【作者】 邵月刚；

【导师】 范宏；

【作者基本信息】 浙江大学 ， 化学工程， 2003， 硕士

【摘要】 本文针对直接法合成二甲基二氯硅烷单体生产中的副产物——高沸点混合物（简称高沸物）、低沸点混合物（简称低沸物），采用氯化氢裂解高沸物与AlCl₃催化高、低沸物歧化反应将其转化为高价值的二甲基二氯硅烷，寻求解决甲基氯硅烷单体生产过程中大量副产高、低沸物综合利用的有效途径，为进一步实现高、低沸物产业化，创造良好的经济效益、社会效益和生态效益奠定基础。全文分为两个部分。 第一部分：高沸物裂解反应中试研究 在500t／a高沸裂解中试装置上，采用正交法对反应温度、搅拌转速、HCl流量、催化剂加入量等工艺条件继续进行了研究；对影响高沸物裂解率及单硅烷收率等因素进行了分析；确定了高沸裂解中试最佳的工艺条件：反应温度为130℃，催化剂加入量为1.25～2％，HCl流量为1.25m³／h（对500L反应釜），搅拌转速为200 r／min。反应产物中高沸裂解率为86.71％，单硅烷收率为67.81％，通过对中试装置上的高沸物吸收液循环套用，可大大提高产物中单硅烷的收率。 第二部分：高、低沸物歧化反应研究 AlCl₃在高、低沸物歧化反应中具有较好的催化效果，通过研究确定了高、低沸歧化反应的最佳工艺条件：高、低沸物配比为5：1，反应物占反应釜容积的50％，反应温度280℃，反应时间为2h，催化剂加入量为4％，搅拌转速在200～250r／min，反应后高、低沸物的利用率在75％以上，产物中二甲含量可达49％（以上均指重量百分比）。结合小试结果以及高、低沸歧化反应的特点，确定了采用316合金作为反应装置的主体材料，并对中试工艺流程进行了总体方案设计。 研究发现不同的高、低沸物组成对歧化反应结果影响很大，采用GC-MS对高、低沸物的组成进行了分析，确定了其基本组成和组分的含量，并根据反应物与产物组成对比，探讨了高、低沸歧化反应的机理，认为反应过程中主要为脱氯、富氯硅烷与与富甲基二硅烷基团之间再分配反应；高沸物在高温高压、催化剂、HCl作用下裂解成单硅烷；裂解产生的单硅烷之间、低沸物组分之间，裂解单硅浙江大学硕士学位论文烷与低沸物组分之间再发生基团之间的歧化、再分配反应。此外，本文还对如何将高沸物裂解反应与高、低沸歧化反应两段工艺优化组合进行探讨，认为采用高沸裂解一高、俪沸歧化组合工艺更适合进行中试研究。更多还原

【Abstract】 The paper is concerned with the research on treating and reusing the high-boling residue and low-boiling residue ,which formed in the direct process for the synethesis of dimethyldichlorosilane, by converting the high-boiling residue in the presence of hydrogen chloride to monosilane and by converting the high-boiling residue and low-boiling residue through disproportion reaction using A1C13 catalyst. The main object is to find optimal methods and ways to utilize the above by-product and make good economic ,social and ecological benefits.This paper includes two parts.Part one:Pilot investigating of high-boiling cleavaging with hydrogen chloride.In the 500t/a scale set for cleavage reaction, the orthogonal experiments were carried out to study the effects of reaction temperature, stirring rate,flux of HC1 and catalyst quantity and the factors of affecting the high-boiling cleavage ration and monosilane yeild were analyzed. The optimum reaction conditions were obtained:reaction temperature is 130 , stirring rate is 200r/min, catalyst quantity is 1.25~2%, flux of HC1 is 1.00L/h.At this condition, high-boiling cleavage ration is 86.71% and monosilane yeild is 67.81 %.The monosilane yeild can be increased by the recyling of high-boiling adsorbed mixtures.Part two: Disproportion reaction between high-boiling residue with low-boiling residue.AlCl3 is a good catalyst for the disproportion reaction. By investigating, the optimum conditions for the disproportion reaction were obtained: the quantity ration of reaction materials is 5: 1, reaction temperature is 280 , reaction time is 2h, catalyst quantity is 4%, stirring rate is 200~250r/min, The utilization of high-boling residue and low-boiling residue attain 75%, the content of dimethyldichlorosilane attain 49 % .Combining the result and the feature of disproportion reaction, we choose the 316 alloy materials for the design of reactor. Also the assemble project was designed.The composition of high-boiling residue and low-boiling residue have great influence composition of the above by-product.Based on the analysis results,the mechanism ofdisproportion reaction was investigated.We consider that chlorine escaping reaction, redistribution reaction, disproportion reaction and cleavge reaction were occurred between the high-boiling, low-boiling and monosilanes.At the end of the paper, assembled process of cleavage reaction of high-boiling residue and disproportion reaction were investigated.更多还原