蒙脱土基HZSM-5的制备及其在二甲醚水蒸气重整制氢中的应用

张家慷; 王欢; 张森晗; 冯效迁; 张启俭; 赵永华

蒙脱土基HZSM-5的制备及其在二甲醚水蒸气重整制氢中的应用

辽宁工业大学　化学与环境工程学院, 辽宁锦州 121001

基金项目: 国家自然科学基金(22075120)，辽宁省应用基础研究计划项目(2023JH2/101300216)

详细信息

通讯作者:
赵永华，博士，教授，硕士生导师，研究方向为多相催化　E-mail: lgdzyh@163.com

中图分类号: O643.3
计量
- 文章访问数: 48
- HTML全文浏览量: 30
- 被引次数: 0
出版历程
- 收稿日期: 2024-05-23
- 修回日期: 2024-06-22
- 录用日期: 2024-07-20
- 网络出版日期: 2024-08-03

HZSM-5 synthesized by montmorillonite and its application for production of hydrogen via steam reforming of dimethyl ether

School of Chemistry & Environmental Engineering, Liaoning University of Technology, Jinzhou 121001,Liaoning, China

Funds: Natural Science Foundation of China (No. 22075120), Liaoning Provincial Applied Basic Research Project of China (No. 2023JH2/101300216)

摘要

摘要: 以亚熔岩活化蒙脱土为原料，采用传统水热法、晶种导向法、蒸汽辅助晶化法和气溶胶晶化法制备了具有不同织构和酸性的HZSM-5，并以其为固体酸与商品化的Cu/ZnO/Al₂O₃物理混合组成双功能催化剂，并考察其二甲醚水蒸气重整(SRD)反应性能。通过XRD、FT-IR、SEM、N₂低温吸附-脱附和NH₃-TPD对样品进行表征。结果表明，合成方法影响了HZSM-5的晶体尺寸、织构及酸性等，进而影响了以其为固体酸的双功能催化剂的SRD性能。传统水热法合成的TH-HZSM-5因其具有适宜的酸量以及相对大的表面积、孔容和孔径，以其为固体酸与Cu/ZnO/Al₂O₃以质量比为1∶1组成的双功能催化剂表现出较好的SRD反应性能，在压力为0.1 MPa、温度为300 ℃、空速为5000 mL/(g·h)的反应条件下，二甲醚初始转化率和氢气收率分别达到了100%和91%。
- 二甲醚 /
- 水蒸气重整 /
- 制氢 /
- HZSM-5 /
- 蒙脱土
Abstract: HZSM-5 with different texture and acidity was prepared using sub-molten salt activated montmorillonite as raw material by traditional hydrothermal method, seed-directed method, steam-assisted crystallization method and aerosol crystallization method. And the HZSM-5 used as solid acid was physically mixed with commercial Cu/ZnO/Al₂O₃ to obtain bifunctional catalysts for steam reforming of dimethyl ether (SRD) reaction. The samples were systematically characterized by XRD, FT-IR, SEM, N₂ adsorption-desorption at low temperature, and NH₃-TPD techniques. The results showed that the crystal size, textural and acidity properties of HZSM-5 could be effectively regulated by the synthesis method, and then affecting the SRD performance of the corresponding bifunctional catalyst. TH-HZSM-5 synthesized by the traditional hydrothermal method exhibited suitable acid content and relatively large surface area, pore volume and pore size, and thus bifunctional catalyst composed of TH-HZSM-5 as solid acid and Cu/ZnO/Al₂O₃ with a mass ratio of 1∶1 showed better SRD reaction performance, and the dimethyl ether conversion and H₂ yield reached 100% and 91% under the conditions of reaction temperature 300 ℃, pressure 0.1 MPa, space velocity 5000 mL/(g·h), respectively.
- dimethyl ether /
- steam reforming /
- hydrogen production /
- HZSM-5 /
- montmorillonite

HTML全文

图 1 HZSM-5结构

Figure 1. The structure of HZSM-5

下载: 全尺寸图片幻灯片

图 2 不同方法合成HZSM-5的XRD图

Figure 2. XRD pattern of HZSM-5 synthesized by different methods

TH-HZSM-5, SD-HZSM-5, SAC-HZSM-5, AC-HZSM-5—HZSM-5 synthesized by traditional hydrothermal, seed-directed, steam-assisted crystallization and aerosol crystallization method, respectively.

下载: 全尺寸图片幻灯片

图 3 不同方法合成HZSM-5的FT-IR光谱

Figure 3. FT-IR spectra of HZSM-5 synthesized by different methods

下载: 全尺寸图片幻灯片

图 4 不同方法合成HZSM-5的SEM图

Figure 4. SEM spectra of HZSM-5 synthesized by different methods

下载: 全尺寸图片幻灯片

图 5 不同方法合成HZSM-5的N₂吸附等温线

Figure 5. N₂ adsorption isotherm of HZSM-5 synthesized by different methods

下载: 全尺寸图片幻灯片

图 6 不同方法合成HZSM-5分子筛的NH₃-TPD图

Figure 6. NH₃-TPD spectra of HZSM-5 synthesized by different methods

下载: 全尺寸图片幻灯片

图 7 不同方法合成的HZSM-5+Cu/ZnO/Al₂O₃双功能催化剂的DME转化率(a)和H₂收率(b)

Figure 7. DME conversion (a) and H₂ yield (b) of bifunctional catalysts composed of HZSM-5 synthesized by different methods and Cu/ZnO/Al₂O₃

下载: 全尺寸图片幻灯片

图 8 不同方法合成的HZSM-5+Cu/ZnO/Al₂O₃双功能催化剂的含碳产物选择性

Figure 8. The selectivity of carbon containing products of bifunctional catalyst composed of HZSM-5 synthesized by different methods and Cu/ZnO/Al₂O₃

下载: 全尺寸图片幻灯片

图 9 不同质量比的TH-HZSM-5+Cu/ZnO/Al₂O₃双功能催化剂的DME转化率(a)和H₂收率(b)

Figure 9. DME conversion (a) and H₂ yield (b) of bifunctional catalysts composed of TH-HZSM-5 and Cu/ZnO/Al₂O₃ with different mass ratios

下载: 全尺寸图片幻灯片

图 10 不同质量比的HZSM-5+Cu/ZnO/Al₂O₃双功能催化剂的含碳产物选择性

Figure 10. The selectivity of carbon containing products of bifunctional catalyst composed of HZSM-5 and Cu/ZnO/Al₂O₃ with different mass ratios

下载: 全尺寸图片幻灯片

表 1 不同方法合成的HZSM-5分子筛的织构特征

Table 1. Summary of the textural properties of HZSM-5 synthesized by different methods

Sample	S_BET/(m²·g⁻¹)	V_total/(cm³·g⁻¹)	d_ave/nm	S_micro/(m²·g⁻¹)	V_micro/(cm³·g⁻¹)
TH-HZSM-5	399	0.30	3.03	315	0.15
SD-HZSM-5	380	0.26	2.77	288	0.13
SAC-HZSM-5	416	0.30	2.86	335	0.16
AC-HZSM-5	422	0.33	3.11	371	0.17
Notes: S_BET—BET(Brunner-Emmet-Teller) specific surface area; V_total—total pore volume; d_ave—average pore size; S_micro—microporous surface area; V_micro—microporous volume; TH-HZSM-5, SD-HZSM-5, SAC-HZSM-5, AC-HZSM-5—HZSM-5 synthesized by traditional hydrothermal, seed-directed, steam-assisted crystallization and aerosol crystallization method, respectively.

下载: 导出CSV

表 2 不同方法合成的HZSM-5的组成及硅铝比

Table 2. The composition and molar ratio of SiO₂/Al₂O₃ of HZSM-5 synthesized by different methods

Sample	SiO₂/wt%	Al₂O₃/wt%	Na₂O/wt%	Other impurity/wt%	SiO₂/Al₂O₃ molar ratio
TH-HZSM-5	89.86	3.63	0.66	5.85	42
SD-HZSM-5	93.20	3.43	0.92	2.45	46
SAC-HZSM-5	92.30	3.42	0.74	3.54	46
AC-HZSM-5	92.49	3.40	0.82	3.29	46

下载: 导出CSV

表 3 不同方法合成HZSM-5的酸量

Table 3. The amount of acid site of HZSM-5 synthesized by different methods

Sample	Amount of desorbed NH₃/(mmol·g⁻¹)
Sample	Weak acid	Strong acid	Total acid
TH-HZSM-5	0.13	0.09	0.22
SD-HZSM-5	0.08	0.04	0.12
SAC-HZSM-5	0.22	0.18	0.40
AC-HZSM-5	0.24	0.20	0.44

下载: 导出CSV

[1]	LI J, WU T, CHENG C, et al. A review of the research progress and application of key components in the hydrogen fuel cell system[J]. Processes, 2024, 12(2): 249-277. doi: 10.3390/pr12020249
[2]	YANG M, MEN Y, LI S L, et al. Enhancement of catalytic activity over TiO₂-modifed Al₂O₃ and ZnO-Cr₂O₃ composite catalyst for hydrogen production via dimethyl ether steam reforming[J]. Appl Catal A: Gen, 2012, 433-434: 26-34. doi: 10.1016/j.apcata.2012.04.032
[3]	高天宇, 赵永华, 郑择, 等. 酸活化蒙脱土在二甲醚水蒸气重整制氢中的应用[J]. 燃料化学学报, 2021, 49(10): 1498-1503. GAO Tianyu, ZHAO Yonghua, ZHENG Ze, et al. Acid activation of montmorillonite and its application for production of hydrogen via steam reforming of dimethyl ether[J]. J Fuel Chem Technol, 2021, 49(10): 1498-1503 (in Chinese).
[4]	WEI S, LI C, REN H, et al. Design and optimization of hydrogen production system model for dimethyl ether self-heating steam reforming[J]. International Journal of Hydrogen Energy, 2024, 49: 1450-1467. doi: 10.1016/j.ijhydene.2023.08.369
[5]	YANG W W, MA X, TANG X Y, et al. Review on developments of catalytic system for methanol steam reforming from the perspective of energy-mass conversion[J]. Fuel, 2023, 345: 128234. doi: 10.1016/j.fuel.2023.128234
[6]	LI J, ZHANG Q J, LONG X, et al. Hydrogen production for fuel cells via steam reforming of dimethyl ether over commercial Cu/ZnO/Al₂O₃ and zeolite[J]. Chem Eng J, 2012, 187: 299-305. doi: 10.1016/j.cej.2012.01.126
[7]	GAO T Y, ZHAO Y H, ZHANG Q J, et al. Zinc oxide modified HZSM-5 as an efficient acidic catalyst for hydrogen production by steam reforming of dimethyl ether[J]. React Kinet Mech Catal, 2019, 128: 235-249. doi: 10.1007/s11144-019-01642-5
[8]	LONG X, SONG Y H, LIU Z T, et al. Insights into the long-term stability of the magnesia modified H-ZSM-5 as an efficient solid acid for steam reforming of dimethyl ether[J]. Int J Hydrog Energy, 2019, 44: 21481-21494. doi: 10.1016/j.ijhydene.2019.06.177
[9]	NISHIGUCHI T, OKA K, MATSUMOTO T, et al. Durability of WO₃/ZrO₂-CuO/CeO₂ catalysts for steam reforming of dimethyl ether[J]. Appl Catal A: Gen, 2006, 301: 66-74. doi: 10.1016/j.apcata.2005.11.011
[10]	LUO H X, ZHAO Y H, ZHANG Q J, et al. The role of promoters in Cu/Acid-MMT catalysts for production of hydrogen via steam reforming of dimethyl ether[J]. J Chem Technol Biotechnol, 2023, 98: 718-725. doi: 10.1002/jctb.7275
[11]	FAUNGNAWAKIJ K, KIKUCHI R, SHIMODA N, et al. Effect of thermal treatment on activity and durability of CuFe₂O₄-Al₂O₃ composite catalysts for steam re-forming of dimethyl ether[J]. Angew Chem Int Ed, 2008, 47: 9314-9317. doi: 10.1002/anie.200802809
[12]	LIU Y, HAN S Y, GUAN D D, et al. Rapid green synthesis of ZSM-5 zeolite from leached illite clay[J]. Micropor Mesopor Mat, 2019, 280: 324-330. doi: 10.1016/j.micromeso.2019.02.027
[13]	HAN S Y, LIU Y, YIN C R, et al. Fast synthesis of submicron ZSM-5 zeolite from leached illite clay using a seed-assisted method[J]. Micropor Mesopor Mat, 2019, 275: 223-228. doi: 10.1016/j.micromeso.2018.08.028
[14]	LIU H Y, YUE Y Y, SHEN T, et al. Transformation and crystallization behaviors of titanium species in synthesizing Ti-ZSM-5 zeolites from natural rectorite mineral[J]. Ind Eng Chem Res, 2019, 58(27): 11861-11870. doi: 10.1021/acs.iecr.9b01826
[15]	PAN F, LU X C, YAN Y, et al. Synthesis of nano/micro scale ZSM-5 from kaolin and its catalytic performance[J]. Kinet Catal, 2017, 58(5): 541-548. doi: 10.1134/S0023158417050184
[16]	蔡玉福, 周艳军, 路君凤, 等. 碱活化蒙脱土负载铁类芬顿体系去除亚甲基蓝[J]. 复合材料学报, 2023, 40(8): 4601-4612. CAI Yufu, ZHOU Yanjun, LU Junfeng, et al. Removal of methylene blue by Fenton-like system with alkali-activated montmorillonite supported iron catalyst[J]. Acta Materiae Compositae Sinica, 2023, 40(8): 4601-4612(in Chinese).
[17]	ZHAO Y H, GAO T Y, WANG Y J, et al. Zinc supported on alkaline activated HZSM-5 for aromatization reaction[J]. React Kinet Mech Catal, 2018, 125: 1085-1098. doi: 10.1007/s11144-018-1426-9
[18]	王荧光, 桂建舟, 张晓彤, 等. 纳米ZSM-5分子筛的合成与表征[J]. 光谱实验室, 2005, 22(2): 225-229. doi: 10.3969/j.issn.1004-8138.2005.02.001 WANG Yingguang, GUI Jianzhou, ZHANG Xiaotong, et al. Synthesis and characterization of nanosized ZSM-5 zeolite[J]. Chinese J Spectrosc Lab, 2005, 22(2): 225-229 (in Chinese). doi: 10.3969/j.issn.1004-8138.2005.02.001
[19]	XIAO W Y, WANG F, Xiao G M. Performance of hierarchical HZSM-5 zeolites prepared by NaOH treatments in the aromatization of glycerol[J]. RSC Adv, 2015, 5: 63697-63704. doi: 10.1039/C5RA07593A
[20]	LUO C W, HUANG C, LI A, et al. Influence of reaction parameters on the catalytic performance of alkaline-treated zeolites in the novel synthesis of pyridine bases from glycerol and ammonia[J]. Ind Eng Chem Res, 2016, 55: 893-911. doi: 10.1021/ie504934n
[21]	SHIRAZI L, JAMSHIDI E, GHASEMI M R. The effect of Si/Al ratio of ZSM-5 zeolite on its morphology, acidity and crystal size[J]. Cryst Res Technol, 2008, 43: 1300-1306. doi: 10.1002/crat.200800149
[22]	ZHANG S G, HIGASHIMOTO S, YAMASHITA H, et al. Characterization of vanadium oxide/ZSM-5 zeolite catalysts prepared by the solid-state reaction and their photocatalytic reactivity. In situ photoluminescence, XAFS, ESR, FT-IR, and UV-Vis Investigations[J]. J Phys Chem B, 1998, 102: 5590-5594. doi: 10.1021/jp981230r
[23]	DUMITRIU D, BÂRJEGA R, FRUNZA L, et al. BiOx clusters occluded in a ZSM-5 matrix: preparation, characterization, and catalytic behavior in liquid-phase oxidation of hydrocarbons[J]. J Catal, 2003, 219: 337-351. doi: 10.1016/S0021-9517(03)00216-1
[24]	THOMMES M, KANEKO K, NEIMARK A V, et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report)[J]. Pure Appl Chem, 2015, 87: 1051-1069. doi: 10.1515/pac-2014-1117
[25]	FAUNGNAWAKIJ K, TANAKA Y, SHIMODA N, et al. Influence of solid-acid catalysts on steam reforming and hydrolysis of dimethyl ether for hydrogen production[J]. Appl Catal A: Gen, 2006, 304: 40-48. doi: 10.1016/j.apcata.2006.02.021
[26]	SEMELSBERGER T A, OTT K C, BORUP R L, et al. Generating hydrogen-rich fuel-cell feeds from dimethyl ether (DME) using physical mixtures of a commercial Cu/Zn/Al₂O₃ catalyst and several solid-acid catalysts[J]. Appl Catal B: Environ, 2006, 65(3-4): 291-300. doi: 10.1016/j.apcatb.2006.02.015