Effect of acidic properties of single-crystalline hierarchical ZSM-5 zeolite on its activity and mass transfer in n-heptane catalytic cracking

doi:10.16085/j.issn.1000-6613.2023-2088

Abstract

Abstract:

Single-crystalline hierarchical ZSM-5 zeolite with intracrystalline mesopore was successfully synthesized by using L-lysine as a mesoporous template, and the Si/Al ratio was changed by adjusting the adding amount of aluminum source (sodium metaaluminate). Then the effect of acidic properties on zeolite’s activity and mass transfer in n-heptane catalytic cracking was investigated in detail. The physical structure, acidic properties and micromorphology of single-crystalline hierarchical ZSM-5 zeolite were characterized by using X-ray diffraction (XRD), nitrogen physical adsorption, ammonia temperature-programmed desorption (NH₃-TPD), pyridine infrared (Py-IR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In addition, the zero-length column (ZLC) device was employed to test the apparent diffusivity of n-heptane in single-crystalline hierarchical ZSM-5 zeolite,which was used to characterize its mass transfer performance. The results showed that the physical structure of single-crystalline hierarchical ZSM-5 zeolite kept almost the same with the increase of Si/Al ratio, while the zeolite’s mass transfer performance was improved with the decrease of acid amount, but the catalytic cracking performance was enhanced with the increase of acid amount. When the Si/Al ratio of the single-crystalline hierarchical ZSM-5 zeolite increased from 80 to 140, the apparent diffusivity of n-heptane could be improved by more than 87%. When the Si/Al ratio was 80, the conversion rate of n-heptane could reach up to 97.5%, and the selectivity of ethylene and propylene were 24.3% and 35.1%, respectively.

Key words: L-lysine, Si/Al ratio, single-crystalline hierarchical ZSM-5 zeolite, mass transfer, catalysis, reaction

摘要：

采用L-赖氨酸作为介孔模板剂，通过调控铝源（偏铝酸钠）添加量改变分子筛硅铝比，在单晶分子筛内部引入晶内介孔，成功地合成了一系列具有不同硅铝比的单晶多级孔ZSM-5分子筛，研究了其酸性质对正庚烷催化裂解反应传质性能的影响。利用X射线衍射（XRD）、N₂物理吸附、氨气程序升温脱附（NH₃-TPD）、吡啶红外（Py-IR）、扫描电子显微镜（SEM）和透射电子显微镜（TEM）等表征了单晶多级孔ZSM-5分子筛的物理结构、酸性质和微观形貌。同时，利用零长柱（ZLC）装置测试获取了正庚烷在单晶多级孔ZSM-5分子筛中的表观扩散系数，用于反映其传质性能。研究结果表明，随着硅铝比的提高，单晶多级孔ZSM-5分子筛的物理结构基本保持一致；传质性能随酸量的减少而提升，催化裂解性能随酸量的增加而提高。当单晶多级孔ZSM-5分子筛的Si/Al从80提高至140，正庚烷的表观扩散系数提升了87%以上；当单晶多级孔ZSM-5分子筛的Si/Al=80时，正庚烷的转化率最高可达97.5%，乙烯和丙烯的选择性分别为24.3%和35.1%。

关键词: L-赖氨酸, 硅铝比, 单晶多级孔ZSM-5分子筛, 传质, 催化, 反应

CLC Number:

TQ032.4

XIE Xiaojin, ZHANG Xiaoxue, LIU Xiaoling, CHONG Mingben, CHENG Dangguo, CHEN Fengqiu. Effect of acidic properties of single-crystalline hierarchical ZSM-5 zeolite on its activity and mass transfer in n-heptane catalytic cracking[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2661-2672.

谢小金, 张晓雪, 刘晓玲, 崇明本, 程党国, 陈丰秋. 单晶多级孔ZSM-5分子筛酸性质对正庚烷催化裂解反应传质性能的影响[J]. 化工进展, 2024, 43(5): 2661-2672.

Figures/Tables 13

References 47

1	白宇恩, 张彬瑞, 刘东阳, 等. ZSM-5分子筛酸性能和孔结构的协同作用对C5烯烃催化裂解性能的影响[J]. 化工学报, 2023, 74(1): 438-448.
	BAI Yu’en, ZHANG Binrui, LIU Dongyang, et al. Influence of synergistic effect of acid properties and pore structure of ZSM-5 zeolite on the catalytic cracking performance of pentene[J]. CIESC Journal, 2023, 74(1): 438-448.
2	AKAH Aaron, WILLIAMS Jesse, GHRAMI Musaed. An overview of light olefins production via steam enhanced catalytic cracking[J]. Catalysis Surveys from Asia, 2019, 23(4): 265-276.
3	SHA Yuchen, HAN Lei, WANG Ruoyu, et al. Tailoring ZSM-5 zeolite through metal incorporation: Toward enhanced light olefins production via catalytic cracking: A minireview[J]. Journal of Industrial and Engineering Chemistry, 2023, 126: 36-49.
4	BLAY Vincent, LOUIS Benoît, MIRAVALLES Rubén, et al. Engineering zeolites for catalytic cracking to light olefins[J]. ACS Catalysis, 2017, 7(10): 6542-6566.
5	李正宇, 张忠东, 王刚, 等. 用于催化裂解多产低碳烯烃的ZSM-5分子筛改性[J]. 石化技术与应用, 2021, 39(6): 462-468.
	LI Zhengyu, ZHANG Zhongdong, WANG Gang, et al. Modified of ZSM-5 zeolites for maximizing light olefins by catalytic pyrolysis[J]. Petrochemical Technology & Application, 2021, 39(6): 462-468.
6	潘小燕, 侯珂珂, 郑一帆, 等. 多级孔道ZSM-5分子筛催化正庚烷裂解制烯烃性能[J]. 化学反应工程与工艺, 2022, 38(1): 23-31, 40.
	PAN Xiaoyan, HOU Keke, ZHENG Yifan, et al. Catalytic performance of n-heptane catalytic cracking of to light olefins over hierarchical ZSM-5 zeolites[J]. Chemical Reaction Engineering and Technology, 2022, 38(1): 23-31, 40.
7	RAHIMI Nazi, KARIMZADEH Ramin. Catalytic cracking of hydrocarbons over modified ZSM-5 zeolites to produce light olefins: A review[J]. Applied Catalysis A: General, 2011, 398(1/2): 1-17.
8	SADRAMELI SM. Thermal/catalytic cracking of liquid hydrocarbons for the production of olefins: A state-of-the-art review Ⅱ: Catalytic cracking review[J]. Fuel, 2016, 173: 285-297.
9	DEGNAN T F, CHITNIS G K, SCHIPPER P H. History of ZSM-5 fluid catalytic cracking additive development at Mobil[J]. Microporous and Mesoporous Materials, 2000, 35/36: 245-252.
10	ALIPOUR Shayan Miar. Recent advances in naphtha catalytic cracking by nano ZSM-5: A review[J]. Chinese Journal of Catalysis, 2016, 37(5): 671-680.
11	SCHMIDT Franz, HOFFMANN Claudia, GIORDANINO Filippo, et al. Coke location in microporous and hierarchical ZSM-5 and the impact on the MTH reaction[J]. Journal of Catalysis, 2013, 307: 238-245.
12	MEUNIER Frederic C, VERBOEKEND Danny, GILSON Jean-Pierre, et al. Influence of crystal size and probe molecule on diffusion in hierarchical ZSM-5 zeolites prepared by desilication[J]. Microporous and Mesoporous Materials, 2012, 148(1): 115-121.
13	COPPENS Marc-Olivier, WEISSENBERGER Tobias, ZHANG Qunfeng, et al. Hierarchically structured zeolites: Nature-inspired, computer-assisted optimization of hierarchically structured zeolites[J]. Advanced Materials Interfaces, 2021, 8(4): 2170018.
14	LI Kundao, VALLA Julia, Javier GARCIA-MARTINEZ. Realizing the commercial potential of hierarchical zeolites: New opportunities in catalytic cracking[J]. ChemCatChem, 2014, 6(1): 46-66.
15	Sònia ABELLÓ, BONILLA Adriana, Javier PÉREZ-RAMÍREZ. Mesoporous ZSM-5 zeolite catalysts prepared by desilication with organic hydroxides and comparison with NaOH leaching[J]. Applied Catalysis A: General, 2009, 364(1/2): 191-198.
16	BAN S, VAN LAAK A N C, LANDERS J, et al. Insight into the effect of dealumination on mordenite using experimentally validated simulations[J]. Journal of Physical Chemistry C, 2010, 114(5): 2056-2065.
17	RIMAZ Sajjad, HALLADJ Rouein, ASKARI Sima. Synthesis of hierarchal SAPO-34 nano catalyst with dry gel conversion method in the presence of carbon nanotubes as a hard template[J]. Journal of Colloid and Interface Science, 2016, 464: 137-146.
18	SERRANO David P, AGUADO José, ESCOLA José M, et al. Hierarchical zeolites with enhanced textural and catalytic properties synthesized from organofunctionalized seeds[J]. Chemistry of Materials, 2006, 18(10): 2462-2464.
19	VASENKOV Sergey, Jörg KÄRGER. Evidence for the existence of intracrystalline transport barriers in MFI-type zeolites: A model consistency check using MC simulations[J]. Microporous and Mesoporous Materials, 2002, 55(2): 139-145.
20	VASENKOV Sergey, Winfried BÖHLMANN, GALVOSAS Petrik, et al. PFG NMR study of diffusion in MFI-type zeolites: Evidence of the existence of intracrystalline transport barriers[J]. The Journal of Physical Chemistry B, 2001, 105(25): 5922-5927.
21	NEWSOME David A, SHOLL David S. Molecular dynamics simulations of mass transfer resistance in grain boundaries of twinned zeolite membranes[J]. The Journal of Physical Chemistry B, 2006, 110(45): 22681-22689.
22	GUO Zhongyuan, LI Xin, HU Shen, et al. Understanding the role of internal diffusion barriers in Pt/beta zeolite catalyzed isomerization of n-heptane[J]. Angewandte Chemie International Edition, 2020, 59(4): 1548-1551.
23	ROEFFAERS Maarten B J, AMELOOT Rob, BARUAH Mukulesh, et al. Morphology of large ZSM-5 crystals unraveled by fluorescence microscopy[J]. Journal of the American Chemical Society, 2008, 130(17): 5763-5772.
24	CAO Kaipeng, FAN Dong, GAO Mingbin, et al. Recognizing the important role of surface barriers in MOR zeolite catalyzed DME carbonylation reaction[J]. ACS Catalysis, 2022, 12(1): 1-7.
25	TEIXEIRA Andrew R, CHANG Chun-Chih, COOGAN Timothy, et al. Dominance of surface barriers in molecular transport through silicalite-1[J]. The Journal of Physical Chemistry C, 2013, 117(48): 25545-25555.
26	KNIO Omar, FANG Hanjun, BOULFELFEL Salah Eddine, et al. Molecular dynamics investigation of surface resistances in zeolite nanosheets[J]. The Journal of Physical Chemistry C, 2020, 124(28): 15241-15252.
27	XU Shuman, ZHENG Ke, BORUNTEA Cristian-Renato, et al. Surface barriers to mass transfer in nanoporous materials for catalysis and separations[J]. Chemical Society Reviews, 2023, 52(12): 3991-4005.
28	ZHU Haibo, LIU Zhicheng, WANG Yangdong, et al. Nanosized CaCO₃ as hard template for creation of intracrystal pores within silicalite-1 crystal[J]. Chemistry of Materials, 2008, 20(3): 1134-1139.
29	DONG A, WANG Y, TANG Y, et al. Zeolitic tissue through wood cell templating[J]. Advanced Materials, 2002,14(12): 926-929.
30	HOLLAND Brian T, BLANFORD Christopher F, Thang DO, et al. Synthesis of highly ordered, three-dimensional, macroporous structures of amorphous or crystalline inorganic oxides, phosphates, and hybrid composites[J]. Chemistry of Materials, 1999, 11(3): 795-805.
31	ZHANG Rongxin, ZOU Run, LI Wei, et al. On understanding the sequential post-synthetic microwave-assisted dealumination and alkaline treatment of Y zeolite[J]. Microporous and Mesoporous Materials, 2022, 333: 11736.
32	GROEN Johan C, JANSEN Jacobus C, MOULIJN Jacob A, et al. Optimal aluminum-assisted mesoporosity development in MFI zeolites by desilication[J]. The Journal of Physical Chemistry, 2004, 108(35): 13062-13065.
33	ZHANG Minhua, QIN Yunan, JIANG Haoxi, et al. Protective desilication of β zeolite: A mechanism study and its application in ethanol-acetaldehyde to 1,3-butadiene[J]. Microporous and Mesoporous Materials, 2021, 326: 111359.
34	KARWACKI Lukasz, Marianne H F KOX, MATTHIJS DE WINTER D A, et al. Morphology-dependent zeolite intergrowth structures leading to distinct internal and outer-surface molecular diffusion barriers[J]. Nature Materials, 2009, 8(12): 959-965.
35	GOBIN O C, REITMEIER S J, JENTYS A, et al. Comparison of the transport of aromatic compounds in small and large MFI particles[J]. The Journal of Physical Chemistry C, 2009, 113(47): 20435-20444.
36	YE Guanghua, GUO Zhongyuan, SUN Yuanyuan, et al. Probing the nature of surface barriers on ZSM-5 by surface modification[J]. Chemie Ingenieur Technik, 2017, 89(10): 1333-1342.
37	ZHANG Xiaoxiao, CHENG Dangguo, CHEN Fengqiu, et al. The role of external acidity of hierarchical ZSM-5 zeolites in n-heptane catalytic cracking[J]. ChemCatChem, 2018, 10(12): 2655-2663.
38	XU Shuman, ZHANG Xiaoxiao, CHENG Dangguo, et al. Effect of hierarchical ZSM-5 zeolite crystal size on diffusion and catalytic performance of n-heptane cracking[J]. Frontiers of Chemical Science and Engineering, 2018, 12(4): 780-789.
39	郝靓, 于越洋, 崇明本, 等. 多级孔ZSM-5分子筛酸中心类型对裂解反应性能的影响[J]. 化学反应工程与工艺, 2021, 37(3): 226-234, 252.
	HAO Jing, YU Yueyang, CHONG Mingben, et al. Effect of acid type of hierarchical ZSM-5 zeolite on catalytic reaction performance[J]. Chemical Reaction Engineering and Technology, 2021, 37(3): 226-234, 252.
40	ZHANG Xiaoxue, XU Shuman, HAO Jing, et al. Effect of particle size of single-crystalline hierarchical ZSM-5 on its surface mass transfer in n-heptane catalytic cracking[J]. Chinese Journal of Chemical Engineering, 2023, 63: 148-157.
41	HAAG W O, DESSAU R M, LAGO R M. Kinetics and mechanism of paraffin cracking with zeolite catalysts[M]//Studies in Surface Science and Catalysis. Amsterdam: Elsevier, 1991: 255-265.
42	ZHANG Qiang, MAYORAL Alvaro, TERASAKI Osamu, et al. Amino acid-assisted construction of single-crystalline hierarchical nanozeolites via oriented-aggregation and intraparticle ripening[J]. Journal of the American Chemical Society, 2019, 141(9): 3772-3776.
43	HU Shen, LIU Junru, CHEN Jiaxuan, et al. Reducing external surface diffusion barriers by chemical vapor deposition for improved zeolite catalysis[J]. Industrial & Engineering Chemistry Research, 2022, 61(17): 5747-5756.
44	HUANG Xin, WANG Chuanfu, ZHU Yufei, et al. Facile synthesis of ZSM-5 nanosheet arrays by preferential growth over MFI zeolite [100] face for methanol conversion[J]. Microporous and Mesoporous Materials, 2019, 288: 109573.
45	CHEN Fengqiu, HAO Jing, YU Yueyang, et al. The influence of external acid strength of hierarchical ZSM-5 zeolites on n-heptane catalytic cracking[J]. Microporous and Mesoporous Materials, 2022, 330: 111575.
46	THOMMES Matthias, KANEKO Katsumi, NEIMARK Alexander V, et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report)[J]. Pure and Applied Chemistry, 2015, 87(9/10): 1051-1069.
47	CORMA Avelino, MENGUAL Jesús, MIGUEL Pablo J. Catalytic cracking of n-alkane naphtha: The impact of olefin addition and active sites differentiation[J]. Journal of Catalysis, 2015, 330: 520-532.

样品名称	SiO₂	TPAOH	Al₂O₃	Na₂O	L-赖氨酸	H₂O	温度和时间
Z5-Si/Al-80	1	0.450	0.00625	0.015	0.4	9	90℃ (2天)+170℃ (2天)
Z5-Si/Al-100	1	0.450	0.005	0.015	0.4	9	90℃ (2天)+170℃ (2天)
Z5-Si/Al-140	1	0.450	0.0035	0.015	0.4	9	90℃ (2天)+170℃ (2天)

样品名称	SiO₂	TPAOH	Al₂O₃	Na₂O	L-赖氨酸	H₂O	温度和时间
Z5-Si/Al-80	1	0.450	0.00625	0.015	0.4	9	90℃ (2天)+170℃ (2天)
Z5-Si/Al-100	1	0.450	0.005	0.015	0.4	9	90℃ (2天)+170℃ (2天)
Z5-Si/Al-140	1	0.450	0.0035	0.015	0.4	9	90℃ (2天)+170℃ (2天)

参数	单位	Z5-Si/Al-80	Z5-Si/Al-100	Z5-Si/Al-140
NH₃-W	℃	167	162	159
	mmol/g	0.174	0.136	0.071
NH₃-S	℃	348	343	335
	mmol/g	0.215	0.162	0.114
总酸量	mmol/g	0.389	0.298	0.185
B-200℃	mmol/g	0.085	0.072	0.038
B-350℃	mmol/g	0.060	0.049	0.028
外表面酸量	mmol/g	0.013	0.008	0.007
微孔内部酸量	mmol/g	0.072	0.064	0.031
Si/Al		86.7	98.7	136.6

参数	单位	Z5-Si/Al-80	Z5-Si/Al-100	Z5-Si/Al-140
NH₃-W	℃	167	162	159
	mmol/g	0.174	0.136	0.071
NH₃-S	℃	348	343	335
	mmol/g	0.215	0.162	0.114
总酸量	mmol/g	0.389	0.298	0.185
B-200℃	mmol/g	0.085	0.072	0.038
B-350℃	mmol/g	0.060	0.049	0.028
外表面酸量	mmol/g	0.013	0.008	0.007
微孔内部酸量	mmol/g	0.072	0.064	0.031
Si/Al		86.7	98.7	136.6

温度/℃	表观扩散系数D_eff/10^-18m²·s^-1
温度/℃	Z5-Si/Al-80	Z5-Si/Al-100	Z5-Si/Al-140
100	4.28	5.68	8.01
110	23.13	42.87	44.83
120	36.78	59.26	99.25
130	48.06	76.49	363.47
140	48.84	144.57	2635.33