介孔结构和助剂Zn对不同晶粒大小ZSM-5催化甲醇制芳烃反应性能的影响

doi:10.16085/j.issn.1000-6613.2018-1153

化工进展 ›› 2019, Vol. 38 ›› Issue (04): 1758-1767.DOI: 10.16085/j.issn.1000-6613.2018-1153

介孔结构和助剂Zn对不同晶粒大小ZSM-5催化甲醇制芳烃反应性能的影响

张春梅(),付廷俊(),邵娟,马哲,王玉杰,马倩,崔丽萍,李忠()

太原理工大学煤科学与技术教育部和山西省重点实验室，山西太原 030024

收稿日期:2018-06-01 修回日期:2018-09-20 出版日期:2019-04-05 发布日期:2019-04-05
通讯作者: 付廷俊,李忠
作者简介:张春梅（1993—），女，硕士研究生，研究方向为碳一化学。E-mail：<email>1007331442@qq.com</email>。|付廷俊，副教授，硕士生导师，研究方向为碳一化学。E-mail：<email>futingjun@tyut.edu.cn</email>|李忠，教授，博士生导师，研究方向为碳一化学。E-mail：<email>lizhong@tyut.edu.cn</email>
基金资助:
国家重点研发计划(2018YFB0604901);国家自然科学基金(21606160，21878207);山西省自然科学基金(201701D221039，201701D121025)

Effects of mesoporous structure and Zn promoter on methanol to aromatics performance over different crystal sized ZSM-5 catalysts

Chunmei ZHANG(),Tingjun FU(),Juan SHAO,Zhe MA,Yujie WANG,Qian MA,Liping CUI,Zhong LI()

Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2018-06-01 Revised:2018-09-20 Online:2019-04-05 Published:2019-04-05
Contact: Tingjun FU,Zhong LI

摘要/Abstract

摘要：

通过碱处理和添加助剂Zn对微米ZSM-5和纳米ZSM-5进行改性，获得具有不同孔结构和酸性质的催化剂。采用氮气吸附、X射线衍射、透射电镜、氨气程序升温脱附（NH₃-TPD）和热重（TG）技术对不同催化剂进行表征，结合催化性能评价，考察晶粒尺寸、介孔结构和Zn助剂对其催化甲醇制芳烃（MTA）反应性能的影响。结果表明，碱处理引入介孔后，孔体积均增大，总酸量都降低；微米催化剂外表面积显著增加，但纳米催化剂外表面积却有所下降；负载金属Zn后，比表面积、结晶度和总酸量都降低。在P=0.5MPa、T=430℃、WHSV=2h^-1的反应条件下，负载Zn的微米催化剂由于具有较高的酸量，其芳烃与苯、甲苯和二甲苯（BTX）选择性最高，分别为85.11%和66.85%，但是稳定性较差，催化寿命仅为12h。但相较于未改性的纳米ZSM-5原粉来说，碱处理后又负载Zn的催化剂，液烃中芳烃选择性从纳米原粉的65.20%增加到80.82%，BTX选择性从纳米原粉的42.30%提高到49.56%，而在甲醇进样量增加4倍，即WHSV=8h^-1时，催化剂仍显示出较好的稳定性，寿命可达84h。可见，在小晶粒ZSM-5上碱处理扩孔并引入Zn助剂可以有效提高甲醇制芳烃反应性能。

关键词: 甲醇, 芳烃, ZSM-5, 碱处理, 助剂

Abstract:

ZSM-5 catalysts with different pore structures and acidities were modified by alkali treatment and Zn introduction. The obtained catalysts were characterized by N₂ adsorption, XRD, TEM, NH₃-TPD and TG techniques, and the influences of crystal size, mesoporous structure and Zn metal additive on the catalytic performance of ZSM-5 for conversion of methanol to aromatics (MTA) were investigated in addition to the catalyst evaluation. The results indicated that after the formation of mesopore via alkali treatment, the pore volume of the catalysts increased, and the total acid amount decreased. The external surface area of the micro-ZSM-5 increased significantly but that of the nano-ZSM-5 decreased after alkali treatment. The surface area, crystallinity and total acid amount of ZSM-5 were decreased after the introduction of Zn species. MTA reaction was carried out in a fixed-bed reactor at 430℃ and WHSV of 2h^-1 under 0.5MPa and the Zn-loaded micron catalyst exhibited high acid amount, high aromatic selectivity of 85.11% and BTX selectivity of 66.85% in liquid hydrocarbons, but a short catalytic lifetime of only 12 hours. Compared with the unmodified nano-ZSM-5, the Zn-promoted mesoporous nano-ZSM-5 increased the aromatic selectivity from 65.20% to 80.82%, and the BTX value from 42.30% to 49.56%. The catalyst still displayed good catalytic stability when space velocity was up to 8h^-1 and the catalytic lifetime could reach 84h. This work demonstrated that mesopore fabricating of nano-ZSM-5 catalyst by alkali treatment and then introducing Zn could effectively improve its MTA performance.

Key words: methanol, aromatics, ZSM-5, alkaline treatment, additive

中图分类号:

O643.3

张春梅, 付廷俊, 邵娟, 马哲, 王玉杰, 马倩, 崔丽萍, 李忠. 介孔结构和助剂Zn对不同晶粒大小ZSM-5催化甲醇制芳烃反应性能的影响[J]. 化工进展, 2019, 38(04): 1758-1767.

Chunmei ZHANG, Tingjun FU, Juan SHAO, Zhe MA, Yujie WANG, Qian MA, Liping CUI, Zhong LI. Effects of mesoporous structure and Zn promoter on methanol to aromatics performance over different crystal sized ZSM-5 catalysts[J]. Chemical Industry and Engineering Progress, 2019, 38(04): 1758-1767.

图/表 14

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催化剂	S _BET ^① /m²·g^-1	S _mic ^② /m²·g^-1	S _ext ^② /m²·g^-1	V _total ^③ /cm³·g^-1	V _mic ^② /cm³·g^-1	V _meso ^④ /cm³·g^-1
MZ	350	302	48	0.21	0.12	0.09
MZ-AT	355	176	179	0.50	0.09	0.41
Zn/MZ	318	271	47	0.23	0.12	0.11
Zn/MZ-AT	332	165	167	0.45	0.08	0.37
NZ	402	282	120	0.51	0.13	0.38
NZ-AT	377	271	106	0.60	0.13	0.47
Zn/NZ	365	239	126	0.59	0.12	0.47
Zn/NZ-AT	349	240	109	0.62	0.12	0.50

催化剂	S _BET ^① /m²·g^-1	S _mic ^② /m²·g^-1	S _ext ^② /m²·g^-1	V _total ^③ /cm³·g^-1	V _mic ^② /cm³·g^-1	V _meso ^④ /cm³·g^-1
MZ	350	302	48	0.21	0.12	0.09
MZ-AT	355	176	179	0.50	0.09	0.41
Zn/MZ	318	271	47	0.23	0.12	0.11
Zn/MZ-AT	332	165	167	0.45	0.08	0.37
NZ	402	282	120	0.51	0.13	0.38
NZ-AT	377	271	106	0.60	0.13	0.47
Zn/NZ	365	239	126	0.59	0.12	0.47
Zn/NZ-AT	349	240	109	0.62	0.12	0.50

催化剂	酸量^①/mmol·g^-1
催化剂	总量	弱酸	中强酸	强酸
MZ	1.21	0.48	0.26	0.47
MZ-AT	0.91	0.41	0.28	0.22
Zn/MZ	0.92	0.37	0.24	0.31
Zn/MZ-AT	0.85	0.35	0.34	0.16
NZ	0.76	0.24	0.19	0.33
NZ-AT	0.74	0.24	0.19	0.31
Zn/NZ	0.66	0.25	0.22	0.19
Zn/NZ-AT	0.61	0.23	0.21	0.17

催化剂	酸量^①/mmol·g^-1
催化剂	总量	弱酸	中强酸	强酸
MZ	1.21	0.48	0.26	0.47
MZ-AT	0.91	0.41	0.28	0.22
Zn/MZ	0.92	0.37	0.24	0.31
Zn/MZ-AT	0.85	0.35	0.34	0.16
NZ	0.76	0.24	0.19	0.33
NZ-AT	0.74	0.24	0.19	0.31
Zn/NZ	0.66	0.25	0.22	0.19
Zn/NZ-AT	0.61	0.23	0.21	0.17

催化剂	液烃			积炭容量 /g·g^-1 _cat	积炭速率 /g·g^-1·h^-1
催化剂	液烃产能 /g·g^-1 _cat	最高液烃收率 /%	寿命 /h	积炭容量 /g·g^-1 _cat	积炭速率 /g·g^-1·h^-1
MZ	6.2	19.8	20	0.11	5.3×10^-3
MZ-AT	62.8	24.0	96	0.35	3.6×10^-3
Zn/MZ	1.9	15.6	12	0.07	6.0×10^-3
Zn/MZ-AT	52.0	24.3	84	0.29	3.4×10^-3
NZ	237.4	28.9	149	0.32	2.2×10^-3
NZ-AT	197.2	28.7	132	0.29	2.2×10^-3
Zn/NZ	65.7	25.4	70	0.22	3.1×10^-3
Zn/NZ-AT	93.7	28.0	84	0.28	3.3×10^-3

介孔结构和助剂Zn对不同晶粒大小ZSM-5催化甲醇制芳烃反应性能的影响

Effects of mesoporous structure and Zn promoter on methanol to aromatics performance over different crystal sized ZSM-5 catalysts

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参考文献 39

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催化剂	S _BET ^① /m²·g^-1	S _mic ^② /m²·g^-1	S _ext ^② /m²·g^-1	V _total ^③ /cm³·g^-1	V _mic ^② /cm³·g^-1	V _meso ^④ /cm³·g^-1
MZ	14	0	14	0.06	0	0.06
MZ-AT	48	6	42	0.14	0	0.14
Zn/MZ	4	0	4	0.05	0	0.05
Zn/MZ-AT	24	0	24	0.09	0	0.09
NZ	189	119	70	0.37	0.05	0.32
NZ-AT	199	129	70	0.40	0.06	0.34
Zn/NZ	180	112	68	0.37	0.05	0.32
Zn/NZ-AT	145	79	66	0.34	0.06	0.28

催化剂	苯/%	甲苯/%	二甲苯/%	BTX/%
MZ	3.12	18.43	36.06	57.61
MZ-AT	2.02	12.71	25.49	40.22
Zn/MZ	3.32	25.75	37.78	66.85
Zn/MZ-AT	2.01	17.81	28.81	48.63
NZ	2.66	14.68	24.96	42.30
NZ-AT	2.46	14.25	24.30	41.01
Zn/NZ	2.16	18.53	30.18	50.87
Zn/NZ-AT	2.10	18.00	29.46	49.56

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