CuO-TiO2-ZrO2/HZSM-5催化CO2加氢制二甲醚

引用本文: 王嵩, 毛东森, 郭晓明, 卢冠忠. CuO-TiO₂-ZrO₂/HZSM-5催化CO₂加氢制二甲醚[J]. 物理化学学报, 2011, 27(11): 2651-2658. doi: 10.3866/PKU.WHXB20111018 shu

Citation: WANG Song, MAO Dong-Sen, GUO Xiao-Ming, LU Guan-Zhong. Dimethyl Ether Synthesis from CO₂ Hydrogenation over CuO-TiO₂-ZrO₂/HZSM-5 Catalysts[J]. Acta Physico-Chimica Sinica, 2011, 27(11): 2651-2658. doi: 10.3866/PKU.WHXB20111018 shu

CuO-TiO₂-ZrO₂/HZSM-5催化CO₂加氢制二甲醚

基金项目:
上海市科委(08520513600) (08520513600)

上海市教委重点学科(J51503) (J51503)

上海市优秀青年教师专项基金(yyy10078)资助项目 (yyy10078)

摘要: 采用共沉淀法制备了一系列CuO含量不同(质量分数: 50%-80%)的CuO-TiO₂-ZrO₂复合氧化物, 并利用X射线衍射(XRD)、氮吸附(BET)、程序升温还原(H₂-TPR)、程序升温脱附(H₂/CO₂-TPD)和氧化亚氮(N₂O)反应吸附等多种方法对其进行了表征. 以所制备的CuO-TiO₂-ZrO₂为甲醇合成活性组分与HZSM-5分子筛进行机械混合制成双功能催化剂CuO-TiO₂-ZrO₂/HZSM-5, 在微型固定床流动反应器中, 于250°C、3.0 MPa、H₂/CO₂(体积比2.8)以及空速1500 mL·g^-1·h^-1的条件下, 对其催化CO₂加氢直接合成二甲醚(DME)的性能进行了评价.结果表明: 随着CuO-TiO₂-ZrO₂中CuO含量的增加, CO₂的转化率先逐渐增大, 至70%时达到最大, 之后反而降低. DME的选择性随着催化剂中CuO含量的增加而增加, 至≥70%时基本不变, 故当CuO含量为70%时, DME的收率达到最大值(13.2%). 催化剂上合成含氧化合物(甲醇和DME)的活性与催化剂中金属铜的比表面积之间有较好的对应关系.

关键词:

English

Dimethyl Ether Synthesis from CO₂ Hydrogenation over CuO-TiO₂-ZrO₂/HZSM-5 Catalysts

1.
Research Institute of Applied Catalysis, School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 200235, P. R. China
Received Date: 09 May 2011
Available Online: 27 October 2011
Fund Project:
上海市科委(08520513600)

上海市教委重点学科(J51503)

上海市优秀青年教师专项基金(yyy10078)资助项目

Abstract: A series of CuO-TiO₂-ZrO₂ mixed oxides with different CuO mass fractions (50%-80%) were prepared by co-precipitation and characterized by X-ray diffraction (XRD), N₂ physisorption, temperatureprogrammed reduction of hydrogen (H₂-TPR), temperature-programmed desorption of carbon dioxide (CO₂-TPD) and hydrogen (H₂-TPD), and reactive N₂O adsorption techniques. The prepared CuO-TiO₂-ZrO₂ samples were mixed physically with HZSM-5 zeolite to synthesize dimethyl ether (DME) from CO₂ hydrogenation in a fixed bed reactor at 250°C, 3.0 MPa, gas hourly space velocity (GHSV) of 1500 mL·g^-1· h^-1, and volume ratio of 2.8 for H₂ to CO₂. We found that the conversion of CO₂ increased with an increase in CuO content, reached a maximum at a CuO content of 70% and then decreased. The selectivity of DME increased with an increase in CuO content initially and remained essentially constant when the CuO content was ≥70%. Thus, the yield of DME reached a maximum of 13.2% at 70% CuO content. The productivity of the oxygenated compounds (including methanol and DME) on the CuO-TiO₂-ZrO₂/HZSM-5 catalysts is closely related to the metallic copper surface area.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

CuO-TiO₂-ZrO₂/HZSM-5催化CO₂加氢制二甲醚

English

Dimethyl Ether Synthesis from CO₂ Hydrogenation over CuO-TiO₂-ZrO₂/HZSM-5 Catalysts

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