Acid Strength Controlled Reaction Pathways for the Catalytic Cracking of 1-Heptene over ZSM-5

doi:10.6023/A24070216

Abstract

Heptene (C₇⁼) is an important chemical intermediate. The C₇⁼ catalytic cracking to ethylene/propylene (C₂⁼/C₃⁼) represents an effective approach for the high-value utilization of carbon resources. However, the reaction pathways involved in the catalytic cracking of C₇⁼ and the principles governing their modulation remain to be thoroughly analyzed and clarified. In this study, we established a reaction network for C₇⁼ catalytic cracking based on the carbenium ion mechanism and β-scission mechanism. We investigated the catalytic performance of various zeolite catalysts with different topological structures and found that ZSM-5 zeolite, characterized by its unique pore structure, served as an efficient catalyst for C₇⁼ catalytic cracking. On this basis, a series of ZSM-5 zeolites (ZSM-5(I) to ZSM-5(V)) with comparable acid density and varying acid strength were synthesized via hydrothermal processes using phosphorus-modified and ammonium fluorosilicate-modified methods.The effects of the acidity (acid amount and acid strength) of the ZSM-5 zeolites on the catalytic cracking reaction of C₇⁼ were systematically investigated under 550 ℃. The results indicated that the C₇⁼ catalytic cracking primarily involved unimolecular cracking, hydrogen transfer, dehydrogenative aromatization, and decarbonylation reactions. The reduction of both acid amount and acid strength in ZSM-5 suppressed the reaction pathways for generating non-olefinic products, such as hydrogen transfer and aromatization, while enhancing the cracking pathways that produce olefins, thereby increasing the carbon resource utilization efficiency. Specifically, the acid strength of ZSM-5 played a crucial role in controlling the unimolecular cracking reaction pathways: pathway I (C₇⁼→C₃⁼＋C₄⁼) and pathway II (C₇⁼→C₂⁼＋C₅⁼). An increase in strong acid sites within ZSM-5 enhanced pathway II, leading to increased ethylene yields. Conversely, a higher number of weak acid sites promoted pathway I, resulting in greater propylene production. This research provides new insights into the design of catalysts for the efficient utilization of carbon resources in the catalytic cracking of C₇⁼ to C₂⁼/C₃⁼.

Key words: catalytic cracking, heptene, ZSM-5, acid strength, reaction pathway

Cite this article

Qin Zhao, Fang Li, Penghe Zhang, Yueming Liu. Acid Strength Controlled Reaction Pathways for the Catalytic Cracking of 1-Heptene over ZSM-5[J]. Acta Chimica Sinica, 2024, 82(10): 1013-1021.

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Sample	Si/Al₂^a	Pore property^b
Sample	Si/Al₂^a	S_micro/ (m²•g⁻¹)	S_exter/ (m²•g⁻¹)	V_total/ (cm³•g⁻¹)	V_micr/ (cm³•g⁻¹)
ZSM-5(55)	55	319	56	0.288	0.142
ZSM-5(99)	99	309	72	0.258	0.138
ZSM-5(149)	149	356	53	0.225	0.154
ZSM-5(198)	198	303	55	0.263	0.135
ZSM-5(271)	271	328	68	0.248	0.151

Sample	Si/Al₂^a	Pore property^b
Sample	Si/Al₂^a	S_micro/ (m²•g⁻¹)	S_exter/ (m²•g⁻¹)	V_total/ (cm³•g⁻¹)	V_micr/ (cm³•g⁻¹)
ZSM-5(55)	55	319	56	0.288	0.142
ZSM-5(99)	99	309	72	0.258	0.138
ZSM-5(149)	149	356	53	0.225	0.154
ZSM-5(198)	198	303	55	0.263	0.135
ZSM-5(271)	271	328	68	0.248	0.151

Sample	Si/Al₂^a	Pore property^b
Sample	Si/Al₂^a	S_micro/ (m²•g⁻¹)	S_exter/ (m²•g⁻¹)	V_total/ (cm³•g⁻¹)	V_micr/ (cm³•g⁻¹)
ZSM-5(I)	99	218	65	0.224	0.098
ZSM-5(II)	102	269	57	0.286	0.111
ZSM-5(III)	110	275	58	0.297	0.120
ZSM-5(IV)	105	259	53	0.276	0.116
ZSM-5(V)	120	246	49	0.271	0.111

Sample	Si/Al₂^a	Pore property^b
Sample	Si/Al₂^a	S_micro/ (m²•g⁻¹)	S_exter/ (m²•g⁻¹)	V_total/ (cm³•g⁻¹)	V_micr/ (cm³•g⁻¹)
ZSM-5(I)	99	218	65	0.224	0.098
ZSM-5(II)	102	269	57	0.286	0.111
ZSM-5(III)	110	275	58	0.297	0.120
ZSM-5(IV)	105	259	53	0.276	0.116
ZSM-5(V)	120	246	49	0.271	0.111

Sample	Acidity^a
Sample	WA/ (mmol•g⁻¹)	SA/ (mmol•g⁻¹)	TA/ (mmol•g⁻¹)	S/W
ZSM-5(55)	0.134	0.198	0.332	1.48
ZSM-5(99)	0.076	0.130	0.206	1.71
ZSM-5(149)	0.050	0.088	0.138	1.76
ZSM-5(198)	0.027	0.062	0.089	2.30
ZSM-5(271)	0.020	0.048	0.068	2.40

ZSM-5酸强度控制1-庚烯催化裂解反应路径的研究