CO偶联合成草酸酯催化剂国内专利技术进展

以煤炭为资源,通过CO气相偶联制备草酸酯、进而加氢合成乙二醇,成为间接法合成乙二醇的最佳工艺路线.在中国,已经利用该工艺建成了多套20× 104t/a级的工业装置,在“十二五”期间,还要陆续建设总产能约400×104t/a的乙二醇装置.中国在煤制乙二醇成套技术的开发和应用上走到了世界前列.CO偶联合成草酸酯催化剂技术,催化剂一般由载体、主催化剂和助催化剂组成.该催化剂的载体主要为α-A12O3,也可以是6-A12O3、SiO2、分子筛或以它们为主构成的复合载体；贵金属Pd几乎成为不可或缺的主催化剂.在此基础上,陆续开发了含一种、两种或三种助催化剂的催化剂体系,助催化剂主要选自La系元素、碱土金属元素、Fe、Cu、Mo、W、Co、Zn及Ti等过渡金属元素.同时,综述了复合载体催化剂、规整催化剂及金属骨架催化剂的进展.在一定的工艺条件下,CO单程转化率几乎接近75％,草酸酯选择性接近100％,草酸酯时空产率在1000g/(L·h).

Advances in China＇s Proprietary Catalyst Technology Used in Synthesizing Oxalate by CO Coupling

Using coal and gas-phase coupling of CO to make oxalate and to further synthesize glycol by hydrogenation is currently the best technical route for synthesizing glycol using the indirect method.China has established multiple 20×10^4t/a industrial units using this technology and will add glycol units with a combined capacity of 400×10^4t/a during the Twelfth Five-Year Plan period （2011-2015）.China is at the forefront of the development and application of coal-to-glycol packaged technology.The typical catalysts used in oxalate synthesis by CO coupling consist of carriers,primary catalysts and promoters.α-A1203 is the most commonly used carrier and the carrier can also be 6-Al2O3,SiO2,molecular sieve or a compound carrier based on one of them.Noble metal Pd is almost an indispensable primary catalyst.China has developed a series of catalyst systems containing one,two or three promoters,which are primarily La family elements,alkaline earth metal elements and transition metal elements such as Fe,Cu,Mo,W,Co,Zn and Ti.This article also briefly describes the advances in compound carrier catalysts,structured catalysts and metallic framework catalysts.In certain technical process,the CO conversion per pass can reach nearly 75%,the selectivity of oxalate is nearly 100% and the oxalate space time yield stands at 1000g/（L.h）.