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 (3): 97-101.doi: 10.11962/1006-4990.2020-0419

• 催化材料 • 上一篇    下一篇

甲苯甲醇烷基化制对二甲苯催化剂中试反应性能研究

李孝国(),李永恒,侯章贵,韩国栋,肖家旺,郜金平,常洋   

  1. 中海油炼油化工科学研究院,北京 102209
  • 收稿日期:2020-09-11 出版日期:2021-03-10 发布日期:2021-03-11
  • 作者简介:李孝国(1978— ),男,硕士,高级工程师,主要从事石油化工催化技术研究;E-mail:lixg18@cnooc.com.cn
  • 基金资助:
    中国海油石油集团有限公司课题(CNOOC-KJ 135 FZDXM 00 LH 002 YJY-2017)

Study on pilot catalytic performance of the modified catalyst for alkylation of toluene with methanol to p-xylene

Li Xiaoguo(),Li Yongheng,Hou Zhanggui,Han Guodong,Xiao Jiawang,Gao Jinping,Chang Yang   

  1. CNOOC Research Institute of Refining and Petrochemicals,Beijing 102209,China
  • Received:2020-09-11 Online:2021-03-10 Published:2021-03-11

摘要:

经过多步改性制备了负载二氧化硅(SiO2)、氧化镁(MgO)、五氧化二磷(P2O5)、贵金属铂(Pt)的纳米ZSM-5分子筛催化剂,并在六段固定床反应器上分段装填该催化剂720 g进行甲苯、甲醇烷基化制对二甲苯反应活性评价。实验结果表明,通过调变甲醇和甲苯物质的量比可以使甲苯转化率在22%~30%可调,烷基化液相产物中二甲苯选择性保持在95%以上,二甲苯中对二甲苯选择性保持在95%以上;催化剂单程寿命达到1 300 h,随着反应时间延长催化剂的活性有所下降。通过X射线衍射(XRD)、热重分析(TG-DTG)和氮气吸附-脱附等手段对参加反应前后的催化剂进行了表征,结果表明反应中生成的积炭堵塞了分子筛的孔道或覆盖了催化剂的活性位;经过在反应器内原位再生,催化剂的反应活性基本恢复到新鲜催化剂水平。

关键词: ZSM-5分子筛, 甲苯甲醇烷基化, 对二甲苯, 原位再生

Abstract:

A composite-modified nano ZSM-5 zeolite catalyst was prepared through multi-step impregnation with the precur-sor of SiO2,MgO,P2O5 and Pt.The catalytic performance for alkylation of toluene with methanol was investigated in a six-stage fixed bed reactor,which is filled with more than 720 g of the catalyst.The result shows that the conversion rate of toluene was controllably adjusted in the range of 22%~30% by adjusting the amount-of-substance ratio of toluene to methanol,as well as the selectivity to xylene in liquid products of alkylation and selectivity to p-xylene in xylene(o-xylene,m-xylene and p-xylene) both simultaneously stabilized above 95%.The life of the catalyst reaches 1 300 h in alkylation reaction and the catalytic activity decreased after 1 200 h.The fresh and deactivated catalysts were characterized by XRD,TG-DTG and N2 adsorption-desorption.It is indicated that the generated coke blocked the pores of ZSM-5 zeolite or deposited on the active sites of catalyst,leading to the catalytic deactivation.The catalytic activity of deactivated catalyst almost can be restored after in-situ regeneration.

Key words: ZSM-5 zeolite, alkylation of toluene with methanol, p-xylene, in-situ regeneration

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