ZSM-5酸强度控制1-庚烯催化裂解反应路径的研究

doi:10.6023/A24070216

摘要/Abstract

庚烯(C₇⁼)是一种重要的化工中间原料. C₇⁼催化裂解制乙烯/丙烯(C₂⁼/C₃⁼)过程是烯烃碳资源高值化利用的有效途径, 然而其裂解反应路径及其调控原理仍有待厘清. 本工作根据正碳离子机理和β-裂解机理, 首先建立了C₇⁼催化裂解反应路径网络, 并考察了不同拓扑结构分子筛催化剂的催化裂解性能, 发现ZSM-5分子筛是C₇⁼催化裂解的高效催化剂. 在此基础上, 系统研究了ZSM-5分子筛的酸性质(酸量、酸强度)对反应的影响. 结果表明, ZSM-5分子筛酸量、酸强度的降低, 均抑制了生成非烯烃类产物的氢转移、芳构化等反应路径, 进而提高了烯烃碳资源利用率. 特别的是, ZSM-5分子筛的酸强度控制了C₇⁼单分子裂解反应路径I (C₇⁼→C₃⁼＋C₄⁼)和路径II (C₇⁼→C₂⁼＋C₅⁼), 强酸中心促进裂解路径II而多产乙烯, 弱酸中心利于裂解路径I而多产丙烯. 本研究为C₇⁼催化裂解制C₂⁼/C₃⁼过程中碳资源高效利用的催化剂设计提供了新思路.

关键词: 催化裂解, 庚烯, ZSM-5, 酸强度, 反应路径

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

引用此文

赵勤, 李芳, 张鹏鹤, 刘月明. ZSM-5酸强度控制1-庚烯催化裂解反应路径的研究[J]. 化学学报, 2024, 82(10): 1013-1021.

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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图/表 16

图1. 不同Si/Al2比ZSM-5分子筛XRD谱图

Figure 1. XRD patterns of ZSM-5 with different Si/Al2 ratios

图2. 不同酸强度ZSM-5(I)~ZSM-5(V)的XRD谱图

Figure 2. XRD patterns of ZSM-5(I)~ZSM-5(V) with different acid strengths

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

表1. 不同酸量ZSM-5分子筛的孔道结构参数

Table 1. Textural properties of ZSM-5(55)~ZSM-5(271)

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

表2. 不同酸强度ZSM-5(I)~ZSM-5(V)的孔道结构参数

Table 2. Textural properties of ZSM-5(I)~ZSM-5(V)

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

表3. 不同酸量ZSM-5分子筛的酸性质

Table 3. Acid properties of ZSM-5(55)~ZSM-5(271) zeolites

Sample	Acidity^a
Sample	WA/ (mmol•g⁻¹)	SA/ (mmol•g⁻¹)	TA/ (mmol•g⁻¹)	S/W
ZSM-5(I)	0.109	0.053	0.162	0.49
ZSM-5(II)	0.085	0.093	0.177	1.10
ZSM-5(III)	0.065	0.102	0.167	1.59
ZSM-5(IV)	0.052	0.108	0.159	2.08
ZSM-5(V)	0.049	0.112	0.161	2.29

表4. 不同酸强度ZSM-5分子筛的酸性质

Table 4. Acid properties of ZSM-5(I)~ZSM-5(V) zeolites

图3. 不同吡啶脱附温度下的Br?nsted酸量归一化图

Figure 3. Normalized area relative to Br?nsted acid sites versus evacuation temperature

图4. C7=通过β-裂解生成C3=和C4=可能的情况

Figure 4. The generation pathways of C3= and C4= in the catalytic cracking of C7= by β-scission

图5. C7=通过β-裂解生成C2=和C5=可能的情况

Figure 5. The generation pathways of C2= and C5= in the catalytic cracking of C7= by β-scission

图6. C7=催化裂解反应网络简图

Figure 6. Reaction network of C7= catalytic cracking

图7. 不同拓扑结构分子筛催化1-庚烯的裂解反应性能

Figure 7. Results of 1-heptene cracking catalyzed by zeolite with different topological structures reaction conditions: cat., 0.5 g; temp, 550 ℃; pressure, 0.1 MPa; 1-heptene flow rate, 0.06 mL?min?1; N2 flow rate, 320 mL?min?1; weight hourly space velocity (WHSV), 5.02 h?1; time on stream (TOS), 1 h. None-olefin: C0＋H2＋Aromatic

Sample	Conv./ mol%	Selectivity/mol%
Sample	Conv./ mol%	C₂⁼	C₃⁼	C₄⁼	C₅⁼	C₁⁰~C₂⁰	C₃⁰	C₄⁰~C₅⁰	H₂	C₆⁺
ZSM-5(55)	100	24.78	37.41	9.35	1.93	2.55	2.30	2.22	11.37	8.09
ZSM-5(99)	100	23.94	40.67	10.28	1.60	2.17	2.02	1.55	10.65	7.12
ZSM-5(149)	100	22.38	43.05	14.47	0.95	1.98	1.50	2.04	9.50	4.13
ZSM-5(198)	100	19.90	47.91	19.88	1.09	1.03	1.29	1.44	4.16	3.30
ZSM-5(271)	100	15.52	53.09	25.52	1.79	0.51	0.63	0.68	1.18	1.08

表5. ZSM-5(55)~ZSM-5(271)催化1-庚烯裂解的反应结果

Table 5. Results of 1-heptene cracking catalyzed by ZSM-5(55)~ZSM-5(271)

图8. 不同酸量的ZSM-5上1-庚烯裂解的产物分布

Figure 8. Product distribution of 1-heptene cracking on ZSM-5 with different acid amounts

Sample	Conv./ mol%	Selectivity/mol%
Sample	Conv./ mol%	C₂⁼	C₃⁼	C₄⁼	C₅⁼	C₁⁰~C₂⁰	C₃⁰	C₄⁰~C₅⁰	H₂	C₆⁺
ZSM-5(I)	100	7.55	55.05	30.70	4.72	0.21	0.52	0.89	0.66	1.40
ZSM-5(II)	100	13.34	53.34	27.80	1.77	0.38	0.78	0.78	0.87	0.93
ZSM-5(III)	100	14.20	52.48	23.82	1.57	0.62	0.97	1.30	2.68	2.36
ZSM-5(IV)	100	17.00	52.12	22.97	1.54	0.58	1.11	1.04	1.65	1.99
ZSM-5(V)	100	17.94	51.60	22.30	1.51	0.64	1.21	1.53	1.34	1.93

表6. ZSM-5(I)~ZSM-5(V)上1-庚烯的催化裂解反应结果

Table 6. Results of 1-heptene cracking over ZSM-5(I)~ZSM-5(V)

图9. ZSM-5(I)~ZSM-5(V)上1-庚烯催化裂解的产物分布

Figure 9. Product distribution of catalytic cracking for 1-heptene over ZSM-5(I)~ZSM-5(V)

Sample	P/E	P/B	$\mathrm{C}_{3}^{=}$./$\mathrm{C}_{5}^{=}$	a	b	c	1－b－c
ZSM-5(I)	7.29	1.79	11.66	0.98	0.19	0.17	0.64
ZSM-5(II)	4.00	1.92	30.14	0.96	0.07	0.37	0.56
ZSM-5(III)	3.70	2.20	33.43	0.97	0.06	0.45	0.49
ZSM-5(IV)	3.07	2.27	33.84	0.94	0.06	0.45	0.49
ZSM-5(V)	2.88	2.31	34.17	0.93	0.06	0.45	0.49

表7. ZSM-5(I)~ZSM-5(V)上1-庚烯各裂解路径的相对占比计算结果

Table 7. Relative proportion of 1-heptene cracking pathway over ZSM-5(I)~ZSM-5(V)

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