己二腈催化加氢制备己二胺的工艺及动力学研究
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摘要
己二胺是一种重要的化工原料,主要用于和己二酸反应生产尼龙66,和癸二酸反应生产尼龙610,同时,还可用于生产成聚亚胺羧酸酯泡沫塑料、涂料、粘合剂、橡胶助剂和漂白剂等等,随着科学技术的进步和化工新材料的不断开发,己二胺的用途越来越广泛。
本文以乙醇为溶剂,雷尼镍为催化剂,对己二腈催化加氢制备己二胺的工艺条件进行研究及优化。设计了均匀实验及单因素实验,系统地考察了反应时间,反应温度,氢气压力,催化剂用量和搅拌速率对己二腈加氢工艺的影响。当在高压釜中加入144g己二腈及同体积无水乙醇时,得到了适宜的反应条件是：反应温度为75℃,反应时间为8h,催化剂加入量为己二腈质量的6.6%(9.5g),氢气压力为3.3Mpa及搅拌速率为500r·min-1时,转化率达到100%,收率达96%以上。
在消除了内、外扩散影响的条件下,采用雷尼镍催化剂在间歇高压釜中进行了己二腈催化加氢反应动力学的研究。通过测定己二腈催化加氢过程中己二腈、氨基己腈和己二胺浓度随时间变化的c～t曲线,获得了己二腈催化加氢制备己二胺反应中两阶段的反应级数、速率常数和活化能等动力学参数。在温度328～358K,压力2～3.5 MPa范围内,己二腈催化加氢时对己二腈呈一级反应,对氢压呈1.4级反应；中间产物氨基己腈继续加氢形成己二胺时,对氨基己腈为零级反应,而对氢压则为1.3级反应。再对求得的动力学参数进行拟合,得到了己二腈催化加氢的动力学方程。
本文利用激光监视装置,采用变温溶解法测定了己二胺在甲醇—水以及乙二醇—水中的溶解度。实验的温度范围为5℃～35℃,混合溶剂中水的变化范围为10%～30%。实验结果表明己二胺在不同体系中的溶解度均随温度的升高而增大,在同一温度下随含水量的升高而增大。并用简化的参数方程对实验测定结果进行了关联,计算所得的溶解度与实验结果符合良好。实验所得溶解度数据可对粗产品的分离和提纯提供参考依据。
Hexanediamine is a kind of important chemical raw material, mainly for producing nylon 66 reaction with adipic acid, and for producing nylon 610 reaction with sebacic acid. Recently, with the progress of technology and the development of novel chemical materials, hexanediamine also can be used to produce polyimide acid ester foams, coatings, adhesives, rubber chemicals and bleach, etc. And it has been more and more widely used.
In the process of catalytic hydrogenation of adiponitrile to hexanediamine, ethanol was taken as solvent and Raney Ni as catalyst. Uniform experiments and single-factor experiments were designed to research the effect of reaction time,reaction temperature,hydrogen pressure, catalyst amount and stirring rate on adiponitrile hydrogenation reaction. The results showed that when the amount of adiponitrile was 144 grams, and the same volume of absolute ethylalcohol were used as solvent, the temperature was 75℃, reaction time was 8 hours, the ratio of catalyst mass was 6.6% of adiponitrile mass, hydrogen pressure was 3.3Mpa and stirring rate was 500r·min-1, the percent conversion reached 100% and the yield was more than 96%.
The reaction kinetics of catalytic hydrogenation of adiponitrile on Raney-Ni catalyst had been studied in a high-pressure batch reactor. Under the condition of no inside and outside diffusion, the concentration of adiponitrile, aminocaproic nitrile and hexanediamine versus time over the Raney-Ni catalyst were measured. The kinetic parameters of catalytic hydrogenation of adiponitrile to hexanediamine such as reaction order, rate constant and activated energy in each step were obtained.The results show that in the condition of eliminating the influence of inner and outer diffuse, the catalytic hydrogenation of adiponitrile is the level 1 when the temperature is 328K to 358K and the pressure is 2-3.5MPa. As to hydrogen pressure is 1.4 level reaction; while Hexamethylene diamine formed by continuing to aid hydrogen to the interim production aminocaproicnitrile, the reaction is 0 level to aminocaproicnitrile and 1.3 level to hydrogen pressure. Dynamics function of catalyzing adiponitrile could be got by fitting the dynamics parameter which gives a solid theory basement to understand the reaction.
In this dissertation, laser monitoring device was used, poikilothermic dissolution method was adopted to determine the solubility of hexanediamine in methanol-water and ethylene glycol-water system. The temperature range of this experiment is form 5℃to 35℃, Water range of the mixed solvent is from 10% to 30%. The results showed that hexanediamine's solubility increased with the temperature increasing in different systems, hexanediamine's solubility increased with the increasing of water content at the same temperature. And the experimental results were correlated by using simplified Parameter equation, the calculated results and the experimental data were in good correspondence. Solubility data obtained in this study can supply reference for the separation and purification of the crude products.
本文以乙醇为溶剂,雷尼镍为催化剂,对己二腈催化加氢制备己二胺的工艺条件进行研究及优化。设计了均匀实验及单因素实验,系统地考察了反应时间,反应温度,氢气压力,催化剂用量和搅拌速率对己二腈加氢工艺的影响。当在高压釜中加入144g己二腈及同体积无水乙醇时,得到了适宜的反应条件是：反应温度为75℃,反应时间为8h,催化剂加入量为己二腈质量的6.6%(9.5g),氢气压力为3.3Mpa及搅拌速率为500r·min-1时,转化率达到100%,收率达96%以上。
在消除了内、外扩散影响的条件下,采用雷尼镍催化剂在间歇高压釜中进行了己二腈催化加氢反应动力学的研究。通过测定己二腈催化加氢过程中己二腈、氨基己腈和己二胺浓度随时间变化的c～t曲线,获得了己二腈催化加氢制备己二胺反应中两阶段的反应级数、速率常数和活化能等动力学参数。在温度328～358K,压力2～3.5 MPa范围内,己二腈催化加氢时对己二腈呈一级反应,对氢压呈1.4级反应；中间产物氨基己腈继续加氢形成己二胺时,对氨基己腈为零级反应,而对氢压则为1.3级反应。再对求得的动力学参数进行拟合,得到了己二腈催化加氢的动力学方程。
本文利用激光监视装置,采用变温溶解法测定了己二胺在甲醇—水以及乙二醇—水中的溶解度。实验的温度范围为5℃～35℃,混合溶剂中水的变化范围为10%～30%。实验结果表明己二胺在不同体系中的溶解度均随温度的升高而增大,在同一温度下随含水量的升高而增大。并用简化的参数方程对实验测定结果进行了关联,计算所得的溶解度与实验结果符合良好。实验所得溶解度数据可对粗产品的分离和提纯提供参考依据。
Hexanediamine is a kind of important chemical raw material, mainly for producing nylon 66 reaction with adipic acid, and for producing nylon 610 reaction with sebacic acid. Recently, with the progress of technology and the development of novel chemical materials, hexanediamine also can be used to produce polyimide acid ester foams, coatings, adhesives, rubber chemicals and bleach, etc. And it has been more and more widely used.
In the process of catalytic hydrogenation of adiponitrile to hexanediamine, ethanol was taken as solvent and Raney Ni as catalyst. Uniform experiments and single-factor experiments were designed to research the effect of reaction time,reaction temperature,hydrogen pressure, catalyst amount and stirring rate on adiponitrile hydrogenation reaction. The results showed that when the amount of adiponitrile was 144 grams, and the same volume of absolute ethylalcohol were used as solvent, the temperature was 75℃, reaction time was 8 hours, the ratio of catalyst mass was 6.6% of adiponitrile mass, hydrogen pressure was 3.3Mpa and stirring rate was 500r·min-1, the percent conversion reached 100% and the yield was more than 96%.
The reaction kinetics of catalytic hydrogenation of adiponitrile on Raney-Ni catalyst had been studied in a high-pressure batch reactor. Under the condition of no inside and outside diffusion, the concentration of adiponitrile, aminocaproic nitrile and hexanediamine versus time over the Raney-Ni catalyst were measured. The kinetic parameters of catalytic hydrogenation of adiponitrile to hexanediamine such as reaction order, rate constant and activated energy in each step were obtained.The results show that in the condition of eliminating the influence of inner and outer diffuse, the catalytic hydrogenation of adiponitrile is the level 1 when the temperature is 328K to 358K and the pressure is 2-3.5MPa. As to hydrogen pressure is 1.4 level reaction; while Hexamethylene diamine formed by continuing to aid hydrogen to the interim production aminocaproicnitrile, the reaction is 0 level to aminocaproicnitrile and 1.3 level to hydrogen pressure. Dynamics function of catalyzing adiponitrile could be got by fitting the dynamics parameter which gives a solid theory basement to understand the reaction.
In this dissertation, laser monitoring device was used, poikilothermic dissolution method was adopted to determine the solubility of hexanediamine in methanol-water and ethylene glycol-water system. The temperature range of this experiment is form 5℃to 35℃, Water range of the mixed solvent is from 10% to 30%. The results showed that hexanediamine's solubility increased with the temperature increasing in different systems, hexanediamine's solubility increased with the increasing of water content at the same temperature. And the experimental results were correlated by using simplified Parameter equation, the calculated results and the experimental data were in good correspondence. Solubility data obtained in this study can supply reference for the separation and purification of the crude products.
引文
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