生产甲烷氯化物的氯化反应器设计研究
摘要
中国传统的甲烷氯化物生产工艺是甲烷法，即由甲烷热氯化生成四种甲烷氯化物。其生产工艺消耗高，CH_3Cl、CH_2Cl_2的产品比例不易调节，四氯化碳产品的比例高，用途受限制，而目前国内外大多采用甲醇法甲烷氯化物生产工艺，甲烷法面临着淘汰的危险。正因为如此，四川鸿鹤化工股份有限公司引进西班牙阿拉贡公司(实为杜邦)的甲醇法甲烷氯化物生产技工艺技术，该技术分为两步，第一步甲醇与氯化氢反应生成一氯甲烷和水，第二步一氯甲烷和氯在高温高压下反应生成二氯甲烷、三氯甲烷和少量的四氯化碳。由于对反应器的反应机理及反应器的计算长度存在争议，所以本文先对该反应器内的反应过程及反应动力学进行分析，最后着重对高压氯化反应进行研究核算，对高压氯化反应的数学模型进行计算机模拟计算，计算出反应器的长度。经过计算证明反应器的长度是足够的，反应是安全的。同时也正证明本文的计算方法是正确的。
本文采用MdE公司推荐的动力学模型，用于高压管式反应器的设计，经过计算证实所有加入反应器的氯大约在反应器最初几米处已完全反应。而反应器的长度取为80米，这个理念是基于安全考虑，是因为如果有未完全反应的氯存在于反应器中，则在随后的工艺操作中有可能形成潜在的爆炸性蒸汽。
结果证明鸿化甲烷氯化物装置选用的反应器是合适的。
在甲烷氯化物氯化反应过程中含有三个完全反应。
生产甲烷氛化物的氛化反应器设计研究
CI+C12一CZ+HCI(l)
CZ+C12一C3+HCI(2)
C3+C12一C4+HCI(3)
其中:CI=CH3CI，CZ=C HZC12，C3=CHC13，C4=CCh
推荐的动力学模型是一个二级反应模型，根据幂函数定律动力学方程，即，
每个反应的反应速率可表达如下:
rl=k一[C:][C12]
几=kZ[CZ][C12]
f3=k3[C3][C12]
按阿累尼乌斯方程，kl，场和场可表达如下:
ki=Ai exP[一Ei/(盯)]
关键词:甲烷氯化物氯化反应器设计
In China, methane, as the raw material, is used to produce the methylchlorides. But the effective is not good, it is meaning the consumption is very high and the products ratio is difficult to control. The carbon tetrachloride is very high in the mixture of the products. And we do not hope to see more carbon tetrachloride within the products, hence our Honghe Company import the process of methanol rout from Spanish Aragonesas Company. The process is consisted of two stages. The first stage is to produce methyl chloride from the reaction of methanol and HC1. The second stage is to produce methylene chloride, chloroform and small quantity carbon tetrachloride from methyl chloride and liquid chlorine. The paper descript the phase analysis firstly, and then carry on the kinetic analysis, at the last finish the reactor calculation. The result for the reactor calculation is proved right. The length of the reactor is enough, and the reaction is safe. At the same time, it is proved that the calculation way of this paper is right.The kinetic model for high-pressure chlorination of chloromethanes (CMS) is recommended by Spanish MdE Company. The kinetic model is applied to design of the high-pressure tubular reactor in order to verify that the chlorine fed into the
reactor is consumed in first part of the reactor. The length of the reactor is 80 meters. The concept is based on safety considerations because a potentially explosive vapor may be formed in later process operation.The main objective of the paper is to prove that the proposed reactor is suitable for the chloromethanes Honghe Plant.There are three overall reactions, which are involved in the chlorination of chloromethanes.
本文采用MdE公司推荐的动力学模型，用于高压管式反应器的设计，经过计算证实所有加入反应器的氯大约在反应器最初几米处已完全反应。而反应器的长度取为80米，这个理念是基于安全考虑，是因为如果有未完全反应的氯存在于反应器中，则在随后的工艺操作中有可能形成潜在的爆炸性蒸汽。
结果证明鸿化甲烷氯化物装置选用的反应器是合适的。
在甲烷氯化物氯化反应过程中含有三个完全反应。
生产甲烷氛化物的氛化反应器设计研究
CI+C12一CZ+HCI(l)
CZ+C12一C3+HCI(2)
C3+C12一C4+HCI(3)
其中:CI=CH3CI，CZ=C HZC12，C3=CHC13，C4=CCh
推荐的动力学模型是一个二级反应模型，根据幂函数定律动力学方程，即，
每个反应的反应速率可表达如下:
rl=k一[C:][C12]
几=kZ[CZ][C12]
f3=k3[C3][C12]
按阿累尼乌斯方程，kl，场和场可表达如下:
ki=Ai exP[一Ei/(盯)]
关键词:甲烷氯化物氯化反应器设计
In China, methane, as the raw material, is used to produce the methylchlorides. But the effective is not good, it is meaning the consumption is very high and the products ratio is difficult to control. The carbon tetrachloride is very high in the mixture of the products. And we do not hope to see more carbon tetrachloride within the products, hence our Honghe Company import the process of methanol rout from Spanish Aragonesas Company. The process is consisted of two stages. The first stage is to produce methyl chloride from the reaction of methanol and HC1. The second stage is to produce methylene chloride, chloroform and small quantity carbon tetrachloride from methyl chloride and liquid chlorine. The paper descript the phase analysis firstly, and then carry on the kinetic analysis, at the last finish the reactor calculation. The result for the reactor calculation is proved right. The length of the reactor is enough, and the reaction is safe. At the same time, it is proved that the calculation way of this paper is right.The kinetic model for high-pressure chlorination of chloromethanes (CMS) is recommended by Spanish MdE Company. The kinetic model is applied to design of the high-pressure tubular reactor in order to verify that the chlorine fed into the
reactor is consumed in first part of the reactor. The length of the reactor is 80 meters. The concept is based on safety considerations because a potentially explosive vapor may be formed in later process operation.The main objective of the paper is to prove that the proposed reactor is suitable for the chloromethanes Honghe Plant.There are three overall reactions, which are involved in the chlorination of chloromethanes.
引文
[1] 童景山，李敬，流体热物理性质的计算。北京：清华大学出版社，1982
[2] 朱自强，徐汛，化工热力学(第二版)。北京：化学工业出版社，1991
[3] 李吕辉，吴翔，付玉普，靳长德，秦文渝，物理化学上册，大连：大连理工大学
[4] 吴指南，基本有机化工工艺学。北京：化学工业出版社，1981第1版
[5] 80kt／a甲烷氯化物项目科研报(内部交流) 连云港设计院 2003年11月
[2] 朱自强，徐汛，化工热力学(第二版)。北京：化学工业出版社，1991
[3] 李吕辉，吴翔，付玉普，靳长德，秦文渝，物理化学上册，大连：大连理工大学
[4] 吴指南，基本有机化工工艺学。北京：化学工业出版社，1981第1版
[5] 80kt／a甲烷氯化物项目科研报(内部交流) 连云港设计院 2003年11月