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
催化材料

金属改性甲醇芳构化催化剂的制备及性能研究

  • 彭晓伟 ,
  • 王银斌 ,
  • 臧甲忠 ,
  • 于海斌
展开
  • 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
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

收稿日期: 2020-11-09

  网络出版日期: 2021-09-08

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

  • Xiaowei Peng ,
  • Yinbin Wang ,
  • Jiazhong Zang ,
  • Haibin Yu
Expand
  • 1. CenerTech Tianjin Chemical Research and Design Institute Co.,Ltd.,Tianjin 300131,China
    2. Tianjin Refining and Catalytic Technology Engineering Center

Received date: 2020-11-09

  Online published: 2021-09-08

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。

本文引用格式

彭晓伟 , 王银斌 , 臧甲忠 , 于海斌 . 金属改性甲醇芳构化催化剂的制备及性能研究[J]. 无机盐工业, 2021 , 53(9) : 104 -108 . DOI: 10.19964/j.issn.1006-4990.2020-0599

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.

参考文献

[1] 中国石油和化学工业联合会. 中国石化市场预警报告(2020)[M]. 北京: 化学工业出版社,2020.
[2] 贾曌, 孟宪玲. 煤制芳烃产业化进展及制约因素分析[J]. 当代石油石化, 2018, 26(11):38-42.
[3] 黄格省, 包力庆, 丁文娟, 等. 我国煤制芳烃技术发展现状及产业前景分析[J]. 煤炭加工与综合利用, 2018(2):6-10.
[4] 王银斌, 臧甲忠, 于海斌, 等. 甲醇制汽油技术进展及相关问题探讨[J]. 煤化工, 2011, 39(3):16-19.
[5] 何静宇. HZSM-5催化剂上甲醇芳构化研究[D]. 北京:北京化工大学, 2014.
[6] 贺永德. 现代煤化工技术手册[M]. 北京: 化学工业出版社, 2020.
[7] 徐振刚. 中国现代煤化工近25年发展回顾·反思·展望[J]. 煤炭科学技术, 2020, 48(8):1-25.
[8] 崔滕. 锌改性ZSM-5分子筛催化甲醇制芳烃[D]. 大连:大连理工大学, 2019.
[9] Pinilla Herrero I, Borfecchia E, Cordero Lanzac Tomas, et al. Finding the active species:The conversion of methanol to aromatics over Zn-ZSM-5/alumina shaped catalysts[J]. Journal of Catalysis, 2021, 394:416-428.
[10] 贾艳明. HZSM-5分子筛基催化剂的制备及其催化甲醇制芳烃反应性能研究[D]. 太原:太原理工大学, 2018.
[11] 忻睦迪, 邢恩会, 欧阳颖, 等. Zn/ZSM-5中Zn的赋存状态对其催化性能的影响[J]. 石油炼制与化工, 2019, 50(12):42-50.
[12] 曾昭槐. 择形催化[M]. 北京: 中国石化出版社, 1994.
[13] Ji H, Zhang Q, Wang B, et al. Synergistic effect of nickel species and γ-alumina added to HZSM-5 on the methanol to aromatics[J]. Catalysis Letters, 2014, 144(11):1860-1867.
[14] Jeongnam Kim, Minkee Choi, Ryong Ryoo. Effect of mesoporosity against the deactivation of MFI zeolite catalyst during the methanol-to-hydrocarbon conversion process[J]. Journal of Catalysis, 2010, 269:219-228.
[15] 佟鑫. 多级孔ZSM-5分子筛的制备及应用[D]. 上海:华东理工大学, 2018.
文章导航

/