The thermodynamic property of acetylene hydrochlorination chloride reaction system,both main and side reactions,was calculated. The Gibbs reactor modules of Aspen 11.1,combined with the Sensitivity tool,was used to calculated the equilibrium yield rate in the three cases of single product, regardless of the polymerization reaction and with the consideration of the polymerization in 90-420 ℃. The results show that,from the thermodynamics point of view,all the reactions are strong exothermic reaction and can occur spontaneously in the standard condition. For each independent reaction,the acetylene conversion rate can closely reach 100%below 210 ℃,and with the temperature growing the acetylene equilibrium conversion rate decreases,especially for the non-polymerization reaction. When considered with the non-polymerization side reactions,the yield rate of vinyl chloride can also reach more than 97%. However,the yield rate of vinyl chloride is only 0.6% when the polymerization reaction is counted in,while the yield rate of chloroprene reaches the highest. It is demonstrated that the vinyl chloride product can easily react with acetylene. Therefore,in the actual reactions,the vinyl chloride product shall be promptly removed and excessive acetylene should be avoided. The carbon catalyst deactivation factors should be considered and carbon deactivation should also be reduced.%对乙炔氢氯化反应体系主反应与副反应的热力学性质进行了计算。采用Aspen Plus11.1中的Gibbs反应器模块并结合 Sensitivity 工具对单一产物、不考虑聚合反应与考虑聚合反应3种情况下各产物在90～420℃下的平衡收率进行计算。结果表明：从热力学角度讲，各反应均为强放热反应，标准状态下能自发进行；210℃以下各反应单独进行时均能达到接近100%的转化率，随温度升高，各反应乙炔平衡转化率逐渐降低且非聚合副反应降低的最快；当考虑非聚合副反应时，氯乙烯收率仍能达到97%以上；但当考虑聚合反应时，氯乙烯收率最高仅为0.6%，主要生成氯丁二烯。表明生成的氯乙烯容易与乙炔发生串联聚合，实际反应过程中应及时将氯乙烯移除，并避免乙炔过量。反应过程中应考虑催化剂的积炭失活因素，降低积炭。
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