Brönsted方程动力学模型研究ZSM-5催化乙烯齐聚及芳构化活性和酸强度分布之间的定量关系

doi:10.11949/0438-1157.20191536

化工学报 ›› 2020, Vol. 71 ›› Issue (5): 2076-2087.DOI: 10.11949/0438-1157.20191536

• 催化、动力学与反应器 • 上一篇下一篇

Brönsted方程动力学模型研究ZSM-5催化乙烯齐聚及芳构化活性和酸强度分布之间的定量关系

金放¹(),张鹏¹(),吴桂英¹,吴迪²

^1.武汉工程大学化工与制药学院，绿色化工过程教育部重点实验室, 新型反应器与绿色化学工艺湖北省重点实验室，湖北武汉 430205
^2.美国布莱恩研究与工程公司，Bryan, Texas 77805

收稿日期:2019-12-18 修回日期:2020-02-11 出版日期:2020-05-05 发布日期:2020-05-05
通讯作者: 金放
作者简介:金放(1980—)，男，博士, 教授，fangjin@wit.edu.cn|张鹏（1993—），男，硕士研究生，zp1289365018@163.com
基金资助:
湖北省教育厅科学技术研究项目(B2018054);武汉工程大学校内科学研究基金项目(K201830)

Brönsted equation kinetic modeling for quantitative relationship between activity and acidity strength distribution in oligomerization and aromatization of ethylene over ZSM-5 catalyst

Fang JIN¹(),Peng ZHANG¹(),Guiying WU¹,Di WU²

^1.Key Laboratory for Green Chemical Process of Ministry of Education, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, Hubei, China
^2.Bryan Research & Engineering, LLC, Bryan, Texas 77805, USA

Received:2019-12-18 Revised:2020-02-11 Online:2020-05-05 Published:2020-05-05
Contact: Fang JIN

摘要/Abstract

摘要：

乙烯催化齐聚和芳构化是烯烃高值化和合成液体燃料的关键过程，采用NH₃-TPD谱图分析计算方法得到的探针分子脱附活化能作为催化剂的酸位点强度分布的参数，结合线性自由能理论在Br?nsted方程中引入酸强度对反应的影响因子γ作为动力学方程参数关联探针分子脱附活化能与反应活化能，明确固体酸酸强度的基准在催化动力学方程中的物理意义。建立同为MFI拓扑结构 Si /Al摩尔比为12.5、19、25、60、70的ZSM-5分子筛催化剂上不同酸强度位和乙烯齐聚及芳构化中氢转移、齐聚、芳构化各单元步骤以及对应的烷烃、低碳烯烃和芳烃产物分布的定量关系。根据拟合得到动力学参数γ可以发现不同强度的酸位点对乙烯齐聚及芳构化具有不同的作用系数。氨脱附活化能(DAE)为90 kJ·mol^-1的酸位点是氢转移反应的主要活性位点，而对于乙烯齐聚反应中主要的活性酸位点为DAE 90 kJ·mol^-1和124 kJ·mol^-1，DAE为150 kJ·mol^-1的酸位点是芳构化反应的主要活性位点。

关键词: 酸性, 催化, 沸石, 动力学模型, 齐聚, 芳构

Abstract:

Ethylene catalyzed oligomerization and aromatization are the key processes for the high value of olefins and the synthesis of liquid fuels. The desorption activation energy of the probe molecule calculated in NH₃-TPD was used as a parameter of the acid site intensity distribution of the catalyst, which correlate the information of the acid intensity distribution with the acid-catalyzed reaction activity. According to the linear free energy theory, the Br?nsted equation theory was further developed as the reaction kinetic model for establishing quantitative relationships between different acid strength sites and hydrogen transfer, oligomerization, and aromatization elementary steps corresponding to alkane，light olefins and aromatic products in the oligomerization and aromatization of ethylene on the ZSM-5 catalyst with the different Si/Al molar ratios. Both the elementary steps of hydrocarbon conversion and the basic probe molecule adsorption/desorption on acid sites follow the carbocation mechanism. Therefore, the desorption activation energy is related to the reaction activation energy based on the linear free energy by introducing γ as the kinetic parameter of reaction sensitivity to the acid strength of catalyst, which has a definite physical meaning in catalytic reaction kinetic modeling. The analysis of γ of different acid strength sites can conclude that acid sites with different strengths have different coefficients of action on ethylene oligomerization and aromatization. The acid site with ammonia desorption activation energy (DAE) of 90 kJ·mol^-1 is the main active site for hydrogen transfer reaction, while the main active acid site for ethylene oligomerization is DAE 90 kJ·mol^-1 and 124 kJ·mol^-1.The acid site with DAE of 150 kJ·mol^-1 is the main active site for the aromatization reaction.

Key words: acidity, catalysis, zeolite, kinetic modeling, oligomerization, aromatization

中图分类号:

TQ 028.8

金放,张鹏,吴桂英,吴迪. Brönsted方程动力学模型研究ZSM-5催化乙烯齐聚及芳构化活性和酸强度分布之间的定量关系[J]. 化工学报, 2020, 71(5): 2076-2087.

Fang JIN,Peng ZHANG,Guiying WU,Di WU. Brönsted equation kinetic modeling for quantitative relationship between activity and acidity strength distribution in oligomerization and aromatization of ethylene over ZSM-5 catalyst[J]. CIESC Journal, 2020, 71(5): 2076-2087.

图/表 10

图1 不同起始温度的NH3-TPD谱图(Si/Al摩尔比为12.5)

Fig.1 NH3-TPD spectra at different beginning temperatures

表1 根据式(9)计算单一酸强度位的E和KE

Table 1 E and KEvalues estimated by fitting Eq. (9) from acid sites with uniform acid strength over ZSM-5(Si/Al molar ratio 12.5)

T₀/K	(T₀+ΔT)/K	E/(kJ·mol^-1)	K_E/s^-1
348	398	51.9	1.1×10^-7
373	423	62.9	1.3×10^-8
398	448	71.7	1.8×10^-8
423	473	88.9	5.1×10^-9
448	498	105.6	9.4×10^-11
473	523	128.5	2.2×10^-11
523	573	145.5	6.8×10^-12
573	623	176.2	1.10×10^-13

图2 不同Si/Al比ZSM-5的NH3-TPD 谱图

Fig.2 NH3-TPD spectra of ZSM-5 with different Si/Al molar ratioSi/Al: A—12.5；B—19；C—25；D—60；E—70

图3 不同Si/Al比ZSM-5的酸强度分布

Fig.3 Acid strength distributions for different Si/Al molar ratio of ZSM-5

表2 不同Si /Al摩尔比的ZSM-5 的乙烯齐聚和芳构化活性

Table 2 Activity of xZSM-5 with different Si/Al molar ratio for ethylene oligomerization and aromatization

样品	TOF/(mmol·h^-1·g^-1)	A_c_i/(mmol·h^-1·g^-1)
样品	TOF/(mmol·h^-1·g^-1)	C2	C3	C3⁼	C4⁼	C6A	C7A	C8A
19ZSM-5	67.76	0.51	0.37	28.20	22.67	1.93	12.66	11.65
25ZSM-5	62.06	0.45	0.54	23.68	15.36	1.75	9.80	12.46
60ZSM-5	48.91	0.25	0.24	18.08	10.68	1.32	6.17	6.23
70ZSM-5	45.41	0.16	0.25	13.78	9.87	0.83	5.33	5.63

表3 拟合不同Si /Al摩尔比的ZSM-5的乙烯齐聚和芳构化反应的催化活性和位点强度分布，计算出在平均强度酸位点上的Br?nsted关系的δ, γ值

Table 3 δ, γ values of Br?nsted relation on average strength acid sites calculated by fitting catalytic activity and site strength distribution for ethylene oligomerization and aromatization on different ZSM-5

产物	δ	γ	R²	RSS	TSS
C2	0.0005	0.0031	0.95	3.36×10^-9	6.35×10^-8
C3	0.0003	0.0072	0.77	1.17×10^-8	5.15×10^-8
C3⁼	0.0350	0.0025	0.86	1.62×10^-5	1.20×10^-4
C4⁼	0.0250	0.0021	0.85	1.15×10^-5	7.49×10^-5
C6A	0.0026	0.0018	0.99	1.24×10^-8	1.03×10^-6
C7A	0.0186	0.0010	0.94	2.07×10^-6	3.40×10^-5
C8A	0.0057	0.0100	0.98	1.29×10^-7	3.91×10^-5

图4 Br?nsted方程拟合乙烷、丙烷、丙烯、丁烯、苯、甲苯、二甲苯实验数据(Aci)和计算值(?ci)的奇偶校验图

Fig.4 Parity plots between experimental Aci and model calculated date for ?ciwith Br?nsted ethane, propane, propylane, butene, benzene, toluene, xylene

表4 拟合每种不同Si/Al摩尔比的ZSM-5的乙烯齐聚和芳构化反应的催化活性和位点强度分布，计算出平均强度酸位点上Br?nsted关系的δ、γ值

Table 4 δ,γ values of Br?nsted relation on average strength acid site calculated by fitting catalytic activity and site strength distribution for ethylene oligomerization and aromatization with ZSM-5 of different Si/Al molar ratio

产物		19ZSM-5	25ZSM-5	60ZSM-5	70ZSM-5	R²
C2	δ	0.0005	0.0005	0.0005	0.0005	0.99
C2	γ	0.0030	0.0029	0.0032	0.0031	0.99
C3	δ	0.0003	0.0003	0.0003	0.0003	0.99
C3	γ	0.0060	0.0080	0.0072	0.0085	0.99
C3⁼	δ	0.0350	0.0320	0.0380	0.0360	0.99
C3⁼	γ	0.0025	0.0022	0.0030	0.0028	0.99
C4⁼	δ	0.0250	0.0210	0.0240	0.0270	0.99
C4⁼	γ	0.0025	0.0021	0.0026	0.0025	0.99
C6A	δ	0.0026	0.0025	0.0024	0.0026	0.99
C6A	γ	0.0017	0.0018	0.0019	0.0016	0.99
C7A	δ	0.0186	0.0160	0.0170	0.0170	0.99
C7A	γ	0.0010	0.0010	0.0011	0.0012	0.99
C8A	δ	0.0057	0.0056	0.0055	0.0056	0.99
C8A	γ	0.0100	0.0100	0.0100	0.0095	0.99

表5 拟合不同Si / Al摩尔比的ZSM-5的乙烯齐聚和芳构化反应的催化活性和位点强度分布，计算出在不同强度酸位点上的Br?nsted关系的δ、γi值

Table 5 δ, γi values of Br?nsted relation on different strength acid sites calculated by fitting catalytic activity and site strength distribution for ethylene oligomerization and aromatization on ZSM-5 of different Si/Al molar ratio

Parameter	E_i/(kJ·mol^-1)	C2	C3	C3⁼	C4⁼	C6A	C7A	C8A
δ		0.0004	0.00015	0.0436	0.0119	0.0019	0.011	0.015
γ_i	63	0.0008	-0.0326	-0.0211	-0.0243	-0.0055	-0.0007	0.002
	90	0.0324	0.0488	0.0144	-0.0161	0.0003	0.008	-0.0279
	124	-0.0001	0.0036	-0.0043	0.0133	0.0019	-0.0031	-0.0179
	150	0.0064	0.0144	0.007	0.0121	0.0084	0.01	0.003
	175	-0.0058	0.0021	-0.0078	-0.0131	0.0021	-0.0053	0.005
R²		0.954	0.935	0.912	0.980	0.915	0.919	0.996

图5 改进Br?nsted方程拟合乙烷、丙烷、丙烯、丁烯、苯、甲苯、二甲苯实验数据Aci和计算值?ci的奇偶校验图

Fig.5 Parity plots between experimental Aci and model calculated date for ?ciwith modified Br?nsted equation ethane, propane, propylane, butene, benzene, toluene, xylene

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Brönsted方程动力学模型研究ZSM-5催化乙烯齐聚及芳构化活性和酸强度分布之间的定量关系

Brönsted equation kinetic modeling for quantitative relationship between activity and acidity strength distribution in oligomerization and aromatization of ethylene over ZSM-5 catalyst

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