无机盐工业
主管:中海油天津化工研究设计院有限公司
主办:中海油天津化工研究设计院有限公司
   中海油炼油化工科学研究院(北京)有限公司
   中国化工学会无机酸碱盐专业委员会
ISSN 1006-4990 CN 12-1069/TQ

无机盐工业 ›› 2023, Vol. 55 ›› Issue (9): 140-144.doi: 10.19964/j.issn.1006-4990.2022-0710

• 催化材料 • 上一篇    

碱土金属对铜/三氧化二铝酯加氢催化剂性能的影响

刘伟(), 许岩, 陈永生, 孙春晖, 张景成, 朱金剑, 刘洋   

  1. 中海油天津化工研究设计院有限公司,天津 300131
  • 收稿日期:2022-12-05 出版日期:2023-09-10 发布日期:2023-09-19
  • 作者简介:刘伟(1982— ),女,硕士,高级工程师,主要从事加氢催化剂的制备及应用研究;E-mail:weiwei_198201@sina.com

Effect of alkaline earth metals on performance of Cu/Al2O3 ester hydrogenation catalyst

LIU Wei(), XU Yan, CHEN Yongsheng, SUN Chunhui, ZHANG Jingcheng, ZHU Jinjian, LIU Yang   

  1. CenerTech Tianjin Chemical Research and Design Institute Co. ,Ltd. ,Tianjin 300131,China
  • Received:2022-12-05 Published:2023-09-10 Online:2023-09-19

摘要:

采用超声波强化共沉淀法制备铜/三氧化二铝酯加氢催化剂,制备过程中添加碱土金属硝酸盐对催化剂进行改性。通过丁二酸二甲酯加氢反应对催化剂性能进行评价,考察碱土金属种类及添加量对催化剂加氢性能的影响。通过X射线衍射(XRD)、程序升温还原(H2-TPR)、氨程序升温脱附(NH3-TPD)、N2物理吸附对催化剂进行分析表征,考察钙添加量对催化剂晶型结构、还原性能、酸强度、BET比表面积和孔结构的影响。结果表明,碱土金属改性可以提高催化剂加氢性能,在温度为160 ℃、压力为6.0 MPa、原料质量空速为0.6 h-1、氢酯物质的量比为300工艺条件下,丁二酸二甲酯转化率可达到99.46%、1,4-丁二醇选择性可达到94.39%。适量添加钙后催化剂中活性组分特征峰变宽、分散度提高;还原温度略有降低;酸强度明显降低;比表面积略有下降、孔容略有增大、孔径明显增大。这些物化性质的改变导致催化剂丁二酸二甲酯加氢性能发生改变。

关键词: 丁二酸二甲酯, 酯加氢催化剂, 1,4-丁二醇, 碱土金属

Abstract:

The Cu/Al2O3 ester hydrogenation catalyst was prepared by ultrasonic enhanced coprecipitation method,and the catalyst was modified by adding alkaline earth metal nitrate.The effect of alkaline earth metals and added percent content on the hydrogenation performance of the catalyst was investigated by hydrogenation of dimethyl bisate.The catalyst was characterized by X-ray diffraction(XRD),temperature-programmed reduction(H2-TPR),temperature-programmed desorption of ammonia(NH3-TPD),surface area and pore structure analysis to research the effects of alkaline earth metal calcium addition on the crystal structure,reduction performance,acid strength,BET specific surface area and pore structure of the catalyst were investigated.The results showed that the alkaline earth metal modification could improve the hydrogenation performance of the catalyst.Under the conditions of temperature of 160 ℃,pressure of 6.0 MPa,space velocity of 0.6 h-1 and the molar ratio of the hydrogen ester material was 300,the conversion rate of dimethyl succinate could reach 99.46%,and the selectivity of 1,4-butanediol could reach 94.39%.After adding an appropriate amount of calcium,the characteristic peaks of the active components in the catalyst became wider and the dispersion was increased.The reduction temperature was slightly decreased.The acid strength was significantly decreased.The surface area was slightly decreased,pore volume was slightly increased,pore size was significantly increased.These changes of physicochemical properties led to the change of hydrogenation performance of dimethyl succinate catalyst.

Key words: dimethyl succinate, ester hydrogenation catalyst, 1,4-butanediol, elkali earth metal

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