中国石化双氧水法制环氧丙烷工业开发及关键科技问题

KEY SCIENTIFIC PROBLEMS AND INDUSTRIAL DEVELOPMENT OF SINOPECHPPO TECHNOLOGY FOR GREEN PROPYLENE OXIDE PRODUCTION

为克服现有环氧丙烷(PO)生产技术弊端,中国石化采用表面富硅空心钛硅分子筛为活性组元的催化剂,开发了新型双氧水法制备环氧丙烷(HPPO)成套技术,建成了国内首套100 kt a HPPO工业装置。催化剂以表面富硅多空心钛硅分子筛为活性组元,采用高效羟基偶联黏结剂,提高了活性组元含量和催化剂强度。开发了器内低温原位复活技术。以复合助剂调控双氧水与骨架钛形成“五元环”过渡态,大幅提升PO选择性。开发出PO低温分离、萃取蒸馏和化学脱杂耦合的产品分离精制技术,提升产品质量。将PO废水作为炼油厂催化裂化装置的终止剂,使有机物裂解成乙烯、丙烯等低碳烃。与国外先进技术相比:双氧水转化率高3.3%,PO选择性高3.6%;产品中杂质总醛含量低80%,水分低50%;产品纯度达99.99%,优级品率达到100%。

In order to overcome the disadvantages of the existing technologies for propylene oxide(PO)production,SINOPEC has developed a new hydrogen peroxide propylene oxide(HPPO)process by using silicon-rich surface hollow titanium silicalite molecular sieves as catalytic component,and the first 100 kt a HPPO industrial plant in China has been built.The surface silicon-rich multi-hollow titanium-silicon molecular sieve was invented,and the high-efficiency hydroxyl coupling binder was developed,which could simultaneously increases the active component content and the catalyst strength under low-temperature reaction conditions.A composite auxiliary agent was developed,which regulated the formation of a“five-member ring”transition state between hydrogen peroxide and framework titanium,thus greatly improving PO selectivity.The separation and purification technology of PO by low temperature separation,extractive distillation and chemical de-impurity coupling was explored to enhance the product quality.PO wastewater was used as terminator in catalytic cracking unit to make organic matter cracking into low carbon hydrocarbons such as ethylene and propylene.Compared with foreign reference technologies,the impurity total aldehyde is 80%lower,the moisture content is 50%lower,the hydrogen peroxide conversion rate is 3.3%higher,the PO selectivity is 3.6%higher,the purity of PO product is 99.99%,and the rate of high grade product is 100%.