H-ZSM-5分子筛不同孔道处的酸位在甲醇制烯烃反应中的催化作用

doi:10.1016/S1872-2067(20)63732-9

催化学报 ›› 2021, Vol. 42 ›› Issue (7): 1126-1136.DOI: 10.1016/S1872-2067(20)63732-9

H-ZSM-5分子筛不同孔道处的酸位在甲醇制烯烃反应中的催化作用

王森^a, 李志凯^a, 秦张峰^a^,^*(), 董梅^a, 李俊汾^a, 樊卫斌^a^,^#(), 王建国^a^,^b^,^$()

^a中国科学院山西煤炭化学研究所, 煤转化国家重点实验室, 山西太原030001
^b中国科学院大学, 北京100049

收稿日期:2020-09-14 接受日期:2020-11-10 出版日期:2021-07-18 发布日期:2020-12-10
通讯作者: 秦张峰,樊卫斌,王建国
基金资助:
国家重点研发计划(2018YFB0604802);国家自然科学基金(21991092);国家自然科学基金(21991090);国家自然科学基金(U1910203);国家自然科学基金(21802157);山西省自然科学基金(201901D211581);山西省优秀博士生(BK2018001);煤转化国家重点实验室自主研究项目(2020BWZ004)

Catalytic roles of the acid sites in different pore channels of H-ZSM-5 zeolite for methanol-to-olefins conversion

Sen Wang^a, Zhikai Li^a, Zhangfeng Qin^a^,^*(), Mei Dong^a, Junfen Li^a, Weibin Fan^a^,^#(), Jianguo Wang^a^,^b^,^$()

^aState Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China
^bUniversity of the Chinese Academy of Sciences, Beijing 100049, China

Received:2020-09-14 Accepted:2020-11-10 Online:2021-07-18 Published:2020-12-10
Contact: Zhangfeng Qin,Weibin Fan,Jianguo Wang
About author:^$ Tel: +86-351-4199009; E-mail: iccjgw@sxicc.ac.cn
^# Tel: +86-351-4199009; E-mail: fanwb@sxicc.ac.cn;
^* Tel: +86-351-4046092; Fax: +86-351-4041153; E-mail: qzhf@sxicc.ac.cn;
Supported by:
National Key R&D Program of China(2018YFB0604802);National Natural Science Foundation of China(21991092);National Natural Science Foundation of China(21991090);National Natural Science Foundation of China(U1910203);National Natural Science Foundation of China(21802157);Natural Science Foundation of Shanxi Province of China(201901D211581);Excellent Doctoral Student Award and Subsidy Program of Shanxi Province(BK2018001);Independent Research Project of State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, CAS(2020BWZ004)

摘要/Abstract

摘要：

甲醇制烯烃(MTO)作为一条由煤、天然气和生物质等含碳资源制备重要有机化学品的非石油路线, 近年来备受关注. 作为MTO催化剂, 分子筛的骨架拓扑结构和酸性质对于其催化活性、反应路径和产物分布等具有重要的影响. H-ZSM-5分子筛是一种典型的MTO反应催化剂, 酸位可以分布在MFI拓扑结构的直孔道、正弦孔道和交叉位点处. 虽然目前已普遍认可MTO反应遵循芳烃/烯烃双循环烃池机理, 分子筛的催化性能与其骨架中酸中心的位置相关, 但对于H-ZSM-5分子筛不同孔道位置处的酸中心在甲醇制烯烃反应中的催化作用仍缺乏足够认识.
本文采用密度泛函理论计算和分子动力学模拟方法, 对H-ZSM-5分子筛不同孔道处(包括正弦孔道、直孔道和交叉腔)酸位中心上的MTO反应网络(包括芳烃循环、烯烃循环和芳构化)及甲醇原料和烯烃/芳烃产物的扩散行为进行了比较研究. 结果表明, 与正弦孔道和直孔道相比, 芳烃循环和芳构化反应在交叉腔的酸中心上因具有较低的能垒而更易进行. 相比之下, 在正弦孔道和直孔道中, 多甲基苯的生成受到显著限制, 而烯烃循环却可以在三种酸中心(正弦孔道、直孔道和交叉腔)上以相近的能垒和相似的几率进行. 芳烃循环生成乙烯和丙烯的几率相近, 而烯烃循坏产物以丙烯和较高的烯烃产物为主. 落位于H-ZSM-5交叉腔的酸中心能促进芳烃中间体如多甲基苯的生成, 推动芳烃循环, 提高乙烯选择性, 而正弦孔道和直孔道中的酸中心则能增强烯烃循环, 生成较多的丙烯和较高的烯烃产物. 因此, H-ZSM-5分子筛对MTO的催化性能(包括活性和产物选择性等), 可以通过有目的地调节酸中心在分子筛骨架中的位置分布(即铝落位)而得到有效调变和提升.
本文阐明了H-ZSM-5分子筛酸中心在MTO反应中的催化作用与其骨架中的落位之间的有机联系, 为高效甲醇转化分子筛催化剂的设计和性能提升提供了参考思路.

关键词: 甲醇制烯烃, H-ZSM-5分子筛, 酸位分布, 密度泛函理论计算, 分子动力学模拟

Abstract:

H-ZSM-5 zeolite is a typical catalyst for methanol-to-olefins (MTO) conversion. Although the performance of zeolite catalysts for MTO conversion is related to the actual location of acid sites in the zeolite framework, the catalytic roles of the acid sites in different pore channels of the H-ZSM-5 zeolite are not well understood. In this study, the MTO reaction network, involving the aromatic cycle, alkene cycle, and aromatization process, and also the diffusion behavior of methanol feedstock and olefin and aromatic products at different acid sites in the straight channel, sinusoidal channel, and intersection cavity of H-ZSM-5 zeolite was comparatively investigated using density functional theory calculations and molecular dynamic simulations. The results indicated that the aromatic cycle and aromatization process occurred preferentially at the acid sites in the intersection cavities with a much lower energy barrier than that at the acid sites in the straight and sinusoidal channels. In contrast, the formation of polymethylbenzenes was significantly suppressed at the acid sites in the sinusoidal and straight channels, whereas the alkene cycle can occur at all three types of acid sites with similar energy barriers and probabilities. Consequently, the catalytic performance of H-ZSM-5 zeolite for MTO conversion, including activity and product selectivity, can be regulated properly through the purposive alteration of the acid site distribution, viz., the location of Al in the zeolite framework. This study helps to elucidate the relation between the catalytic performance of different acid sites in the H-ZSM-5 zeolite framework for MTO conversion, which should greatly benefit the design of efficient catalyst for methanol conversion.

Key words: Methanol-to-olefins, H-ZSM-5 zeolite, Acid site distribution, Density functional theory calculation, Molecular dynamic simulation

王森, 李志凯, 秦张峰, 董梅, 李俊汾, 樊卫斌, 王建国. H-ZSM-5分子筛不同孔道处的酸位在甲醇制烯烃反应中的催化作用[J]. 催化学报, 2021, 42(7): 1126-1136.

Sen Wang, Zhikai Li, Zhangfeng Qin, Mei Dong, Junfen Li, Weibin Fan, Jianguo Wang. Catalytic roles of the acid sites in different pore channels of H-ZSM-5 zeolite for methanol-to-olefins conversion[J]. Chinese Journal of Catalysis, 2021, 42(7): 1126-1136.

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https://www.cjcatal.com/CN/Y2021/V42/I7/1126

图/表 9

Fig. 1. 120T cluster models illustrating the intersection cavities, sinusoidal channels, and straight channels (T12, T10, and T8 sites, respectively) of H-ZSM-5 zeolite (Si, yellow; O, red; Al, pink; and H, white). Schematic topological structure of H-ZSM-5 zeolite. Methanol-to-olefins conversion reaction network including aromatic and alkene cycles following the dual-cycle hydrocarbons pool mechanism.

Fig. 2. Reaction networks for the aromatic cycle, alkene cycle, and aromatization process during methanol-to-olefins conversion over H-ZSM-5 zeolite.

Fig. 3. Free energy profiles of (a) ethene (e) and (b) propene (p) formation via the aromatic cycle at 723 K during methanol-to-olefins conversion at the acid sites in the intersection cavities, sinusoidal channels, and straight channels of H-ZSM-5 zeolite. A1 and A2 denote the adsorption of methanol and co-adsorption of p-xylene, respectively, M1-M3 denote methylation reactions, D1 and D2 denote deprotonation reactions, S1-S4 denote alkyl side-chain shifting reactions, and E1 denotes olefin elimination reaction.

Table 1 Calculated free energy barrier (ΔGint≠), rate constant (k), and reaction free energy (ΔGR) of each reaction step for the formation of ethene and propene via the aromatic cycle of methanol-to-olefins conversion at the acid sites in the intersection cavities (T12), sinusoidal channels (T10), and straight channels (T8) of H-ZSM-5 zeolite at 723 K.

Step	ΔG_int^≠ (kJ mol^-1)			k (s^-1)			ΔG_R (kJ mol^-1)
Step	T12	T10	T8	T12	T10	T8	T12	T10	T8
Ethene (e) formation
M1	140	141	171	1.17 × 10³	1.04 × 10³	6.11 × 10⁰	57	60	107
M2	126	136	135	1.23 × 10⁴	3.01 × 10³	3.01 × 10³	-29	-8	-32
D1	91	58	58	3.87 × 10⁶	9.65 × 10⁸	9.75 × 10⁸	39	41	32
S1(e)	50	37	76	3.74 × 10⁹	2.96 × 10¹⁰	4.73 × 10⁷	-30	-39	-13
S2(e)	80	60	101	2.68 × 10⁷	6.70 × 10⁸	7.97 × 10⁵	-16	-2	-1
S3(e)	114	115	117	8.64 × 10⁴	6.75 × 10⁴	5.32 × 10⁴	52	-6	36
S4(e)	70	53	58	1.37 × 10⁸	2.12 × 10⁹	9.92 × 10⁸	-45	-28	-34
E1(e)	103	106	122	5.47 × 10⁵	3.38 × 10⁵	2.50 × 10⁴	-4	-7	-16
Propene (p) formation
M3	114	124	138	8.91 × 10⁴	1.64 × 10⁴	1.50 × 10³	-30	-69	-47
D2	81	77	53	2.03 × 10⁷	4.03 × 10⁷	2.25 × 10⁹	57	49	22
S1(p)	57	36	74	1.05 × 10⁹	4.02 × 10¹⁰	7.05 × 10⁷	-17	-44	-27
S2(p)	82	78	82	1.92 × 10⁷	3.34 × 10⁷	1.85 × 10⁷	7	22	5
S3(p)	75	70	135	5.51 × 10⁷	1.32 × 10⁸	2.85 × 10³	28	36	63
S4(p)	27	42	58	1.67 × 10¹¹	1.32 × 10¹⁰	9.68 × 10⁸	-8	6	-54
E1(p)	30	25	46	9.52 × 10¹⁰	2.34 × 10¹¹	7.10 × 10⁹	-43	-58	-60
AFE ^*	280	293	294

Fig. 4. Free energy profiles for propene formation via the alkene cycle of methanol-to-olefins conversion at the acid sites in the intersection cavities, sinusoidal channels, and straight channels of H-ZSM-5 zeolite at 723 K. A1 and A2 denote the adsorption of methanol and co-adsorption of propene, respectively, M1-M3 denote methylation reactions, D1 and D2 denote deprotonation reactions, and E1 denotes propene elimination reaction.

Table 2 Calculated free energy barrier (ΔGint≠), rate constant (k) and reaction free energy (ΔGR) for each reaction step of the formation of ethene and propene via the alkene cycle of methanol-to-olefins conversion at the acid sites in the intersection cavities (T12), sinusoidal channels (T10), and straight channels (T8) of H-ZSM-5 zeolite at 723 K.

Step	ΔG_int^≠ (kJ mol^-1)			k (s^-1)			ΔG_R (kJ mol^-1)
Step	T12	T10	T8	T12	T10	T8	T12	T10	T8
M1	123	122	134	1.94 × 10⁴	2.30 × 10⁴	3.08 × 10³	38	25	-17
M2	129	120	131	7.17 × 10³	2.97 × 10⁴	5.11 × 10³	27	32	-15
M3	138	137	130	1.73 × 10³	2.02 × 10³	6.07 × 10³	32	38	-29
D1	56	30	39	1.45 × 10⁹	1.06 × 10¹¹	2.26 × 10¹⁰	-24	-37	-54
D2	66	13	17	2.71 × 10⁸	1.73 × 10¹²	9.06 × 10¹¹	-14	-38	-49
E1	109	100	118	1.95 × 10⁵	9.66 × 10⁵	4.74 × 10⁴	39	43	66
E2	156	166	161	8.97 × 10¹	1.41 × 10¹	3.51 × 10¹	104	74	60
AFE ^*	200	208	209

Table 3 Calculated free energy barrier (ΔGint≠), rate constant (k), and reaction free energy (ΔGR) for each reaction step of the formation of benzene via aromatization and the formation of polymethylbenzenes (polyMBs) via successive methylations of benzene at the acid sites in the intersection cavities (T12), sinusoidal channels (T10), and straight channels (T8) of H-ZSM-5 zeolite at 723 K.

Step	ΔG_int^≠ (kJ mol^-1)			k (s^-1)				ΔG_R (kJ mol^-1)
Step	T12	T10	T8	T12	T10	T8		T12	T10			T8
Benzene formation
D1	58	52	32	9.04 × 10⁸	2.68 × 10⁹		7.84 × 10¹⁰	-9		5		-49
HT1	136	159	166	2.43 × 10³	5.15 × 10¹		1.58 × 10¹	90		107		138
C1	75	73	96	5.57 × 10⁷	7.88 × 10⁷		1.79 × 10⁶	-44		-11		24
D2	16	23	30	1.09 × 10¹²	3.17 × 10¹¹		1.07 × 10¹¹	-46		-39		-71
HT2	137	138	148	1.80 × 10³	1.63 × 10³		3.09 × 10²	-41		-1		-11
D3	33	38	25	6.25 × 10¹⁰	2.64 × 10¹⁰		2.39 × 10¹¹	-3		-9		-30
HT3	122	121	132	2.43 × 10⁴	2.78 × 10⁴		4.54 × 10³	-109		-86		-78
D4	2	17	16	1.14 × 10¹³	9.31 × 10¹¹		1.13 × 10¹²	-93		-100		-115
AFE^*	293	311	337
PolyMBs formation
M1	175	161	166	3.71 × 10⁰	3.59 × 10¹	1.52 × 10¹		75		-16		86
M2	157	162	126	7.39 × 10¹	2.86 × 10¹	1.24 × 10⁴		59		61		46
M3	161	135	140	3.80 × 10¹	2.81 × 10¹	1.20 × 10³		79		59		92
M4	159	149	168	5.13 × 10¹	2.73 × 10²	1.06 × 10¹		20		26		30
M5	149	151	170	2.73 × 10²	1.70 × 10²	7.77 × 10⁰		15		20		19
M6	153	186	227	1.37 × 10²	5.21 × 10^-1	5.70 × 10^-4		16			43	21

Fig. 5. Free energy profiles for the formation of (a) benzene and (b) polymethylbenzenes via the successive methylations of the benzene ring during methanol-to-olefins conversion at the acid sites in the intersection cavities, sinusoidal channels, and straight channels of H-ZSM-5 zeolite at 723 K. Here, D1-D4 denote deprotonation reactions, HT1-HT3 denote hydride transfer reactions, C1 denotes cyclization of olefin carbenium ion, and M1-M6 denote benzene ring methylation reactions.

Fig. 6. Contour lines for the diffusion of (a) methanol, (b) propene, (c) p-xylene, and (d) hexamethylbenzene molecules in the straight and sinusoidal channels of H-ZSM-5 zeolite at 723 K. The density maps were constructed according to the two-dimensional projections of the mass centers of guest molecules in a 2 × 2 × 2 supercell. The color bars represent the density of guest molecules distributed in different channels with the unit of 1; the red areas with higher density values indicate higher diffusion probability.

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H-ZSM-5分子筛不同孔道处的酸位在甲醇制烯烃反应中的催化作用

Catalytic roles of the acid sites in different pore channels of H-ZSM-5 zeolite for methanol-to-olefins conversion

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