铜系材料的制备及其催化丁二酸二甲酯加氢的性能探究

Study on preparation of copper⁃based materials and its catalytic performance for hydrogenation of dimethyl succinate

目前,工业上多用炔醛法、顺酐法、丁二烯法和环氧丙烷法生产1,4-丁二醇(BDO),但由于高能耗、高污染问题,使用更绿色环保的生物法生产BDO逐渐显示出更大优势。当前对由生物质平台化合物丁二酸酯化制得的丁二酸二甲酯(DMS)加氢制BDO研究较少。选用硝酸铜、硝酸锌和硝酸铝3种无机盐材料,通过共沉淀法制备了用于DMS加氢制备BDO反应的铜系催化剂;对产物进行XRF、BET、H_(2)-TPR、XRD、XPS等表征,并对催化材料性能进行测试,以期得到性能良好的催化材料,为后续研究提供思路。经分析,铜的质量分数为20%、锌铝物质的量比为0.3的催化材料在反应温度为185℃、反应压力为5 MPa、氢酯体积比为150、液时空速为1 h^(-1)时,催化DMS加氢反应性能良好,DMS转化率为98.6%、BDO选择性为87.3%,且连续运转1000 h稳定性良好,具有较好的工业化前景。

At present,acetylene aldehyde method,maleic anhydride method,butadiene method and propylene oxide method are used in the industry to produce 1,4-butanediol(BDO).However,due to the high energy consumption and pollution,the use of more green biological method to produce BDO gradually shows more advantages.At present,there are few researches on the hydrogenation of dimethyl succinic acid(DMS),which can be obtained from the esterification of succinic acid platform molecule,to BDO.Three inorganic materials of copper nitrate,zinc nitrate and aluminum nitrate,were selected to prepare the copper catalyst for the hydrogenation of dimethyl succinic acid(DMS)to 1,4-butanediol(BDO)by coprecipitate method.The products were characterized by XRF,BET,H_(2)-TPR,XRD and XPS.And the catalytic material properties were tested in order to obtain catalytic materials with good performance,providing ideas for subsequent research.The results showed that the catalytic material with copper mass fraction of 20%and zinc⁃aluminum molar ratio of 0.3 had good hydroge⁃nation performance at 185℃,5 MPa,hydrogen⁃ester ratio of 150 and space velocity of 1 h^(-1),with DMS conversion rate of 98.6%and BDO selectivity of 87.3%.And it had good stability after 1000 h continuous operation which showed good industrial prospect.