再生时间对甲醇制烯烃催化剂水蒸气再生过程的影响

doi:10.16085/j.issn.1000-6613.2021-0222

化工进展 ›› 2022, Vol. 41 ›› Issue (1): 221-226.DOI: 10.16085/j.issn.1000-6613.2021-0222

再生时间对甲醇制烯烃催化剂水蒸气再生过程的影响

安怀清¹^,²(), 周吉彬¹, 张今令¹, 张涛¹, 叶茂¹(), 刘中民¹^,²

^1.中国科学院大连化学物理研究所甲醇制烯烃国家工程实验室，辽宁大连 116023
^2.中国科学院大学，北京 100049

收稿日期:2021-01-31 修回日期:2021-03-08 出版日期:2022-01-05 发布日期:2022-01-24
通讯作者: 叶茂
作者简介:安怀清（1994—），女，硕士研究生，研究方向为甲醇制烯烃水蒸气再生。E-mail：anhuaiqing@dicp.ac.cn。
基金资助:
国家自然科学基金(91834302)

Effect of regeneration time on steam regeneration of spent catalyst in methanol to olefins process

AN Huaiqing¹^,²(), ZHOU Jibin¹, ZHANG Jinling¹, ZHANG Tao¹, YE Mao¹(), LIU Zhongmin¹^,²

^1.National Engineering Laboratory for Methanol to Olefins, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^2.University of Chinese Academy of Sciences, Beijing 100049, China

Received:2021-01-31 Revised:2021-03-08 Online:2022-01-05 Published:2022-01-24
Contact: YE Mao

摘要/Abstract

摘要：

对甲醇制烯烃（MTO）过程失活催化剂采用水蒸气再生不仅可以减少二氧化碳排放，而且能提高低碳烯烃选择性，具有很好的应用前景。本文针对工业MTO过程使用的SAPO-34分子筛催化剂，研究了再生时间对水蒸气再生过程的影响。采用XRD、NH₃-TPD、TGA、FTIR、GC-MS以及N₂物理吸脱附表征手段对再生催化剂样品的晶体结构、酸性、残炭性质以及结构参数进行了表征，并考察再生催化剂的MTO反应性能。结果表明，再生时间越长，再生催化剂上残炭量越低，其酸性、比表面积和孔结构等能较好地恢复，在MTO反应中表现出更长的催化寿命。在再生过程中，催化剂上的残炭物种由芘、菲等大分子量的有机物转变为对MTO具有反应活性的萘等小分子有机物；但是可溶性残炭物种随着再生时间的延长而减少，从而使得初始低碳烯烃选择性有所降低。

关键词: 甲醇制烯烃, SAPO-34催化剂, 失活催化剂, 水蒸气再生

Abstract:

The SAPO-34 zeolite catalyzed methanol to olefins (MTO) process has been shown of practical significance. Recent study has demonstrated that steam regeneration is superior to air combustion in terms of CO₂emission reduction and light olefins selectivity enhancement. In this work we investigated the effect of regeneration time on the steam regeneration of spent catalyst used in MTO process. The crystal structure, acidity, residual coke properties and structural parameters of the catalyst samples regenerated under different regeneration time were characterized by XRD, NH₃-TPD, FTIR, TGA, GC-MS and N₂ physical adsorption-desorption. The results showed that the increase of regeneration time would reduce the amount of residual coke on the regenerated catalyst, and yield better recovery of the acidity, BET surface area and pore structure of the catalyst samples, which could prolong catalyst's lifetime. Furthermore, it is shown that the residual coke species on the catalyst changed from pyrene and phenanthrene to naphthalene during the steam regeneration. However, the soluble residual coke species decreased with the extension of regeneration time, which would reduce the selectivity of light olefins at the beginning of MTO reaction.

Key words: methanol to olefins, SAPO-34 catalyst, deactivated catalyst, steam regeneration

中图分类号:

TQ546.2

安怀清, 周吉彬, 张今令, 张涛, 叶茂, 刘中民. 再生时间对甲醇制烯烃催化剂水蒸气再生过程的影响[J]. 化工进展, 2022, 41(1): 221-226.

AN Huaiqing, ZHOU Jibin, ZHANG Jinling, ZHANG Tao, YE Mao, LIU Zhongmin. Effect of regeneration time on steam regeneration of spent catalyst in methanol to olefins process[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 221-226.

图/表 11

图1 不同再生时间再生后SAPO-34催化剂的XRD图

表1 不同再生时间水蒸气再生之后SAPO-34样品残留积炭质量分数

再生催化剂	残炭质量分数/%
SAPO-34-Spent	12.96
SAPO-34-SG-10min	11.02
SAPO-34-SG-30min	9.03
SAPO-34-SG-60min	6.75
SAPO-34-SG-90min	5.08
SAPO-34-SG-180min	2.68

图2 不同再生时间再生后SAPO-34催化剂溶碳结果

图3 不同再生时间再生之后SAPO-34催化剂GC-MS结果

图4 不同再生时间再生后SAPO-34催化剂的NH3-TPD结果

表2 不同再生时间水蒸气再生之后SAPO-34样品上酸量值

催化剂	NH₃-TPD酸量值（STP）/cm³·g^-1
催化剂	总量	周量	强酸
SAPO-34-Spent	4.02	4.02	—
SAPO-34-SG-10min	5.69	5.69	—
SAPO-34-SG-30min	6.73	3.64	3.09
SAPO-34-SG-60min	8.74	3.70	5.04
SAPO-34-SG-90min	10.73	4.48	6.25
SAPO-34-SG-180min	13.94	5.89	8.05

图5 不同再生时间再生后SAPO-34催化剂FTIR结果

图6 不同再生时间再生后SAPO-34催化剂N2物理吸附/脱附结果

表3 不同再生时间水蒸气再生之后SAPO-34催化剂BET和孔体积

催化剂	S_BET/m²·g^-1	S_micro/m²·g^-1	V_micro/cm³·g^-1
SAPO-34-Spent	42.6	—	—
SAPO-34-SG-10min	45.9	2.6	0.0007
SAPO-34-SG-30min	148.0	92.7	0.043
SAPO-34-SG-60min	205.8	154.1	0.076
SAPO-34-SG-90min	241.3	191.9	0.094
SAPO-34-SG-180min	305.9	258.5	0.121

图7 不同再生时间再生之后催化剂MTO反应结果

图8 初始低碳烯烃选择性和催化剂寿命随再生时间的变化

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再生时间对甲醇制烯烃催化剂水蒸气再生过程的影响

Effect of regeneration time on steam regeneration of spent catalyst in methanol to olefins process

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