合成气直接制二甲醚的Cu基双功能催化剂研究  

Cu-based bi-function catalysts for direct synthesis of dimethyl ether from syngas

作　　者：沙雪清[1] 林红[1] 宫丽红[2] 史克英[3] 

机构地区：[1]哈尔滨师范大学阿城学院 [2]哈尔滨师范大学化学系,黑龙江哈尔滨150080 [3]黑龙江大学化工学院,黑龙江哈尔滨150080

出　　处：《哈尔滨工业大学学报》2005年第10期1384-1387,共4页Journal of Harbin Institute of Technology

基　　金：黑龙江省博士后基金;黑龙江省教育厅科学技术研究项目(10541086)

摘　　要：为对催化研究和二甲醚的实际生产提供参考,采用共沉淀沉积法制备了一系列CuO/ZnO/ZrO2/MnO2/HZSM-5比例不同的二甲醚合成催化剂,并在固定床高压流动反应装置上,以自制的含氮合成气(V(H2)∶V(CO)=2.13)为原料考察了催化剂制备条件和组分比例对催化剂性能的影响.结果表明,当共沉淀温度在75℃、pH值在10左右,n(CuO)∶n(ZnO)∶n(ZrO2)∶n(MnO2)=1∶1∶0.5∶0.01、m(MnO2-(CuO-ZnO-ZrO2)∶m(HZSM-5)=3∶1时,催化剂的活性和选择性最好,在反应压力为4.0 MPa,原料空速为1 000 h-1,反应温度为250℃时,CO转化率达到87.81%,二甲醚收率达到65.07%.TPR、XRD、XPS等测试结果表明,在MnO2-(CuO-ZnO-ZrO2)/HZSM-5催化剂中,ZnO能提高CuO组分的分散度,使活性中心增加,并与MnO2协同作用,促进电子传递,增强了催化剂的活性和选择性.A series of catalysts （ MnO2-（CuO-ZnO-ZrO2 ）/HZSM-5） were produced by using precipitation of joint sedimentation, the influence of the preparing conditions of those catalysts and components proportion on the catalysts performance was investigated by the＇self-made syngas（ H2/CO=2.13, ratio of volume） with a fixed- bed flow apparatus so as to make references to the realistic production of dimethyl ether and to the studying on the catalysts. The results indicated that both the temperature of the joint sedimentation and pH value affected the activity of the catalysts. When the temperature of the joint sedimentation was 75℃, and the pH value was around 10, and the proportions of CuO/ZnO/ZrO2/MnO2 being 1：1 ： 0.5： 0. 01 （ molar ratio） and of [ MnO2-（CuO-ZnO-ZrO2 ）]/HZSM-5 being 3： 1 （ mass ratio）, the prepared catalysts were at the higher catalyst activity. The catalysts were determined by means of TPR, XPD and XPS, the results of tests indicated that the ZnO additives could increase the dispersing degree of active component of CuO, and being combined with MnO, quicken the electronic transfering and make the catalyst activity increasing and on the technologic conditions of the reactive pressure being 4.0MPa, space velocity being 1000 h^-1, reactive temperature being 250℃, the ConvCO reaches to 87. 81% and the SelDME goes to 65.07%.

关 键 词：催化剂 二甲醚(DME) 助剂 

分 类 号：O611.4[理学—无机化学]