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 ›› 2021, Vol. 53 ›› Issue (9): 104-108.doi: 10.19964/j.issn.1006-4990.2020-0599

• 催化材料 • 上一篇    下一篇

金属改性甲醇芳构化催化剂的制备及性能研究

彭晓伟1,2(),王银斌1,2,臧甲忠1,2,于海斌1,2()   

  1. 1.中海油天津化工研究设计院有限公司,天津 300131
    2.天津市炼化催化工程技术中心
  • 收稿日期:2020-11-09 出版日期:2021-09-10 发布日期:2021-09-08
  • 通讯作者: 于海斌
  • 作者简介:彭晓伟(1990— ),男,助理工程师,从事化工催化材料及工艺技术的开发与应用;E-mail: mervin666@163.com
  • 基金资助:
    中国海洋石油集团有限公司项目(CNOOC-KJ 125 ZDXM 26 TJY 04 TJY 2013-04)

Research on preparation of metal modified catalysts and catalytic performances of methanol aromatization

Peng Xiaowei1,2(),Wang Yinbin1,2,Zang Jiazhong1,2,Yu Haibin1,2()   

  1. 1. CenerTech Tianjin Chemical Research and Design Institute Co.,Ltd.,Tianjin 300131,China
    2. Tianjin Refining and Catalytic Technology Engineering Center
  • Received:2020-11-09 Online:2021-09-10 Published:2021-09-08
  • Contact: Yu Haibin

摘要:

甲醇制芳烃是中国煤基甲醇深加工技术的重点发展方向之一,目前甲醇芳构化催化剂存在芳烃选择性低、收率低等问题。鉴于此,采用等体积浸渍法制备了一系列氧化锌、氧化镍复合改性催化剂,通过X射线荧光光谱(XRF)、氮气物理吸-脱附以及氨的程序升温脱附(NH3-TPD)等方法对催化剂进行表征分析,通过固定床小试评价装置对催化剂的甲醇芳构化反应性能进行考察,并通过300 t/a固定床中试评价装置对优选催化剂的反应稳定性进行考察。小试实验结果表明,当氧化锌与氧化镍负载比例为2.0(质量比)、负载总量为6.2%(质量分数)时,催化剂具有最佳的甲醇芳构化性能,芳烃选择性为62.98%、收率为19.46%。中试实验结果表明,180 h内甲醇转化率保持100%、芳烃选择性不低于73%、芳烃收率不低于32%。以中国丰富的甲醇资源为原料,生产中国短缺的芳烃产品,一方面可以完善煤化工产业链、优化产品结构,另一方面可以缓解中国石油基芳烃供应不足的局势。

关键词: 氧化锌改性, 氧化镍改性, 甲醇芳构化, 苯/甲苯/二甲苯(BTX)

Abstract:

Aromatization is one of the key development directions of processing technology of coal based methanol in China. At present,the aromatics selectivity and yield of methanol-to-aromatics catalysts are relatively low. In view of this,a series of modified ZnO and NiO catalysts were prepared by an incipient-wetness impregnation method,then these catalysts were char-acterized by X-ray fluorescence spectrum(XRF),physical adsorption desorption of nitrogen and temperature programmed desorption of ammonia(NH3-TPD),and were systematically investigated in a fixed bed reactor to discover the influence of the ratio and loading of bimetal on the reaction performance.A 300 t/a fixed-bed pilot plant was used to investigate the reaction performance of the best catalyst.The small scale experiment results showed that when the ratio of ZnO and NiO(mass ratio) was 2.0 and the total loading(mass fraction) was 6.2%,the catalyst achieved the best synergistic effect,while the aromatics selectivity was 62.98% and the aromatics yield was 19.46%.The medium scale experiment results showed that the methanol conversion rate remained 100% within 180 h,while the aromatics selectivity remained above 73% and the aromatics yield was higher than 32%.Using domestic abundant methanol in China as raw material to produce domestic shortage of aromatics,on the one hand,it can improve the industrial chain and optimize the product structure of coal chemical industry,on the other hand,it can alleviate the shortage of petroleum based aromatics.

Key words: modified ZnO, modified NiO, methanol aromatization, benzene/toluene/xylene BTX

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