乙醛氧化制备乙二醛的反应和分离过程研究
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摘要
乙二醛是重要的化工原料和中间体，广泛地应用于纺织印染、医药、造纸等领域，尤其是随着医药行业的发展高纯度乙二醛的需求逐渐增加。目前，乙二醛的工业生产工艺存在着环境污染严重、纯度低、能耗高、收率低、易爆炸等问题。乙醛法生产乙二醛工艺具有产品质量高、能耗低等优点，本文对硝酸氧化乙醛法制备乙二醛的氧化反应机理、合成及分离过程进行深入研究。研究内容如下：
采用离子排阻色谱法测定乙二醛溶液组成，选用示差检测器、氨基色谱柱、稀硫酸为流动相进行乙二醛溶液中各组分的定性分析，并采用外标法对其中乙醛酸、乙醇酸、草酸、甲酸、乙酸等组分建立了定量分析方法，实现了乙二醛溶液的快速、准确的测定。
通过分析硝酸氧化乙醛过程，可知氧化反应是按自由基机理进行，从而推导出硝酸氧化乙醛制备乙二醛的反应体系中主、副产物的生成机理。实验研究了乙二醛、甲酸和乙酸的生成反应动力学，得出了这三个反应的动力学模型。
对电渗析法分离硝酸进行了实验研究。使用J-1-18膜组装的电渗析装置分离硝酸，建立该过程的传质过程方程并得到传质模型。研究膜堆电压以及不同硝酸初始浓度等因素对电渗析分离硝酸过程的影响，结果表明在低电压条件下，电渗析法可有效的分离硝酸。
实验研究气提法分离乙醛的过程，并建立了该过程的稳态非平衡级模型，采用收敛性很好的Newton同伦算法进行模型的求解，模拟结果与实验结果吻合度很高。利用模型分析了气提过程的稳态特性，系统考察了液气比、进料温度、塔板数等对于产品中乙醛浓度的影响。研究结果表明气提法可在较低温度下有效地脱除乙醛，解决了乙二醛溶液在高温下变质的问题。
采用J-18均相离子交换膜和大孔离子交换树脂组装电去离子装置，对电去离子分离乙酸进行了实验研究，建立了该过程的传质过程方程并得到传质模型。考察了不同的操作条件对乙酸分离的影响，实现乙二醛溶液中乙酸的深度分离。
Glyoxal is a kind of important chemical material and intermediate with a widerange of applications in printing and dyeing textile, medicine, paper making et al.Especially with the development of pharmaceutical industry, there is an increasingdemand for high-purity glyoxal gradually. At present, the industrial manufactureprocess suffered from severe pollution, lower purity, high energy consumption, lowyields and tends to explode et al.. While the production process of glyoxal fromacetaldehyde has merits of higher quality product and lower power consumption etc..The reaction mechanism, synthesis and separation process of the method of nitric acidoxidizing acetaldehyde were investigated intensively in this paper. And the researchcontents are as follows:
Ion-exclusive chromatography analysis was selected to analyze glyoxal solution.Qualitative analysises of each component in glyoxal solution were obtained with theapplication of differential refraction detector, column aminex HPX-87H and dilutesulphuric acid as the mobile phase. Quantitative analysis of glyoxylic acid, glycollicacid, oxalic acid, formic acid and acetic acid et al. was estabilished by externalstandard method. Then the rapid and accurate analysis for the oxidation solution wasachieved.
The possible formation mechanism of the principal product and byproduct in thereaction system of the glyoxal preparation with the method of nitric acid oxidizingacetaldehyde were deduced by means of oxidation process analysis. It can beconsidered that the reactions were conducted in term of free radical mechanism. Theformation kinetics of glyoxal, formic acid and acetic acid were researchedexperimentally and the kinetic models of the three reactions were concluded.
Nitric acid separation using electrodialysis technique was researchedexperimentally. The experiments were conducted in electrodialysis equipmentequipped with membrane J-1-18. The mass transfer equation was established and themass transfer model was obtained. The effects of membrane stack voltage, the initialconcentration of nitric acid et al. on separation process were investigated. Theresearch results show that nitric acid can be removed effectively at low-voltage.
Experimental study about the separation of acetaldehyde with the method ofgas-stripping was researched. A non-equilibrium model for describing the GS process was proposed and solved with a Newton-Homotopy method. This model is verifiedby the comparison of simulation results with experimental results. The steady-stateperformance of GS process, such as the influence of liquid-gas ratio, feedingtempearure and theoretical plate was investigated systematically using the model. Theresearch results show that the acetaldehyde in the solution can be removed effectivelywith the application of GS technique. Furthermore, the separation temperature can belowered to the level of avoiding the metachromatism of the glyoxal solution athigh-temperature.
Acetic acid separation using EDI technique was studied experimentally. Theexperiments were conducted in electrodialysis equipment packed with membraneJ-1-18and macroporous ion-exchange resin. The mass transfer equation wasestablished and the mass transfer model was obtained. The effects of differentoperation conditions on acetic acid separation were investigated. The research resultsshow that the deep deacidification of glyoxal solution can be obtained.
采用离子排阻色谱法测定乙二醛溶液组成，选用示差检测器、氨基色谱柱、稀硫酸为流动相进行乙二醛溶液中各组分的定性分析，并采用外标法对其中乙醛酸、乙醇酸、草酸、甲酸、乙酸等组分建立了定量分析方法，实现了乙二醛溶液的快速、准确的测定。
通过分析硝酸氧化乙醛过程，可知氧化反应是按自由基机理进行，从而推导出硝酸氧化乙醛制备乙二醛的反应体系中主、副产物的生成机理。实验研究了乙二醛、甲酸和乙酸的生成反应动力学，得出了这三个反应的动力学模型。
对电渗析法分离硝酸进行了实验研究。使用J-1-18膜组装的电渗析装置分离硝酸，建立该过程的传质过程方程并得到传质模型。研究膜堆电压以及不同硝酸初始浓度等因素对电渗析分离硝酸过程的影响，结果表明在低电压条件下，电渗析法可有效的分离硝酸。
实验研究气提法分离乙醛的过程，并建立了该过程的稳态非平衡级模型，采用收敛性很好的Newton同伦算法进行模型的求解，模拟结果与实验结果吻合度很高。利用模型分析了气提过程的稳态特性，系统考察了液气比、进料温度、塔板数等对于产品中乙醛浓度的影响。研究结果表明气提法可在较低温度下有效地脱除乙醛，解决了乙二醛溶液在高温下变质的问题。
采用J-18均相离子交换膜和大孔离子交换树脂组装电去离子装置，对电去离子分离乙酸进行了实验研究，建立了该过程的传质过程方程并得到传质模型。考察了不同的操作条件对乙酸分离的影响，实现乙二醛溶液中乙酸的深度分离。
Glyoxal is a kind of important chemical material and intermediate with a widerange of applications in printing and dyeing textile, medicine, paper making et al.Especially with the development of pharmaceutical industry, there is an increasingdemand for high-purity glyoxal gradually. At present, the industrial manufactureprocess suffered from severe pollution, lower purity, high energy consumption, lowyields and tends to explode et al.. While the production process of glyoxal fromacetaldehyde has merits of higher quality product and lower power consumption etc..The reaction mechanism, synthesis and separation process of the method of nitric acidoxidizing acetaldehyde were investigated intensively in this paper. And the researchcontents are as follows:
Ion-exclusive chromatography analysis was selected to analyze glyoxal solution.Qualitative analysises of each component in glyoxal solution were obtained with theapplication of differential refraction detector, column aminex HPX-87H and dilutesulphuric acid as the mobile phase. Quantitative analysis of glyoxylic acid, glycollicacid, oxalic acid, formic acid and acetic acid et al. was estabilished by externalstandard method. Then the rapid and accurate analysis for the oxidation solution wasachieved.
The possible formation mechanism of the principal product and byproduct in thereaction system of the glyoxal preparation with the method of nitric acid oxidizingacetaldehyde were deduced by means of oxidation process analysis. It can beconsidered that the reactions were conducted in term of free radical mechanism. Theformation kinetics of glyoxal, formic acid and acetic acid were researchedexperimentally and the kinetic models of the three reactions were concluded.
Nitric acid separation using electrodialysis technique was researchedexperimentally. The experiments were conducted in electrodialysis equipmentequipped with membrane J-1-18. The mass transfer equation was established and themass transfer model was obtained. The effects of membrane stack voltage, the initialconcentration of nitric acid et al. on separation process were investigated. Theresearch results show that nitric acid can be removed effectively at low-voltage.
Experimental study about the separation of acetaldehyde with the method ofgas-stripping was researched. A non-equilibrium model for describing the GS process was proposed and solved with a Newton-Homotopy method. This model is verifiedby the comparison of simulation results with experimental results. The steady-stateperformance of GS process, such as the influence of liquid-gas ratio, feedingtempearure and theoretical plate was investigated systematically using the model. Theresearch results show that the acetaldehyde in the solution can be removed effectivelywith the application of GS technique. Furthermore, the separation temperature can belowered to the level of avoiding the metachromatism of the glyoxal solution athigh-temperature.
Acetic acid separation using EDI technique was studied experimentally. Theexperiments were conducted in electrodialysis equipment packed with membraneJ-1-18and macroporous ion-exchange resin. The mass transfer equation wasestablished and the mass transfer model was obtained. The effects of differentoperation conditions on acetic acid separation were investigated. The research resultsshow that the deep deacidification of glyoxal solution can be obtained.
引文
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