Chemical Industry and Engineering Progress ›› 2017, Vol. 36 ›› Issue (08): 2955-2961.DOI: 10.16085/j.issn.1000-6613.2016-2217

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Influence of different precipitants on the properties of Cu-ZnO-ZrO2 catalyst for methanol synthesis through CO2 hydrogenation

CHENG Pengze1,2, GAO Wengui1,3, NA Wei1,3, WANG Yuhao1,3, LI Yanyan1,2, XU Maomao1,2   

  1. 1. State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan, China;
    2. Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China;
    3. Faculty of Metallurgy and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China
  • Received:2016-11-30 Revised:2017-04-11 Online:2017-08-05 Published:2017-08-05

不同沉淀剂对CO2加氢合成甲醇Cu-ZnO-ZrO2催化剂性能的影响

程鹏泽1,2, 高文桂1,3, 纳薇1,3, 王禹皓1,3, 李艳艳1,2, 徐毛毛1,2   

  1. 1. 昆明理工大学省部共建复杂有色金属资源清洁利用国家重点实验室, 云南 昆明 650093;
    2. 昆明理工大学化学工程学院, 云南 昆明 650093;
    3. 昆明理工大学冶金与能源工程学院, 云南 昆明 650093
  • 通讯作者: 高文桂,副教授,主要从事冶金节能减排的研究。
  • 作者简介:程鹏泽(1989-),男,硕士研究生,从事甲醇合成催化剂的研究。E-mail:chpz2017@126.com。
  • 基金资助:
    国家自然科学基金(51304099)、云南省应用基础研究计划(2013FZ035)、国家科技支撑计划(2011BAC01B03)及昆明理工大学分析测试基金(2016T20080007)项目。

Abstract: Cu-ZnO-ZrO2(molar ratio CuO:ZnO:ZrO2=5:4:1) catalysts were prepared using different precipitants(NH3·H2O、NaHCO3、Na2CO3)by concurrent-flow co-precipitation method. XRD,XPS,H2-TPR and CO2-TPD were used to characterize the physico-chemical properties of the catalysts,and the catalysts activity were evaluated in a high temperature and high pressure micro-reactor. The influences of different precipitants on the catalyst precursors and catalysts component structure,CuO-ZnO interaction for methanol synthesis through carbon dioxide hydrogenation were studied. Results show that the influence of different precipitants on the physico-chemical properties and activity of catalysts was very great. When the precipitants of NaHCO3 and Na2CO3 were used,they was helpful to produce aurichalcites in catalyst precursors,which,after calcination,were effective to prevent the growth of CuO particles,and to improve the dispersion of the metal copper oxide,increase the metal surface basic sites,enhance CuO-ZnO interaction,and raise the catalysts activity. More aurichalcites were produced in the catalyst precursors by using NaHCO3 as the precipitant,and the particle size of the CuO was 8.6nm,the copper specific surface area was 15.38m2/g,the dispersion degree of copper was 11.9%,the selectivity of methanol was 42.29%,the yield of methanol was 0.094g/(gcat·h),and the catalyst activity was the highest.

Key words: precipitants, carbon dioxide, catalysts, hydrogenation, methanol

摘要: 分别以NH3·H2O、NaHCO3、Na2CO3为沉淀剂,采用并流沉淀法制备Cu-ZnO-ZrO2(摩尔比为5:4:1)催化剂,通过XRD、XPS、H2-TPR、CO2-TPD表征技术对催化剂进行理化性能测试,并在高温高压微反应器上对催化剂活性进行评价。研究了CO2加氢制甲醇反应中不同沉淀剂对催化剂前体、催化剂母体组分结构以及CuO-ZnO间相互作用的影响。结果表明,不同沉淀剂对催化剂理化性能及催化活性有较大影响。以NaHCO3、Na2CO3为沉淀剂,有利于催化剂前体中形成绿铜锌矿相,经焙烧后,抑制CuO颗粒长大,提高铜的分散度,使表面碱性位浓度增大,CuO-ZnO间相互作用增强,最终提高催化剂活性。其中,以NaHCO3为沉淀剂,有利于催化剂前体形成更多的绿铜锌矿相,焙烧过程产生更多的铜锌固溶体,促使形成强的CuO-ZnO相互作用,形成的CuO颗粒粒径为8.6nm,铜的比表面积为15.38m2/g,铜分散度为11.9%,甲醇的选择性和收率分别为42.29%和0.094g/(gcat·h),催化剂活性最好。

关键词: 沉淀剂, 二氧化碳, 催化剂, 加氢, 甲醇

CLC Number: 

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