原位还原Cu／ZnO催化剂上CO2加氢合成甲醇反应研究  

Synthesis methanol reactions by CO_2 hydrogenation on in-situ reduction Cu/ZnO catalyst

作　　者：徐钉[1,2] 张培培 李航杰 吕成学[1,2] 盖希坤[1,2] 杨瑞芹[1,2] 

机构地区：[1]浙江科技学院生物与化学工程学院,浙江杭州310023 [2]浙江省农产品化学与生物加工技术重点实验室,浙江杭州310023 [3]富山大学,日本富山9308555

出　　处：《应用化工》2017年第4期663-667,共5页Applied Chemical Industry

基　　金：国家自然科学基金项目(21528302);浙江省自然科学基金项目(LY14B030004)

摘　　要：采用室温固相研磨法制备原位还原Cu/ZnO催化剂,并将其用于CO_2加氢合成甲醇反应。利用XRD、BET、TG-DTG等手段对催化剂性能进行了表征,利用高压固定床反应装置对催化剂活性进行了评价,考察了甲酸用量、焙烧温度及升温速率等条件对催化剂性能的影响。结果表明,室温固相研磨得到的前驱体在N_2中焙烧,前驱体氧化分解和还原活化一步完成,无需外加H_2还原,直接制得了原位还原Cu/ZnO催化剂。随甲酸用量、焙烧温度、升温速率增加,催化活性呈现先增加后减小趋势。Cu/Zn摩尔比为1∶1和HCOOH/(Cu+Zn)摩尔比11∶1,前驱体于N_2中焙烧温度573 K和升温速率3 K/min时,制得的原位还原Cu/ZnO催化剂在CO_2加氢合成甲醇反应中呈现最佳活性,CO_2转化率和甲醇产率分别达到了33.44%和28.17%。与空气中焙烧再外加5%H_2还原的Cu/ZnO催化剂相比,原位还原Cu/ZnO催化剂比表面积较高,Cu^0粒径较小,催化活性较高。The in-situ reduction Cu/ZnO catalyst was prepared by solid phase grinding method at room temperature, and applied to the CO： hydrogenation synthesis methanol reactions. The performances of the catalysts were characterized by the means such as XRD, BET and TG-DTG. The activity of the catalysts was evaluated by the high pressure fixed bed reaction device. The influences of the dosage of formic acid, caleinating temperature and heating rate on the Cu/ZnO catalyst properties were investigated. The results show when the precursor obtained by solid phase grinding at room temperature was calcinated in N2, its oxidation decomposition and the reduction activation was completed by one step without reduction by extra H2, and the in-situ reduction Cu/ZnO catalyst was directly prepared. With the increase of dosage of formic acid, calcinating temperature and heating rate, the catalytic activity appeared a trend of decrease after the first increase. When the precursor of the Cu/ZnO catalyst with Cu/Zn molar ratio of 1/1 and HCOOH/ （Cu ＋ Zn） mole ratio of 11/1 was calcined at 573 K and heating rate of 3 K/rain in N2 ,the activity of the in-situ reduction Cu/ZnO catalyst in the C02 hydrogenation synthesis methanol reaction was the best, and C02 conversion and methanol yield reached 33.44% and 28. 17%, respectively. The surface area was higher, and the Cu^0 particle diameter was smaller, and the catalytic activity was higher for the in-situ re- duction Cu/ZnO catalyst compared to those for the Cu/ZnO catalyst calcined in air and then reduced by extra 5% HE.

关 键 词：研磨法 Cu/ZnO CO2加氢 甲醇 

分 类 号：TQ032.41[化学工程]