氯乙烯单体合成工艺研究进展

氯乙烯单体(VCM)主要用来合成聚氯乙烯(PVC).聚氯乙烯是世界五大工程塑料之一,聚氯乙烯在各行各业具有十分广泛的应用.目前氯乙烯单体的工业合成工艺主要有电石乙炔法、乙烯法、乙炔-乙烯法和乙烷法等.本文详尽地综述了各工艺的原理、流程及应用现状,并对氯乙烯单体合成工艺发展趋势进行了展望.     

电石法氯乙烯单体质量的提高

为了提高电石法氯乙烯单体品质,在氯乙烯生产中采用了先进的氯乙烯合成工艺、变压吸附脱水技术和高效导向筛板精馏塔技术,降低了精氯乙烯单体中的杂质含量,单体含水质量分数≤100×10~(-6),从而保证了PVC树脂的质量。     

氯乙烯生产及其工艺技术新进展

介绍了聚氯乙烯基本原料乙烯以及其单体氯乙烯和二氯乙烷的生产发展状况,特别对氯乙烯单体的在生产工艺上近期开发的一些新技术、新工艺作了比较细地论述。另外,对我国近年新建、扩建的乙烯、氯乙烯和二氯乙烷装置分布及产能情况作了重点介绍。     

荷兰阿克苏公司氯乙烯单体/纯碱新工艺搁浅了

<正> 荷兰阿克苏公司已经暂停了原来庞大的氯乙烯单体/纯碱联合计划,并放弃了原计划采用新技术建立生产氯乙烯单体/纯碱的工厂。该工艺生产的氯乙烯单体改变了传统的电解工艺,用乙烯和氯化钠二步工艺生产二氯乙烯和碳酸氢钠。如果该公司废除电解工艺而采用新工艺,能量可节省一半。尽管如此,为该     

电石乙炔法合成氯乙烯单体高汞触媒的现状分析

氯乙烯单体(VCM)主要用来合成聚氯乙烯(PVC)。聚氯乙烯是世界五大工程塑料之一,聚氯乙烯在各行各业具有十分广泛的应用。由于能源结构形式和潜在的成本优势,目前,我国氯乙烯单体工业合成工艺主要以电石乙炔法为主。但该法催化剂高汞触媒的使用会带来系列问题,是其发展的瓶颈。本文指出了高汞触媒一系列弊端,对其现状进行了分析,并对电石乙炔法氯乙烯单体合成工艺催化剂的发展趋势进行了展望。     

乙炔法合成氯乙烯用无汞触媒研究进展

氯乙烯单体的工业合成方法主要有乙炔氢氯化法和乙烯氧氯化法。我国大约70%氯乙烯单体(VCM)采用乙炔氢氯化法生产。使用新型无汞催化剂替代目前剧毒的氯化汞/活性炭催化剂是该工艺亟待解决的难题。综述了乙炔法合成氯乙烯用无汞触媒的研究进展,探讨了无汞触媒的种类、结构与性能,并展望了今后的发展趋势。     

化工部氯乙烯聚合反应工程学习班

由化工部委托浙江大学高分子化工教研组,于84年12月24日至85年1月12日举办了一期氯乙烯聚合反应工程学习班。学员系来自聚氯乙烯生产、研究、设计、设备制造的工程技术人员,计45人,分属31个单位。 学习内容有氯乙烯聚合反应工程(聚合过程,氯乙烯单体,氯乙烯树脂品种和主要质量指标,氯乙烯聚合机理和动力学,引发剂,热稳定性,聚氯乙烯树脂形态学和成粒过程,分散剂,聚合釜传热,搅拌等十章)理论教学和新技术专题讲座(包括吸附脱水,氯乙烯合成的工程分析,粉料密相气流     

聚氯乙烯主要原料生产技术和市场新动态

介绍了聚氯乙烯基本原料乙烯以及其单体氯乙烯和二氯乙烷的生产发展状况，特别对氯乙烯单体在生产工艺上近期开发的某些新技术、新工艺作了比较详细地论述。对我国近年新建、扩建的乙烯、氯乙烯和二氯乙烷装置分布及产能情况作了重点介绍。最后讨论了废旧聚氯乙烯回收利用已取得的一些新成果。     

氯乙烯聚合尾气回收工艺的改进

介绍了一种简单的氯乙烯聚合尾气回收的工艺,将氯乙烯聚合反应后产生的尾气引至氯乙烯合成和精馏工序,通过合成工序的碱洗塔除去影响生产和产品质量的杂质,利用精馏工序的变压吸附装置,吸附回收氯乙烯单体和排放氮气等杂质气体,工艺流程简单,建设投资小,可降低生产成本,实现清洁生产。     

偏氯乙烯生产过程中质量和消耗的控制

阐述了偏氯乙烯合成过程中氯化、皂化、精馏等工序的生产要点,通过严格的工艺控制,使偏氯乙烯的纯度稳定在99％以上（氯乙烯含量小于0．5％）,每生产1t偏氯乙烯消耗氯乙烯单体为780kg。     

氯乙烯-醋酸乙烯酯共聚物的后功能化研究

通过将氯乙烯－醋酸乙烯酯－丙烯酸羟乙醋共聚物（VAGF）与马来酸酐酯化接枝，制得带羟基的氯醋三元共聚物。探索了原料配比、催化剂用量、反应时间及反应温度对酯化接枝反应的影响，并用红外光谱进行表征。得到酯化反应的最佳条件为：催化剂用量为VAGF质量的0．8％，VAGF质量分数为15％，温度100℃，时间9h。氯乙烯－醋酸乙烯酯－丙烯酸羟乙酯三元共聚物的马来酸酐酯化活性高于氯乙烯－醋酸乙烯酯－乙烯醇三元共聚物。     

The in situ polymerization of vinyl chloride in poly(butyl acrylate)

The in situ polymerization of vinyl chloride with poly(butyl acrylate) has been studied. Vinyl chloride was polymerized using a peroxydicarbonate initiator in sealed ampoules in the presence of various weights of poly(butyl acrylate). The products were examined by dynamic mechanical analysis and electron microscopy. It was found that if about 50% or less vinyl chloride was present in the mixture homogeneous blends were formed. If more than 50% vinyl chloride was present the polymerization passed through a two phase region in the three component phase diagram and inhomogeneous blends were formed. If homogeneous blends prepared as above were reswollen with vinyl chloride and the latter polymerized, then homogeneous blends containing more poly(vinyl chloride) could be prepared, avoiding the two phase region. The interaction parameters between vinyl chloride and both poly(vinyl chloride) and poly(butyl acrylate) were estimated using inverse gas chromatography. Using these and an estimate of the polymer/polymer interaction parameter the three component phase diagram could be qualitatively explained.     

乙炔法合成氯乙烯催化剂的研究进展

The synthesis of vinyl chloride is the key of polyvinyl chloride production.There are two main methods for synthesis of vinyl chloride:hydrochlorination of acetylene and oxychlorination of ethylene.The synthesis process of vinyl chloride from acetylene hydrochlorination was introduced in this paper.The research progress in novel low-mercury and mercury-free catalysts at home and abroad was reviewed.The development prospects of the catalyst for synthesis of vinyl chloride from acetylene were also outlined.     

Study of Vinyl Acetate Partitioning in Emulsion Copolymerization of Vinyl Chloride-Vinyl Acetate by FTIR and HNMR Spectroscopy

Emulsion copolymerization of vinyl chloride with vinyl acetate comonomer was performed. Potassium persulfate, a mixture of stearyl alcohol and sodium lauryl sulfate, was used and reactions were performed at 55 °C in a pressurized reactor. By sampling during the reaction in different intervals copolymer composition was investigated using FTIR and NMR spectroscopy. The results showed that the partitioning of vinyl acetate in the copolymerization in general follows the Mayo-Lewis copolymerization equation with some discrepancy. This was attributed to the gaseous nature of vinyl chloride monomer and the differences between polymerization in heterogeneous and homogeneous systems. Both FTIR and NMR spectroscopy showed two peaks in vinyl acetate content of copolymer beyond 65% conversion which was attributed to the elimination of vinyl chloride droplets in the media and replacing them with vinyl acetate monomer. The first increase is related to the consumption of vinyl chloride droplets and the second is related to the consumption of gaseous vinyl chloride; in both instances vinyl acetate governs the polymerization.     

氯乙烯气柜排水系统密闭改造及安全仪表改造

对氯乙烯气柜进行了密闭排水改造,完善了 SIS系统和氯乙烯气柜报警及监控系统,提高了氯乙烯气柜运行的安全性.     

二硫化碳萃取气相色谱法测定废水中的氯乙烯

用二硫化碳萃取工业废水中的氯乙烯,用岛津GC-14B气相色谱仪FID检测器检测。方法在0.005～2.680 mg/L范围内线性良好,检出限为0.005 mg/L,标准样品测定的相对标准偏差为2.6%～3.7%,实际样品的加标回收率为93%～98%。使用纯度较高的气体氯乙烯单体作标准样品,既经济又方便。试验发现对超出检出限的氯乙烯废水样品,采用稀释法比提高萃取液的使用量更能提高氯乙烯的萃取效率,为监测废水中的氯乙烯提供了试验依据和理论支持。     

氯乙烯尾气回收装置变压吸附改造

介绍了氯乙烯尾气回收变温变压吸附和恒温变压吸附原理,阐述了对氯乙烯尾气回收工艺改造的目的和方案。通过改造,吸附塔长期稳定运行,产品气的质量能满足转化装置的要求,且能回收大量的氯乙烯和乙炔。     

Toxicity of pyrolysis and combustion products of poly-(vinyl chloride)

The pyrolysis and combustion products of poly-(vinyl chloride) and those of some of its polymer, especially of vinyl chloride with vinylidene chloride, were analysed using gas chromatography and gas chromatography mass spectrometry. The toxic effect of the individual products on the human organism was evaluated and presumed total toxicity of the poly-(vinyl chloride) combustion products (0.3g PVC products per m³) was determined.     

氯乙烯精馏装置的控制方案

介绍了氯乙烯精馏的工艺流程,详细论证了基于扰动观测器设计的氯乙烯精馏装置控制方案。     

含氯乙烯的接枝聚醚及其制备

介绍了单一VC单体或VC单体与其他乙烯基单体共同接枝聚醚的制备方法,接枝后VC-POP与TDI(MDI)反应后制得试样的拉伸强度、撕裂强度、压缩强度提高。