water in the organic phase from the column top were95.71%,0.028%,1.09%and2.95%respectively, almost did not contain acid. The conversion per pass of ethanol was97.35%and the yield of ethyl acetate was98.27%. When butanol fed in at Y9near tower bottom, acetic acid fed in at Y3near tower top, catalyst amount was0.05gcat·gA-1, mole ratios of acetic acid to ethanol was3:1, reflux ratio was2.0, the proportion of butyl acetate, butanol and water in the organic phase from the column top were97.46%,1.9%and1.45%respectively, almost did not contain acid. The conversion per pass of butanol was97.15%and the yield of butyl acetate was97.88%.
引文
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