煤气化渣合成ZSM-5分子筛及其甲醇制芳烃性能

doi:10.15541/jim20260049

摘要/Abstract

摘要：

煤气化渣(CGS)富含硅铝物种, 是分子筛制备的潜在大宗原料, 但CGS中硅铝物种的传统活化方法存在能耗高、污染大、成本高等问题。本研究采用亚熔盐法低温活化CGS, 然后采用水热法合成ZSM-5分子筛, 并考察其甲醇制芳烃(MTA)性能。结果表明, 亚熔盐活化CGS合成ZSM-5分子筛较为适宜的活化条件为CGS/NaOH质量比1 : 1.2、碱浓度6.10 mol/L、活化时间3 h、活化温度200 ℃; 活化CGS合成ZSM-5分子筛较为适宜的晶化条件为合成体系pH 11、晶化温度160 ℃、晶化时间72 h、四丙基溴化铵(TPABr)/SiO₂摩尔比0.10, 在上述条件下合成的ZSM-5分子筛结晶度良好、骨架完整、形貌较为规整。合成的ZSM-5分子筛经离子交换和等体积浸渍后, 制得Zn/H-ZSM-5催化剂, MTA性能评价结果表明, Zn/H-ZSM-5催化剂在反应温度400~500 ℃和质量空速5~20 h^-1范围内甲醇转化率均达100%; 随着反应温度的逐渐升高, 芳烃的选择性先增加后降低; 随着质量空速的逐渐升高, 芳烃的选择性逐渐降低。反应温度450 ℃、质量空速5 h^-1时, Zn/H-ZSM-5催化剂展现出良好的MTA性能, 此时甲醇转化率达100%, 芳烃选择性为45.0%。本研究可为CGS绿色高效合成分子筛提供新途径。

关键词: 煤气化渣, ZSM-5分子筛, 亚熔盐活化, 催化剂, 甲醇制芳烃

Abstract:

Coal gasification slag (CGS), rich in silicon and aluminum species, represents a potential raw material for the preparation of molecular sieves. However, the traditional activation method of silicon and aluminum species in CGS has the problems of high energy consumption, significant pollution and substantial cost. In this study, CGS was activated by sub-molten salt method at low temperature, and then ZSM-5 molecular sieve was synthesized by hydrothermal method with activated CGS as raw material, and its methanol to aromatics (MTA) performance was evaluated. The results showed that the suitable activation conditions for the synthesis of ZSM-5 zeolite by CGS activated by sub-molten salt were as follows: CGS/NaOH mass ratio of 1 : 1.2, alkali concentration of 6.10 mol/L, activation time of 3 h, and activation temperature of 200 ℃. The suitable crystallization conditions for the synthesis of ZSM-5 molecular sieve by activating CGS are as follows: the synthesis system of pH 11, crystallization temperature of 160 ℃, crystallization time of 72 h, and molar ratio of tetrapropyl ammonium bromide (TPABr)/SiO₂ of 0.10. The ZSM-5 molecular sieve synthesized has good crystallinity, complete skeleton and regular morphology. The Zn/H-ZSM-5 catalyst was prepared by ion exchange and equal volume impregnation of the synthesized ZSM-5 zeolite. The results of MTA performance evaluation showed that the methanol conversion of Zn/H-ZSM-5 catalyst reached 100% in the range of 400-500 ℃ and 5-10 h^-1. With the increase of reaction temperature, the selectivity of aromatics increased firstly and then decreased. With the increase of weight hourly space velocity, the selectivity of aromatics gradually decreased. The reaction temperature of 450 ℃ and the weight hourly space velocity of 5 h^-1 are the suitable conditions for MTA reaction on Zn/H-ZSM-5 catalyst. At this time, the methanol conversion rate reached 100% and the aromatics selectivity was 45.0%, showing good MTA performance and application potential. This study can provide a new pathway for the green and efficient synthesis of molecular sieves using CGS.

Key words: coal gasification slag, ZSM-5 molecular sieve, sub-molten salt activation, catalyst, methanol to aromatic

中图分类号:

TQ426

陈治平, 段振洋, 于皓山, 周文武, 杨志远, 周安宁. 煤气化渣合成ZSM-5分子筛及其甲醇制芳烃性能[J]. 无机材料学报, 2026, 41(10): 1507-1516.

CHEN Zhiping, DUAN Zhenyang, YU Haoshan, ZHOU Wenwu, YANG Zhiyuan, ZHOU Anning. ZSM-5 Molecular Sieves: Preparation from Coal Gasification Slag and Performance in Methanol to Aromatics[J]. Journal of Inorganic Materials, 2026, 41(10): 1507-1516.

图/表 21

参考文献 42

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Sample	S_BET/(m²·g^-1)	S_Micro/(m²·g^-1)	S_Meso/(m²·g^-1)	V_total/(cm³·g^-1)
CGS	36	7	29	0.04
A-CGS	8	1	7	0.01
ZSM-5	193	118	75	0.15

Sample	S_BET/(m²·g^-1)	S_Micro/(m²·g^-1)	S_Meso/(m²·g^-1)	V_total/(cm³·g^-1)
CGS	36	7	29	0.04
A-CGS	8	1	7	0.01
ZSM-5	193	118	75	0.15

T/℃	Sample	Acid amount/(μmol·g^-1)
T/℃	Sample	B	L	B+L	B/L
150	ZSM-5	224.95	71.09	296.04	3.16
150	Zn/H-ZSM-5	128.24	458.48	586.72	0.28
250	ZSM-5	208.82	34.14	242.96	6.12
250	Zn/H-ZSM-5	111.48	314.49	425.97	0.35
350	ZSM-5	197.50	28.35	225.85	6.97
350	Zn/H-ZSM-5	66.72	192.85	259.58	0.35

T/℃	Sample	Acid amount/(μmol·g^-1)
T/℃	Sample	B	L	B+L	B/L
150	ZSM-5	224.95	71.09	296.04	3.16
150	Zn/H-ZSM-5	128.24	458.48	586.72	0.28
250	ZSM-5	208.82	34.14	242.96	6.12
250	Zn/H-ZSM-5	111.48	314.49	425.97	0.35
350	ZSM-5	197.50	28.35	225.85	6.97
350	Zn/H-ZSM-5	66.72	192.85	259.58	0.35

Alkane/%	Alkene/%	Aromatic/%	BTX/%	Catalyst	Reaction condition	Ref.
17.8	33.0	45.0	31.4	Zn/H-ZSM-5	0.1 MPa, 450 ℃, 5 h^-1	This work
36.8	33.7	23.1	19.0	Zn/ZSM-5	0.1 MPa, 450 ℃, 10 h^-1	[35]
-	-	59.1	34.6	Zn-Z5-2	0.1 MPa, 440 ℃, 1 h^-1	[41]
13.9	50.6	26.9	13.3	ZSM-5-5%	0.1 MPa, 450 ℃, 2 h^-1	[42]