有序介孔HZSM-5分子筛的合成及其在甲醇制芳烃中的催化性能

杨星; 慕红梅; 高鹏; 王思远; 田海锋; 查飞

doi:10.19906/j.cnki.JFCT.2022064

有序介孔HZSM-5分子筛的合成及其在甲醇制芳烃中的催化性能

doi: 10.19906/j.cnki.JFCT.2022064

杨星^1,,
慕红梅^2,,
高鹏^1,,
王思远^1,,
田海锋^1, ,,
查飞^1, ,

1.
西北师范大学化学化工学院, 甘肃兰州 730070
2.
兰州资源环境职业技术大学环境与化工学院, 甘肃兰州 730070

基金项目: 甘肃省青年科技基金计划项目（20JR10RA107）和甘肃省高等学校创新基金（2021A-254）资助

详细信息

通讯作者:
E-mail: thfnwnu@163.com

zhafei@nwnu.edu.cn

中图分类号: TQ426.6
计量
- 文章访问数: 1128
- HTML全文浏览量: 279
- PDF下载量: 38
- 被引次数: 0
出版历程
- 收稿日期: 2022-06-01
- 修回日期: 2022-07-12
- 录用日期: 2022-07-25
- 网络出版日期: 2022-07-28
- 刊出日期: 2022-12-28

Synthesis of sequential mesoporous HZSM-5 molecular sieve and its catalytic performance in methanol to aromatics

YANG Xing^1
,,
MU Hong-mei^2
,,
GAO Peng^1
,,
WANG Si-yuan^1
,,
TIAN Hai-feng^{1
, ,},
ZHA Fei^{1
, ,}

1.
Northwest Normal University Chemistry and Chemical Engineering, Lanzhou 730070, China
2.
Resources & Environment Voc-Tech University, Lanzhou 730070, China

Funds: The project was supported by Gansu Provincial Youth Science and Technology Fund Program (20JR10RA107) and Gansu Province Higher Education Innovation Fund Project (2021A-254).

摘要

摘要: 本研究采用模板法以及水热法，成功制备了不同粒径(20、30和40 nm)、硅铝比约为50的有序介孔HZSM-5分子筛。采用XRD、SEM、TEM、N₂等温吸附-脱附和Py-FTIR等手段对合成样品的结构、形貌和表面酸性等性质进行了表征，并在固定床反应器上测试了其在甲醇制芳烃过程中的催化活性。实验结果表明，不同粒径的有序介孔HZSM-5分子筛对甲醇制芳烃反应的催化性能不同，其中，20 nm的有序介孔HZSM-5分子筛展示了优异的催化性能，轻质芳烃的选择性高达60.0%，催化剂在连续运行51 h之后没有明显的失活现象。
- 有序介孔分子筛 /
- 不同粒径 /
- 甲醇制芳烃
Abstract: In this paper, ordered mesoporous HZSM-5 zeolite with different particle sizes (20, 30 and 40 nm) and the Si/Al ratio of 50 was successfully prepared by the hydrothermal method. The structure, morphology and surface acidity of the synthesized samples were characterized by XRD, SEM, TEM, N₂ isothermal adsorption/desorption and Py-FTIR, and their catalytic activities were tested in the methanol to aromatics process on a fixed-bed reactor. The experimental results showed that the catalytic performance of ordered mesoporous HZSM-5 zeolite with different particle sizes was different for the methanol to aromatics reaction. The ordered mesoporous HZSM-5 zeolite of 20 nm exhibited excellent catalytic performance with the selectivity of light aromatics up to 60.0% and no significant deactivation of the catalyst after 51 h of continuous operation.
- ordered mesoporous zeolite /
- particle sizes /
- methanol to aromatics

HTML全文

FIG. 2024. FIG. 2024.

下载: 全尺寸图片幻灯片

图 1 样品的XRD谱图

Figure 1 XRD patterns of the sample

下载: 全尺寸图片幻灯片

图 2 (a) 20 nm，(b) 30 nm，(c) 40 nm SiO₂微球；(d) 20 nm，(e) 30 nm，(f) 40 nm有序介孔碳；(h) 20 nm，(i) 30 nm，(g) 40 nm有序介孔HZSM-5分子筛的SEM照片和(k) 20 nm SiO₂微球；(l) 20 nm有序介孔碳；(m) 20 nm有序介孔HZSM-5分子筛的TEM照片

Figure 2 SEM images of (a) 20 nm, (b) 30 nm, (c) 40 nm SiO₂ microspheres; (d) 20 nm, (e) 30 nm, (f) 40 nm ordered mesoporous carbon; (h) 20 nm, (i) 30 nm, (g) 40 nm ordered mesoporous HZSM-5 zeolite; TEM images of (k) 20 nm SiO₂ microspheres; (l) 20 nm ordered mesoporous carbon; (m) 20 nm ordered mesoporous HZSM-5 zeolite

下载: 全尺寸图片幻灯片

图 3 不同样品的(a) N₂吸附-脱附等温曲线和(b)、(c)孔径分布

Figure 3 (a) N₂ adsorption/desorption isotherms and (b), (c) pore size distribution of different samples

下载: 全尺寸图片幻灯片

图 4 不同样品的NH₃-TPD谱图

Figure 4 NH₃-TPD profiles of different samples

下载: 全尺寸图片幻灯片

图 5 (a) 20 nm；(b) 30 nm；(c) 40 nm HZSM-5在150和350 ℃下的Py-FTIR谱图

Figure 5 Py-FTIR spectra of (a) 20 nm; (b) 30 nm; (c) 40 nm HZSM-5 at 150 and 350 ℃

下载: 全尺寸图片幻灯片

图 6 不同样品的 ²⁷Al MAS NMR光谱谱图

Figure 6 ²⁷Al MAS NMR spectra of different samples

下载: 全尺寸图片幻灯片

图 7 不同催化剂上甲醇转化率随时间的变化

Figure 7 Relation of methanol conversion with the time on stream (TOS) over different catalysts

下载: 全尺寸图片幻灯片

图 8 不同催化剂上MTA反应中产物选择性随时间的变化

Figure 8 Selectivity of products for MTA with the time on stream (TOS) over different catalysts (a): 20 nm HZSM-5; (b): 30 nm HZSM-5; (c): 40 nm HZSM-5

下载: 全尺寸图片幻灯片

表 1 催化剂的结构性质

Table 1 Textural properties of the catalysts

Sample	S_BET^a /(m²·g^–1)	S_micro^b /(m²·g^–1)	S_meso^c /(m²·g^–1)	v_total^d /(cm³·g^–1)	v_micro^e /(cm³·g^–1)	v_meso^f /(cm³·g^–1)	Si/Al^g
20 nm HZSM-5	275.78	187.34	88.44	0.16	0.05	0.11	38
30 nm HZSM-5	201.45	133.11	68.34	0.15	0.07	0.09	43
40 nm HZSM-5	198.37	159.52	38.85	0.13	0.08	0.05	37
S_BET^a(surface area calculated by BET), S_micro^b (surface area of micropores by t-plot method)，S_meso^c = S_BET^a – S_micro^b, v_micro^e (micropore volume by t-plot method), v_total^d (total pore volume), Si/Al^g (ICP analysis)

下载: 导出CSV

表 2 不同样品的酸性位点含量

Table 2 Concentrations of acid sites in different samples

Sample	Concentration of acid sites /(a.u.·g^–1)
Sample	weak	medium	strong	total
20 nm HZSM-5	54.31	88.73	141.39	284.43
30 nm HZSM-5	50.64	60.18	166.31	277.13
40 nm HZSM-5	55.92	28.32	139.84	224.08

下载: 导出CSV

表 3 不同样品的B酸和L酸性位点分布

Table 3 Distribution of B and L acid sites on different samples

Sample	Amount of B /(mmol·g^–1)			Amount of L /(mmol·g^–1)			B/L
Sample	150 ℃	350 ℃	total	150 ℃	350 ℃	total	B/L
20 nm HZSM-5	0.056	0.049	0.105	0.068	0.033	0.101	1.04
30 nm HZSM-5	0.040	0.017	0.057	0.075	0.023	0.098	0.58
40 nm HZSM-5	0.025	0.012	0.037	0.046	0.015	0.061	0.61

下载: 导出CSV

表 4 不同催化剂用于MTA反应的产物选择性

Table 4 Product selectivity of different catalysts for MTA reaction

Catalyst	Production selectivity /%
Catalyst	C_1-2	C₃	C₄	C_{5 +}	B^a	T^b	X^c	C_{9 +}	aro^d	BTX
20 nm HZSM-5	4.7	9.9	18.1	3.3	1.0	6.1	53.0	4.1	64.1	60.0
30 nm HZSM-5	5.7	11.7	24.7	4.6	0.7	5.1	42.3	5.3	53.4	48.1
40 nm HZSM-5	6.7	16.7	21.2	6.8	6.5	7.9	31.1	3.1	48.6	45.5
Reaction conditions：0.1 MPa，450 ℃，0.5 g catalyst， $p_{{\rm{CH}}_3 {\rm{OH}}} $=20 kPa，WHSV=1.9 h⁻¹，time on stream (TOS)=3 h；B^a=benzene，T^b= toluene，X^c=xylene，aro^d=B + T + X + C_{9 +}

下载: 导出CSV

参考文献(42)

[1]	TIAN P L, SHEN K, CHEN J Y, FAN T, FANG R Q, LI Y W. Self-templated formation of Pt@ZIF-8/SiO₂ composite with 3D-ordered macropores and size-selective catalytic properties[J]. Small Methods,2018,2(12):1800219. doi: 10.1002/smtd.201800219
[2]	SHEN K, CAI S, LING R, XIE D, LI X, SUN J, WEI J, SUN X. Flexible, three-dimensional ordered macroporous ZnO electrode with enhanced electrochemical performance in lithium-ion batteries[J]. Microporous Mesoporous Mater,2019,289:109618. doi: 10.1016/j.micromeso.2019.109618
[3]	YAN H, BLANFORD C F, LYTLE J C, CARTER C B, SMYRL W H, STEIN A. Influence of processing conditions on structures of 3D ordered macroporous metals prepared by colloidal crystal templating[J]. Chem Mater,2001,13(11):4314−4321. doi: 10.1021/cm0105716
[4]	WU Z S, SUN Y, TAN Y Z, YANG S B, FENG X L, MÜLLEN K. Three-dimensional graphene-based macro-and mesoporous frameworks for high-performance electrochemical capacitive energy storage[J]. J Am Chem Soc,2012,134(48):19532−19535. doi: 10.1021/ja308676h
[5]	YANG W, YANG W, KONG L SONG A L, QIN X J. Synthesis of three-dimensional hierarchical porous carbon for high-performance supercapacitors[J]. Ionics,2018,24(10):3133−3141. doi: 10.1007/s11581-017-2432-z
[6]	FENG J X, ZHENG D, GAO X L, QUE W B, SHI W H, LIU W X, WU F F, CAO X H. Three-dimensional ordered porous carbon for energy conversion and storage applications[J]. Front Energy Res,2020,8:210. doi: 10.3389/fenrg.2020.00210
[7]	CHEN Y, ZHU Y J, CHEN Z G. Three-dimensional ordered macroporous carbon as counter electrodes in dye-sensitized solar cells[J]. Thin Solid Films,2013,539:122−126. doi: 10.1016/j.tsf.2013.05.096
[8]	ARANDIYAN H, DAI H X, JI K, SUN H Y, LI J H. Pt nanoparticles embedded in colloidal crystal template derived 3D ordered macroporous Ce_0.6Zr_0.3Y_0.1O₂: Highly efficient catalysts for methane combustion[J]. ACS Catal,2015,5(3):1781−1793. doi: 10.1021/cs501773h
[9]	XUE H, TANG J, GONG H, GUO H, FAN X L, WANG T, HE J P, YAMAUCHI Y. Fabrication of PdCo bimetallic nanoparticles anchored on three-dimensional ordered N-doped porous carbon as an efficient catalyst for oxygen reduction reaction[J]. ACS Appl Mater Interfaces,2016,8(32):20766−20771. doi: 10.1021/acsami.6b05856
[10]	DAVIS M E. Ordered porous materials for emerging applications[J]. Nature,2002,417(6891):813−821. doi: 10.1038/nature00785
[11]	COLIN S, CUNDY, PAUL A C. The hydrothermal synthesis of zeolites: History and development from the earliest days to the present time[J]. Chem Rev,2003,103:663−702.
[12]	PéREZ-RAMíREZ J, CHRISTENSEN C H, EGEBLAD K, CHRISTENSEND C H. GROENEF J C. Hierarchical zeolites: Enhanced utilisation of microporous crystals in catalysis by advances in materials design[J]. Chem Soc Rev,2008,37(11):2530−2542. doi: 10.1039/b809030k
[13]	HARTMANN M. Hierarchical zeolites: A proven strategy to combine shape selectivity with efficient mass transport[J]. Angew Chem Int Ed,2004,43(44):5880−5882. doi: 10.1002/anie.200460644
[14]	陈思姝, 李光兰, 谢洋洋. 胶体晶体模板法制备三维有序多孔碳材料及其电化学性能[J]. 中国科学: 化学,2015,45(6):614−623. CHEN Si-mei, LI Guang-lan, XIE Yang-yang. Preparation of three-dimensional ordered porous carbon materials and their electrochemical properties by colloidal crystal template method[J]. Sci China Chem,2015,45(6):614−623.
[15]	YU C, TIAN B, FAN J, STUCKY G D, ZHAO D Y. Salt effect in the synthesis of mesoporous silica templated by non-ionic block copolymers[J]. Chem Commun,2001,24:2726−2727.
[16]	KIM J M, RYOO R. Synthesis of MCM-48 single crystals[J]. Chem Commun,1998,2:259−260.
[17]	JACOBSEN C J H, MADSEN C, JANSSENS T V W, JJAKOBSENB H, SKIBSTED. Zeolites by confined space synthesis-characterization of the acid sites in nanosized ZSM-5 by ammonia desorption and ²⁷Al/²⁹Si-MAS NMR spectroscopy[J]. Microporous Mesoporous Mater,2000,39(1/2):393−401.
[18]	SCHMIDT I, MADSEN C, JACOBSEN C J H. Confined space synthesis. A novel route to nanosized zeolites[J]. Inorg Chem,2000,39(11):2279−2283. doi: 10.1021/ic991280q
[19]	LI Q, CREASER D, STERTE J. The nucleation period for TPA-silicalite-1 crystallization determined by a two-stage varying-temperature synthesis[J]. Microporous Mesoporous Mater,1999,31(1/2):141−150.
[20]	AGUADO J, SERRANO D P, ESCOLA J M, RODRíGUEZ. Low temperature synthesis and properties of ZSM-5 aggregates formed by ultra-small nanocrystals[J]. Microporous Mesoporous Mater,2004,75(1/2):41−49.
[21]	NIU X J, GAO J, WANG K, MIAO Q, DONG M, WANG G F, FAN W B, QIN Z F, WANG J G. Influence of crystal size on the catalytic performance of H-ZSM-5 and Zn/H-ZSM-5 in the conversion of methanol to aromatics[J]. Fuel Process Technol,2017,157:99−107. doi: 10.1016/j.fuproc.2016.12.006
[22]	KIM H S, KANG S K, ZHANG H X, TIKUE E T, LEE J H, LEE P S. Al-ZSM-5 nanocrystal catalysts grown from Silicalite-1 seeds for methane conversion[J]. Energies,2021,14(2):485. doi: 10.3390/en14020485
[23]	XUE T, CHEN L, WANG Y M, HE M Y. Seed-induced synthesis of mesoporous ZSM-5 aggregates using tetrapropylammonium hydroxide as single template[J]. Microporous Mesoporous Mater,2012,156:97−105. doi: 10.1016/j.micromeso.2012.02.022
[24]	MI X T, HOU Z G, LI X G. Controllable synthesis of nanoscaled ZSM-5 aggregates with multivariate channel under the synergistic effect of silicate-1 and TPABr using dual-silica source[J]. Microporous Mesoporous Mater,2021,323:111224. doi: 10.1016/j.micromeso.2021.111224
[25]	REN N, YANG Z J, LV X C, SHI J, ZHANG Y H, TANG Y. A seed surface crystallization approach for rapid synthesis of submicron ZSM-5 zeolite with controllable crystal size and morphology[J]. Microporous Mesoporous Mater,2010,131(1/3):103−114.
[26]	FERNÁNDEZ-REYES B, MORALES JIMÉNEZ S, SÁNCHEZ-MARRERO G, MUÑOZ-SENMACHE J C, HERNÁNDES-MALDONADO A J. Hierarchical three-dimensionally ordered mesoporous carbon (3DOm) zeolite composites for the adsorption of contaminants of emerging concern[J]. J Hazard Mater Lett,2021,2:100017. doi: 10.1016/j.hazl.2021.100017
[27]	WANG J, YANG M F, SHANG W J, SU X P, HAO Q Q, CHEN H Y, MA X X. Synthesis, characterization and catalytic application of hierarchical SAPO-34 zeolite with three-dimensionally ordered mesoporous-imprinted structure[J]. Microporous Mesoporous Mater,2017,252:10−16. doi: 10.1016/j.micromeso.2017.06.012
[28]	YOKOI T, SAKAMOTO Y, TERASAKI O, KUBOTA Y, OKUBO T, TATSUMI T. Periodic arrangement of silica nanospheres assisted by amino acids[J]. J Am Chem Soc,2006,128(42):13664−13665. doi: 10.1021/ja065071y
[29]	FAN W, SNYDER M A, KUMAR S, LEE P S, YOO W C, MCCORMICK A V, LEE PENN R, STEIN A, TSAPATSIS, M. Hierarchical nanofabrication of microporous crystals with ordered mesoporosity[J]. Nat Mater,2008,7(12):984−991. doi: 10.1038/nmat2302
[30]	WANG Z, DORNATH P, CHANG C C, CHEN H Y, FAN W. Confined synthesis of three-dimensionally ordered mesoporous-imprinted zeolites with tunable morphology and Si/Al ratio[J]. Microporous Mesoporous Mater,2013,181:8−16. doi: 10.1016/j.micromeso.2013.07.010
[31]	GIERSZAL K P, JARONIEC M. Carbons with extremely large volume of uniform mesopores synthesized by carbonization of phenolic resin film formed on colloidal silica template[J]. J Am Chem Soc,2006,128(31):10026−10027. doi: 10.1021/ja0634831
[32]	CHEN H Y, WYDRA J, ZHANG X Y, LEE P S, WANG Z P, FAN W, TSAPATSIS M. Hydrothermal synthesis of zeolites with three-dimensionally ordered mesoporous-imprinted structure[J]. J Am Chem Soc,2011,133(32):12390−12393. doi: 10.1021/ja2046815
[33]	BI Y, WANG Y L, CHEN X, YU Z G, XU L. Methanol aromatization over HZSM-5 catalysts modified with different zinc salts[J]. Chin J Catal,2014,35(10):1740−1751. doi: 10.1016/S1872-2067(14)60145-5
[34]	NIU X J, GAO J, MIAO Q, DONG M, WANG G F, FAN W B, QIN Z F, WANG J G. Influence of preparation method on the performance of Zn-containing HZSM-5 catalysts in methanol-to-aromatics[J]. Microporous Mesoporous Mater,2014,197:252−261. doi: 10.1016/j.micromeso.2014.06.027
[35]	WEI Z H, XIA T F, LIU M H, CAO Q S, XU Y R, ZHU K, ZHU X D. Alkaline modification of ZSM-5 catalysts for methanol aromatization: The effect of the alkaline concentration[J]. Front Chem Sci Eng,2015,9(4):450−460. doi: 10.1007/s11705-015-1542-2
[36]	WANG Z L, CHU W F, ZHAO Z C, LIU Z M, CHEN H Y, XIAO D, GONG K, LI F, LI X J, HOU G J. The role of organic and inorganic structure-directing agents in selective Al substitution of zeolite[J]. J Phys Chem Lett,2021,12(38):9398−9406. doi: 10.1021/acs.jpclett.1c01448
[37]	WAN Z J, WU W, LI G, WANG C F, YANG H, ZHANG D K. Effect of SiO₂/Al₂O₃ ratio on the performance of nanocrystal ZSM-5 zeolite catalysts in methanol to gasoline conversion[J]. Appl Catal A: Gen,2016,523:312−320. doi: 10.1016/j.apcata.2016.05.032
[38]	HE Y P, LIU M, DAI C Y, XU S T, WEI Y X, LIU Z M, GUO X W. Modification of nanocrystalline HZSM-5 zeolite with tetrapropylammonium hydroxide and its catalytic performance in methanol to gasoline reaction[J]. Chin J Catal,2013,34(6):1148−1158. doi: 10.1016/S1872-2067(12)60579-8
[39]	LIN X L, FAN Y, LIU Z H, SHI G, LIU H Y, BAO X J. A novel method for enhancing on-stream stability of fluid catalytic cracking (FCC) gasoline hydro-upgrading catalyst: Post-treatment of HZSM-5 zeolite by combined steaming and citric acid leaching[J]. Catal Today, 2007, 125 (3/4): 185–191.
[40]	ZHANG H B, MA Y C, SONG K S, ZHANG Y H, TANG Y. Nano-crystallite oriented self-assembled ZSM-5 zeolite and its LDPE cracking properties: effects of accessibility and strength of acid sites[J]. J Catal,2013,302:115−125. doi: 10.1016/j.jcat.2013.03.019
[41]	JIA Y M, SHI Q H, WANG J W, DING C M, ZHANG K. Synthesis, characterization, and catalytic application of hierarchical nano-ZSM-5 zeolite[J]. RSC Adv,2020,10(50):29618−29626. doi: 10.1039/D0RA06040B
[42]	HU Z J, ZHANG H B, WANG L, ZHANG H X, ZAHNG Y H, XU H L, SHEN W, TANG Y. Highly stable boron-modified hierarchical nanocrystalline ZSM-5 zeolite for the methanol to propylene reaction[J]. Catal Sci Technol,2014,4(9):2891−2895. doi: 10.1039/C4CY00376D