环氧氯丙烷生产又添绿色新路径
A new green path is added to epichlorohydrin production
7月29日，由山东凯泰科技股份有限公司和中科院大连化学物理研究所合作开发的8万吨/年丙丙法环氧氯丙烷(ECH)工艺包通过中国石油和化学工业联合会组织的专家评审。该工艺包融合了双氧水氧化法和甘油法两种ECH工艺的优点，通过技术耦合，实现废盐酸的资源化利用，从而解决由于大量副产酸严重制约生产平衡的问题，提升装置的经济和环保效益。专家组认为该工艺为环氧氯丙烷产品的绿色化发展提供了一种新的技术路径。
Ltd. and Dalian Institute of Chemical Physics of Chinese Academy of Sciences jointly developed 80,000 tons/year propylene-based epichlorohydrin (ECH) process package, which passed the expert review organized by China Petroleum and Chemical Industry Federation on July 29. The process package combines the advantages of two ECH processes, hydrogen peroxide oxidation and glycerol process, and realizes the resource utilization of waste hydrochloric acid through technical coupling, thus solving the problem that the production balance is severely restricted by a large amount of by-product acid and improving the economic and environmental benefits of the plant. The expert group believes that this process provides a new technical path for the green development of epichlorohydrin products.
据凯泰科技副总经理孟凡新介绍，双氧水氧化法工艺是大连化物所开发的一条ECH绿色合成工艺，原料氯丙烯生产过程副产氯化氢;而甘油法则是当前生产ECH的另一条绿色工艺，生产过程正好需要氯化氢。丙丙法ECH工艺则巧妙地以双氧水氧化法工艺中合成氯丙烯副产的氯化氢作为两种工艺的结合点，整条工艺以丙烯、丙三醇(甘油)为主要原料，以双氧水氧化法作为核心工艺，以氯丙烯副产的氯化氢作为甘油法原料对其进行技术耦合，在产出ECH的同时，实现高盐废水和废盐酸的资源化利用。“我们据此创新开发了8万吨/年丙丙法环氧氯丙烷工艺包，包括5万吨/年双氧水氧化法和3万吨/年甘油法两套装置。”孟凡新说。
According to Meng Fanxin, deputy general manager of Kaitai Technology, hydrogen peroxide oxidation process is an ECH green synthesis process developed by Dalian Chemical Institute. Hydrogen chloride is produced byproduct in the production process of raw material propylene chloride. The glycerol rule is another green technology for ECH production, and hydrogen chloride is needed in the production process. C c method of ECH process is ingeniously with hydrogen peroxide oxidation process in the synthesis of allyl chloride by-product hydrogen chloride as a point of two kinds of process, the whole process in propylene, glycerin (glycerol) as the main raw material, with hydrogen peroxide oxidation method as the core technology, with allyl chloride by-product hydrogen chloride as raw materials for the glycerine method for coupling technology, at the same time of output ECH, To realize the resource utilization of high salt wastewater and waste hydrochloric acid. "Based on this innovation, we developed an 80,000-ton/year epichlorohydrin process package, including a 50,000-ton/year hydrogen peroxide oxidation process and a 30,000-ton/year glycerol process." Meng Fanxin said.
丙丙法工艺包在相关工艺技术和关键设备上进行了多项改进和创新。
Propylene-propylene process package has made many improvements and innovations in related process technology and key equipment.
“我们在5000吨/年双氧水氧化法工艺中试成果基础上，与工程技术人员一起对其进行了进一步优化改进和工程化开发，完成了5万吨/年DECH工艺包的开发。”大连化物所高爽研究员说。
"On the basis of the pilot test results of the 5,000-ton/year hydrogen peroxide oxidation process, we have further optimized and improved it together with engineers and technicians, and completed the development of the 50,000-ton/year DECH process package." Gao Shuang, a researcher at Dalian Institute of Chemical Technology, said.
氯丙烯新装置采用每台2.5万吨/年高温氯化反应器，提高了单台氯化反应器生产能力，降低了投资成本。双氧水氧化法工艺采用两级管式反应器及一级釜式反应器，增加了反应过程的安全性，有利于催化剂的结晶和分离;甘油法反应釜采用无机械搅拌混合反应器，避免了泄漏，降低了电耗。同时，丙丙法工艺中的高盐废水经处理后可作为离子膜烧碱的生产原料，废气、废液经焚烧无害化处置实现资源化利用，减排减污效果显著。
The new ALLyl chloride unit adopts a 25,000-ton/year high temperature chlorination reactor, which improves the production capacity of a single chlorination reactor and reduces the investment cost. The hydrogen peroxide oxidation process adopts two-stage tubular reactor and one-stage tank reactor, which increases the safety of the reaction process and is conducive to the crystallization and separation of the catalyst. The glycerol process reactor adopts mixing reactor without mechanical stirring, which can avoid leakage and reduce power consumption. At the same time, the high-salt wastewater in the propylene and propylene process can be used as raw materials for the production of ionic membrane caustic soda after treatment, and the waste gas and liquid can be incinerated to achieve resource utilization, and the emission reduction and pollution reduction effect is significant.
“丙丙法工艺解决了氯丙烯副产大量盐酸的问题，实现了氯、钠、氢的循环利用，同时还合并了氧化法和甘油法的ECH精制工序，两种方法生产的粗ECH可合并精制，这样就减少了装置占地，投资和能耗也进一步降低。此外该工艺的项目建设和运行模式也更灵活，既可根据需求扩展至产业链上游的双氧水装置、烧碱装置和下游的环氧树脂装置，也可根据原料供应和市场价格等情况灵活调整两种工艺的生产规模，实现利润最大化。”凯泰科技副总工程师高正宁说。
"The propyl process solves the problem of by-production of large amount of hydrochloric acid from allyl chloride, and realizes recycling of chlorine, sodium and hydrogen. At the same time, it combines the ECH refining process of oxidation method and glycerol method. The crude ECH produced by the two methods can be combined for refining, which reduces the footprint of the plant and further reduces the investment and energy consumption. In addition, the project construction and operation mode of the process is also more flexible, which can be expanded to the hydrogen peroxide plant, caustic soda plant and epoxy resin plant in the upstream of the industrial chain according to the demand, and the production scale of the two processes can be flexibly adjusted according to the raw material supply and market price, so as to maximize the profit." Kaitai technology deputy chief engineer Gao Zhengning said.
据记者了解，目前国内ECH生产普遍采用的氯醇法工艺因存在能耗高、副产物多、含盐有机废水处理难度大等问题，已被《产业结构调整指导目录(2019)》列为限制类工艺，氯丙烯直接氧化法合成ECH技术则被列为行业“十三五”重大关键核心技术加快组织研发，丙丙法工艺的研发契合政策要求，顺应了行业节能减污降碳的发展趋势。
According to the reporter, the chloro-alcohol process widely used in ECH production in China has been listed as a restricted process in the Guidance Catalog of Industrial Structure Adjustment (2019) due to its high energy consumption, many by-products and difficulty in treating saline organic wastewater. The ECH technology of direct oxidation synthesis of allyl chloride has been listed as the key core technology of the industry in the "13th Five-Year Plan" to accelerate the organization of research and development. The research and development of propylene and propylene process conforms to the policy requirements and complies with the development trend of energy saving, pollution reduction and carbon reduction in the industry.
