Secondary growth mechanism of nano-ZSM-5 in solution of high SiO2/Al2O3 ratio and its performance of methanol to aromatics

doi:10.16085/j.issn.1000-6613.2022-0363

Abstract

Abstract:

Low selectivity is the main issue in methanol to aromatics (MTA) reaction catalyzed by ZSM-5. Rational design and control of the acid properties of ZSM-5 catalysts is an effective strategy to promote highly selective generation of aromatic hydrocarbons. In this study, nano ZSM-5 with SiO₂/Al₂O₃ ratio of 50 was placed in ZSM-5 synthesis system with different SiO₂/Al₂O₃ ratios (50, 110, 220, 440 and 660) for secondary growth to prepare a series of samples to optimize the surface acidities and improve the selectivity of light aromatics. The morphology, texture properties and acid properties of the ZSM-5 zeolites were characterized by using X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray fluorescence (XRF), pyridine adsorption Fourier-transform infrared (Py-IR) and temperature-programmed desorption of ammonia (NH₃-TPD), and the crystal growth mechanism was studied accordingly. During the crystal growth, the parent powder was partially dissolved and small crystals were formed firstly, surrounding the surface of the parent ZSM-5. The crystals grown over N50 to form nanosized single-crystal coated ZSM-5. The particle size distribution of the sample was not uniform after secondary growth in the feed solution with low SiO₂/Al₂O₃ ratio. But on the whole, with the increase of SiO₂/Al₂O₃ ratio, the crystal particles tended to be uniform and zeolites with rough protrusions structure. The secondary growth significantly changed the acid properties of the zeolite surface and aromatization properties. The total acid amount increased to 194.9μmol/g, after secondary growing in the feed solution with a higher SiO₂/Al₂O₃ ratio (220), which was significantly higher than that of the parent powder (169.7μmol/g). It is worth noting that the proportion of strong acid on the catalyst surface also increased significantly from 37% of the parent powder to 53%, and B/L ratio also increased from 0.56 to 3.19. The acidity modulation not only facilitated the conversion of methanol to aromatics, but also strengthened the dealkylation conversion of aromatics and BTX selectivity increased accordingly. Thus, the selectivities of aromatics and BTX were increased from 16.1% and 8.2% to 23.8% and 13.5%, respectively.

Key words: zeolite, hydrothermal, preparation, catalysis, selectivity, methanol to aromatics

摘要：

芳烃选择性低是ZSM-5催化甲醇制芳烃反应的难点问题，调变ZSM-5酸性质是提升选择性的重要方法。本研究将SiO₂/Al₂O₃为50的纳米ZSM-5分别置于硅铝比为50、110、220、440和660的料液中继续水热生长，优化其表面酸性，以提高轻质芳烃选择性。采用X射线衍射（XRD）、透射电子显微镜（TEM）、X射线荧光光谱（XRF）、吡啶红外（Py-IR）、氨气程序升温脱附（NH₃-TPD）等手段分析所得ZSM-5形貌、织构和酸性质，研究其水热再生长规律。发现生长过程中原粉部分溶解，包围在其表面的料液先形成小晶粒，经逐步堆积完成对原粉的包覆，最终形成孔道贯通性良好的单晶。在较低硅铝比料液中样品粒径分布不均匀，然而随着料液硅铝比的增加，包覆趋向均匀且表面呈现凸起结构。二次生长显著改变了表面酸性质及芳构化性能，在硅铝比为220的料液中生长后总酸量增加到194.9μmol/g，高于原粉的169.7μmol/g。值得注意的是，催化剂表面的强酸占比由原粉的37%显著增加至53%，B/L值也由原粉的0.56增加至3.19。该酸性的变化在促进甲醇芳构化的同时，还能强化芳烃的脱烷基化而提高BTX选择性，使总芳烃选择性和BTX选择性分别由16.1%和8.2%提高到23.8%和13.5%。

关键词: 沸石, 水热, 制备, 催化, 选择性, 甲醇制芳烃

CLC Number:

O643.3

HUI Yan, FU Tingjun, MA Qian, LI Zhong. Secondary growth mechanism of nano-ZSM-5 in solution of high SiO₂/Al₂O₃ratio and its performance of methanol to aromatics[J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6364-6376.

惠燕, 付廷俊, 马倩, 李忠. 纳米ZSM-5在高硅铝比料液中的再生长机制及其甲醇制芳烃性能[J]. 化工进展, 2022, 41(12): 6364-6376.

Figures/Tables 15

References 41

1	LI Teng, SHOINKHOROVA Tuiana, GASCON Jorge, et al. Aromatics production via methanol-mediated transformation routes[J]. ACS Catalysis, 2021, 11(13): 7780-7819.
2	陈嵩嵩, 张国帅, 霍锋, 等. 煤基大宗化学品市场及产业发展趋势[J]. 化工进展, 2020, 39(12): 5009-5020.
	CHEN Songsong, ZHANG Guoshuai, HUO Feng, et al. Market and technology development trends of coal-based bulk chemicals[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 5009-5020.
3	米多, 王涛, 田佰和. 国内外芳烃主要产品市场分析[J]. 化学工业, 2020, 38(4): 57-67.
	MI Duo, WANG Tao, TIAN Baihe. Analysis of the main aromatics market at home and abroad[J]. Chemical Industry, 2020, 38(4): 57-67.
4	ZHANG Dan, YANG Minbo, FENG Xiao, et al. Integration of methanol aromatization with light hydrocarbon aromatization toward increasing aromatic yields: conceptual process designs and comparative analysis[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(30): 11376-11388.
5	ZHANG Jingui, QIAN Weizhong, KONG Chuiyan, et al. Increasing para-xylene selectivity in making aromatics from methanol with a surface-modified Zn/P/ZSM-5 catalyst[J]. ACS Catalysis, 2015, 5(5): 2982-2988.
6	CHANG Clarence D, SILVESTRI Anthony J. The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts[J]. Journal of Catalysis, 1977, 47(2): 249-259.
7	MA Yunhai, CAI Dali, LI Yiru, et al. The influence of straight pore blockage on the selectivity of methanol to aromatics in nanosized Zn/ZSM-5: an atomic Cs-corrected STEM analysis study[J]. RSC Advances, 2016, 6(78): 74797-74801.
8	YARULINA Irina, CHOWDHURY Abhishek Dutta, MEIRER Florian, et al. Recent trends and fundamental insights in the methanol-to-hydrocarbons process[J]. Nature Catalysis, 2018, 1(6): 398-411.
9	METZGER Kara E, MOYER Megan M, TREWYN Brian G. Tandem catalytic systems integrating biocatalysts and inorganic catalysts using functionalized porous materials[J]. ACS Catalysis, 2021, 11(1): 110-122.
10	YARULINA Irina, DE WISPELAERE Kristof, BAILLEUL Simon, et al. Structure-performance descriptors and the role of Lewis acidity in the methanol-to-propylene process[J]. Nature Chemistry, 2018, 10(8): 804-812.
11	GAO Yan, ZHENG Binghui, WU Guang, et al. Effect of the Si/Al ratio on the performance of hierarchical ZSM-5 zeolites for methanol aromatization[J]. RSC Advances, 2016, 6(87): 83581-83588.
12	MA Hao, SUN Yuan, YU Junping, et al. Theoretical study on the influence of ZSM-5 zeolite with different structures for methanol to aromatics[J]. Microporous and Mesoporous Materials, 2020, 294: 109838-109847.
13	MANDERSLOOT W G B, NICOLAIDES C P, SCURRELL M S. Comments on the effect of the acidic strength of silica-alumina in the conversion of methanol to hydrocarbons[J]. Applied Catalysis, 1986, 27(2): 393-396.
14	BI Yi, WANG Yingli, CHEN Xin, et al. Methanol aromatization over HZSM-5 catalysts modified with different zinc salts[J]. Chinese Journal of Catalysis, 2014, 35(10): 1740-1751.
15	LI Junhua, WANG Lina, ZHANG Dan, et al. Effect of ZSM-5 acid modification on aromatization performance of methanol[J]. Journal of Fuel Chemistry and Technology, 2019, 47(8): 957-963.
16	MIYAKE Koji, HIROTA Yuichiro, Kaito ONO, et al. Selective production of benzene, toluene and p-xylene (BTpX) from various C_1-3 feedstocks over ZSM-5/silicalite-1 core-shell zeolite catalyst[J]. ChemistrySelect, 2016, 1(5): 967-969.
17	YANG Junhao, GONG Ke, MIAO Dengyun, et al. Enhanced aromatic selectivity by the sheet-like ZSM-5 in syngas conversion[J]. Journal of Energy Chemistry, 2019, 35: 44-48.
18	WANG Kai, DONG Mei, NIU Xianjun, et al. Highly active and stable Zn/ZSM-5 zeolite catalyst for the conversion of methanol to aromatics: effect of support morphology[J]. Catalysis Science & Technology, 2018, 8(21): 5646-5656.
19	董道敏, 刘宾, 柴永明, 等. 动态水热法制备silicalite-1分子筛膜包覆多孔缺陷Al₂O₃微球[J]. 化工进展, 2018, 37(10): 3943-3948.
	DONG Daomin, LIU Bin, CHAI Yongming, et al. Dynamic hydrothermal synthesis of silicalite-1 zeolite membrane to encapsulate defective porous alumina spheres[J]. Chemical Industry and Engineering Progress, 2018, 37(10): 3943-3948.
20	XIE Chenlu, CHEN Chen, YU Yi, et al. Tandem catalysis for CO₂ hydrogenation to C₂—C₄ hydrocarbons[J]. Nano Letters, 2017, 17(6): 3798-3802.
21	XU Yanfei, MA Guangyuan, BAI Jingyang, et al. Yolk@shell FeMn@hollow HZSM-5 nanoreactor for directly converting syngas to aromatics[J]. ACS Catalysis, 2021, 11(8): 4476-4485.
22	XU Guohao, ZHU Xuedong. A core-shell structured Zn/SiO₂@ZSM-5 catalyst: preparation and enhanced catalytic properties in methane co-aromatization with propane[J]. Applied Catalysis B: Environmental, 2021, 293: 120241-120249.
23	WANG Xiaoxing, ZHANG Junfeng, ZHANG Tao, et al. Mesoporous ZnZSM-5 zeolites synthesized by one-step desilication and reassembly: a durable catalyst for methanol aromatization[J]. RSC Advances, 2016, 6(28): 23428-23437.
24	CUI Tianlu, LI Xinhao, Libing LYU, et al. Nanoscale Kirkendall growth of silicalite-1 zeolite mesocrystals with controlled mesoporosity and size[J]. Chemical Communications, 2015, 51(63): 12563-12566.
25	JIA Yanming, WANG Junwen, ZHANG Kan, et al. Hierarchical ZSM-5 zeolite synthesized via dry gel conversion-steam assisted crystallization process and its application in aromatization of methanol[J]. Powder Technology, 2018, 328: 415-429.
26	SUN Minghui, ZHOU Jian, HU Zhiyi, et al. Hierarchical zeolite single-crystal reactor for excellent catalytic efficiency[J]. Matter, 2020, 3(4): 1226-1245.
27	TAO Shuo, LI Xiaolei, WANG Xiaoge, et al. Facile synthesis of hierarchical nanosized single-crystal aluminophosphate molecular sieves from highly homogeneous and concentrated precursors[J]. Angewandte Chemie International Edition, 2020, 59(9): 3455-3459.
28	ZHU Jie, ZHU Yihan, ZHU Liangkui, et al. Highly mesoporous single-crystalline zeolite beta synthesized using a nonsurfactant cationic polymer as a dual-function template[J]. Journal of the American Chemical Society, 2014, 136(6): 2503-2510.
29	JAMIL Anas Karrar, MURAZA Oki, AL-AMER Adnan M. The role of alcohols and diols as co-solvents in fabrication of TON zeolite[J]. Journal of Industrial and Engineering Chemistry, 2015, 29: 112-119.
30	CHEN Xiaoxin, YAN Wenfu, CAO Xuejing, et al. Fabrication of silicalite-1 crystals with tunable aspect ratios by microwave-assisted solvothermal synthesis[J]. Microporous and Mesoporous Materials, 2009, 119(1/2/3): 217-222.
31	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.
32	GOODARZI Farnoosh, HERRERO Irene Pinilla, KALANTZOPOULOS Georgios N, et al. Synthesis of mesoporous ZSM-5 zeolite encapsulated in an ultrathin protective shell of silicalite-1 for MTH conversion[J]. Microporous and Mesoporous Materials, 2020, 292: 109730-109739.
33	JONES Andrew J, IGLESIA Enrique. The strength of Brønsted acid sites in microporous aluminosilicates[J]. ACS Catalysis, 2015, 5(10): 5741-5755.
34	JONES Andrew J, CARR Robert T, ZONES Stacey I, et al. Acid strength and solvation in catalysis by MFI zeolites and effects of the identity, concentration and location of framework heteroatoms[J]. Journal of Catalysis, 2014, 312: 58-68.
35	KATADA Naonobu, Hirofumi IGI, KIM Jong Ho. Determination of the acidic properties of zeolite by theoretical analysis of temperature-programmed desorption of ammonia based on adsorption equilibrium[J]. The Journal of Physical Chemistry B, 1997, 101(31): 5969-5977.
36	KALITA Pranjal, GUPTA Narendra M, KUMAR Rajiv. Synergistic role of acid sites in the Ce-enhanced activity of mesoporous Ce-Al-MCM-41 catalysts in alkylation reactions: FTIR and TPD-ammonia studies[J]. Journal of Catalysis, 2007, 245(2): 338-347.
37	WANG Chao, CHU Yueying, ZHENG Anmin, et al. New insight into the hydrocarbon-pool chemistry of the methanol-to-olefins conversion over zeolite H-ZSM-5 from GC-MS, solid-state NMR spectroscopy, and DFT calculations[J]. Chemistry—a European Journal, 2014, 20(39): 12432-12443.
38	Róbert BARTHOS, Tamás BÁNSÁGI, SÜLI ZAKAR Tímea, et al. Aromatization of methanol and methylation of benzene over Mo₂C/ZSM-5 catalysts[J]. Journal of Catalysis, 2007, 247(2): 368-378.
39	FENG Chaoqun, SU Xiaofang, WANG Wei, et al. Facile synthesis of ultrafine nanosized ZSM-5 zeolite using a hydroxyl radical initiator for enhanced catalytic performance in the MTG reaction[J]. Microporous and Mesoporous Materials, 2021, 312: 110780-110790.
40	FU Tingjun, SHAO Juan, LI Zhong. Catalytic synergy between the low Si/Al ratio Zn/ZSM-5 and high Si/Al ratio HZSM-5 for high-performance methanol conversion to aromatics[J]. Applied Catalysis B: Environmental, 2021, 291: 120098-120113.
41	SCHULZ Hans. “Coking” of zeolites during methanol conversion: basic reactions of the MTO-, MTP- and MTG processes[J]. Catalysis Today, 2010, 154(3/4): 183-194.

样品	比表面积/m²·g^-1			体积/cm³·g^-1
样品	总比表面积（S_BET^①）	外比表面积（S_Exter^②）	微孔比表面积（S_Micro^②）	总体积（V_Total^③）	介孔体积（V_Meso^④）	微孔体积（V_Micro^②）
N50	408	53	355	0.49	0.31	0.18
N50@N50	383	31	352	0.30	0.13	0.17
N50@N110	394	32	362	0.32	0.14	0.18
N50@N220	401	37	364	0.42	0.25	0.17
N50@N440	431	44	387	0.48	0.29	0.19
N50@N660	434	44	390	0.46	0.28	0.18

样品	比表面积/m²·g^-1			体积/cm³·g^-1
样品	总比表面积（S_BET^①）	外比表面积（S_Exter^②）	微孔比表面积（S_Micro^②）	总体积（V_Total^③）	介孔体积（V_Meso^④）	微孔体积（V_Micro^②）
N50	408	53	355	0.49	0.31	0.18
N50@N50	383	31	352	0.30	0.13	0.17
N50@N110	394	32	362	0.32	0.14	0.18
N50@N220	401	37	364	0.42	0.25	0.17
N50@N440	431	44	387	0.48	0.29	0.19
N50@N660	434	44	390	0.46	0.28	0.18

样品	SiO₂/Al₂O₃^①	SiO₂/Al₂O₃^②	酸量^③/μmol·g^-1				强酸/弱酸	酸量^④/μmol·g^-1		B/L
样品	SiO₂/Al₂O₃^①	SiO₂/Al₂O₃^②	总量	弱酸	中强酸	强酸	强酸/弱酸	B酸	L酸	B/L
N50	72	21	169.7	84.0	22.5	63.2	0.75	26.8	47.6	0.56
N50@N50	70	—	247.5	100.1	41.8	105.6	1.06	—	—	—
N50@N110	77	27	194.9	85.2	33.8	75.9	0.89	37.1	19.8	1.87
N50@N220	87	46	194.9	70.4	21.0	103.4	1.47	38.2	12.0	3.19
N50@N440	94	—	142.6	41.9	19.6	81.1	1.93	—	—	—
N50@N660	106	50	125.6	42.3	15.4	67.9	1.61	4.0	15.6	0.25

样品	SiO₂/Al₂O₃^①	SiO₂/Al₂O₃^②	酸量^③/μmol·g^-1				强酸/弱酸	酸量^④/μmol·g^-1		B/L
样品	SiO₂/Al₂O₃^①	SiO₂/Al₂O₃^②	总量	弱酸	中强酸	强酸	强酸/弱酸	B酸	L酸	B/L
N50	72	21	169.7	84.0	22.5	63.2	0.75	26.8	47.6	0.56
N50@N50	70	—	247.5	100.1	41.8	105.6	1.06	—	—	—
N50@N110	77	27	194.9	85.2	33.8	75.9	0.89	37.1	19.8	1.87
N50@N220	87	46	194.9	70.4	21.0	103.4	1.47	38.2	12.0	3.19
N50@N440	94	—	142.6	41.9	19.6	81.1	1.93	—	—	—
N50@N660	106	50	125.6	42.3	15.4	67.9	1.61	4.0	15.6	0.25

样品	选择性/%							氢转移指数^①	丙烯/乙烯（P/E）
样品	甲烷	乙烷	丙烷	丁烷	乙烯	丙烯	丁烯	氢转移指数^①	丙烯/乙烯（P/E）
N50	0.7	0.4	4.4	17.1	8.5	21.5	16.3	0.17	2.53
N50@N50	1.8	0.3	6.0	17.4	9.5	19.9	13.5	0.23	2.09
N50@N110	1.3	0.2	5.3	16.9	8.8	19.9	14.0	0.21	2.27
N50@N220	1.7	0.3	6.9	15.6	8.4	18.8	13.1	0.27	2.23
N50@N440	1.4	0.3	5.6	13.4	8.2	22.3	16.7	0.20	2.72
N50@N660	1.7	0.3	5.2	12.8	9.0	24.3	18.3	0.18	2.71

Secondary growth mechanism of nano-ZSM-5 in solution of high SiO₂/Al₂O₃ratio and its performance of methanol to aromatics

纳米ZSM-5在高硅铝比料液中的再生长机制及其甲醇制芳烃性能

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 15

References 41

Related Articles 15

Recommended Articles

Metrics

Comments

样品	积炭量/g·g_cat^-1	积炭速率/g·g_cat^-1·h^-1
N50	0.21	2.8×10^-3
N50@N50	0.13	2.6×10^-3
N50@N110	0.14	2.1×10^-3
N50@N220	0.14	2.1×10^-3
N50@N440	0.13	1.8×10^-3
N50@N660	0.12	2.4×10^-3

[1]	ZHENG Qian, GUAN Xiushuai, JIN Shanbiao, ZHANG Changming, ZHANG Xiaochao. Photothermal catalysis synthesis of DMC from CO₂ and methanol over Ce_0.25Zr_0.75O₂ solid solution [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 319-327.
[2]	WANG Zhengkun, LI Sifang. Green synthesis of gemini surfactant decyne diol [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 400-410.
[3]	CHEN Chongming, CHEN Qiu, GONG Yunqian, CHE Kai, YU Jinxing, SUN Nannan. Research progresses on zeolite-based CO₂ adsorbents [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 411-419.
[4]	DENG Liping, SHI Haoyu, LIU Xiaolong, CHEN Yaoji, YAN Jingying. Non-noble metal modified vanadium titanium-based catalyst for NH₃-SCR denitrification simultaneous control VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 542-548.
[5]	GENG Yuanze, ZHOU Junhu, ZHANG Tianyou, ZHU Xiaoyu, YANG Weijuan. Homogeneous/heterogeneous coupled combustion of heptane in a partially packed bed burner [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4514-4521.
[6]	WANG Jingang, ZHANG Jianbo, TANG Xuejiao, LIU Jinpeng, JU Meiting. Research progress on modification of Cu-SSZ-13 catalyst for denitration of automobile exhaust gas [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4636-4648.
[7]	GAO Yanjing. Analysis of international research trend of single-atom catalysis technology [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4667-4676.
[8]	GE Yafen, SUN Yu, XIAO Peng, LIU Qi, LIU Bo, SUN Chengying, GONG Yanjun. Research progress of zeolite for VOCs removal [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4716-4730.
[9]	LI Dongze, ZHANG Xiang, TIAN Jian, HU Pan, YAO Jie, ZHU Lin, BU Changsheng, WANG Xinye. Research progress of NO _x reduction by carbonaceous substances for denitration in cement kiln [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4882-4893.
[10]	WANG Chen, BAI Haoliang, KANG Xue. Performance study of high power UV-LED heat dissipation and nano-TiO₂ photocatalytic acid red 26 coupling system [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4905-4916.
[11]	ZHU Chuanqiang, RU Jinbo, SUN Tingting, XIE Xingwang, LI Changming, GAO Shiqiu. Characteristics of selective non-catalytic reduction of NO _x with solid polymer denitration agent [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4939-4946.
[12]	WANG Xueting, GU Xia, XU Xianbao, ZHAO Lei, XUE Gang, LI Xiang. Effectiveness of hydrothermal pretreatment on valeric acid production during food waste fermentation [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4994-5002.
[13]	PAN Yichang, ZHOU Rongfei, XING Weihong. Advanced microporous membranes for efficient separation of same-carbon-number hydrocarbon mixtures: State-of-the-art and challenges [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3926-3942.
[14]	WU Haibo, WANG Xilun, FANG Yanxiong, JI Hongbing. Progress of the development and application of 3D printing catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3956-3964.
[15]	MAO Shanjun, WANG Zhe, WANG Yong. Group recognition hydrogenation: From concept to application [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3917-3922.