改性HZSM-5/Cu-ZnO-Al2O3 催化剂用于二甲醚水蒸气重整制氢

doi:10.11901/1005.3093.2024.239

材料研究学报

2025, Vol. 39

Issue (4): 251-258 DOI: 10.11901/1005.3093.2024.239

研究论文

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改性HZSM-5/Cu-ZnO-Al₂O₃ 催化剂用于二甲醚水蒸气重整制氢

张森晗, 王欢, 张家慷, 冯效迁, 张启俭, 赵永华(

)

辽宁工业大学化学与环境工程学院锦州 121001

Alkali-modified HZSM-5 Zeolite/Cu-ZnO-Al₂O₃ Bifunctional Catalyst for Hydrogen Production via Steam Reforming of Dimethyl Ether

ZHANG Senhan, WANG Huan, ZHANG Jiakang, FENG Xiaoqian, ZHANG Qijian, ZHAO Yonghua(

)

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

引用本文:

张森晗, 王欢, 张家慷, 冯效迁, 张启俭, 赵永华. 改性HZSM-5/Cu-ZnO-Al₂O₃ 催化剂用于二甲醚水蒸气重整制氢[J]. 材料研究学报, 2025, 39(4): 251-258.
Senhan ZHANG, Huan WANG, Jiakang ZHANG, Xiaoqian FENG, Qijian ZHANG, Yonghua ZHAO. Alkali-modified HZSM-5 Zeolite/Cu-ZnO-Al₂O₃ Bifunctional Catalyst for Hydrogen Production via Steam Reforming of Dimethyl Ether[J]. Chinese Journal of Materials Research, 2025, 39(4): 251-258.

全文: PDF(4369 KB) HTML

摘要:

用不同浓度的NaOH溶液对HZSM-5进行改性，然后作为固体酸与Cu-ZnO-Al₂O₃催化剂物理混合制备出改性HZSM-5/Cu-ZnO-Al₂O₃催化剂，并将其用于二甲醚水蒸气重整制氢(SRD)。采用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、扫描电子显微镜(SEM)、N₂低温吸附-脱附和NH₃程序升温脱附(NH₃-TPD)等手段表征改性HZSM-5样品及其SRD性能。结果表明，改变NaOH的浓度可调控HZSM-5的酸性和结构性质，进而影响固体酸双功能催化剂的SRD性能。用0.4 mol/L NaOH溶液改性的HZSM-5-0.4与Cu-ZnO-Al₂O₃组成的双功能催化剂性能良好，在温度为350 ℃、压力为0.1 MPa、空速为3000 mL/(g·h)条件下，初始二甲醚转化率和氢气收率分别为100%和93%，且在反应10 h内性能没有显著降低，表明其稳定性较高。

关键词 ：复合材料, 碱改性HZSM-5, 水蒸气重整, 二甲醚, 制氢

Abstract：

A series of alkali-modified HZSM-5 zeolite were prepared via chemical treatment of the parent HZSM-5 with NaOH solution of different concentrations. And then, as solid acid, the alkali-modified HZSM-5 was physically mixed with commercial Cu-ZnO-Al₂O₃ to obtain bifunctional catalysts of HZSM-5 zeolite/Cu-ZnO-Al₂O₃ for steam reforming of dimethyl ether (SRD) reaction. The products were systematically characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), N₂ adsorption-desorption at low temperature, and NH₃ temperature-programmed desorption (NH₃-TPD) techniques. The results showed that the acidity and structure of the HZSM-5 could be effectively adjusted by altering the concentration of NaOH, and then affecting the SRD performance of the corresponding bifunctional catalyst. The bifunctional catalyst composed of the HZSM-5-0.4 treated by 0.4 mol/L NaOH and Cu-ZnO-Al₂O₃ exhibited the best SRD performance, i.e., the initial dimethyl ether conversion and H₂ yield reached 100% and 93% under the conditions of reaction temperature 350 ^oC, pressure 0.1 MPa, space velocity 3000 mL/(g·h), respectively, and dimethyl ether conversion and H₂ yield remained basically constant in 10 h, indicating that the catalyst had better stability.

Key words： composite alkali-modified HZSM-5 steam reforming dimethyl ether hydrogen production

收稿日期: 2024-05-27

ZTFLH:

O643.3

基金资助:国家自然科学基金(22075120);辽宁省应用基础研究计划(2023JH2/101300216)

通讯作者: 赵永华，教授，lgdzyh@163.com，研究方向为多相催化与能源化学

Corresponding author: ZHAO Yonghua, Tel: (0416)4199013, E-mail: lgdzyh@163.com

作者简介: 张森晗，女，2000年生，硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2024.239 或 https://www.cjmr.org/CN/Y2025/V39/I4/251

图1 不同HZSM-5-m的XRD谱

Samples	BET surface area / m²·g^-1	Pore volume / cm³·g^-1	Average pore size / nm	Relative crystallinity^a / %	I₅₄₆ / I $451 b$
HZSM-5	397	0.20	1.99	100	0.79
HZSM-5-0.2	353	0.34	2.86	85.8	0.41
HZSM-5-0.4	214	0.55	10.17	31.8	0.12
HZSM-5-0.5	71	0.79	16.34	4.3	0.01

表1 HZSM-5-m的结构和织构特征

图2 不同HZSM-5-m的FT-IR谱

图3 不同HZSM-5-m的N2吸脱附等温线

图4 不同HZSM-5-m的孔径分布

图5 不同HZSM-5-m的SEM照片

图6 不同HZSM-5-m的NH3-TPD谱

图7 HZSM-5-m/Cu-ZnO-Al2O3双功能催化剂的DME转化率和H2收率

图8 HZSM-5-m/Cu-ZnO-Al2O3双功能催化剂的含碳产物选择性

1	Bernay C, Marchand M, Cassir M. Prospects of different fuel cell technologies for vehicle applications [J]. J. Power Sources, 2002, 108(1-2): 139
2	Gao T Y, Zhao Y H, Zheng Z, 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): 1495
2	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): 1495
3	Yang M, Men Y, Li S L, et al. Enhancement of catalytic activity over TiO₂-modified Al₂O₃ and ZnO-Cr₂O₃ composite catalyst for hydrogen production via dimethyl ether steam reforming [J]. Appl. Catal., 2012, 433-434A: 26
4	Singh S, Jain S, Venkateswaran P S, et al. Hydrogen: a sustainable fuel for future of the transport sector [J]. Renew. Sustain. Energy Rev., 2015, 51: 623
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
6	Long X, Zhang Q J, Liu Z T, et al. Magnesia modified H-ZSM-5 as an efficient acidic catalyst for steam reforming of dimethyl ether [J]. Appl. Catal., 2013, 134-135B: 381
7	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
8	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
9	Tanaka Y, Kikuchi R, Takeguchi T, et al. Steam reforming of dimethyl ether over composite catalysts of γ-Al₂O₃ and Cu-based spinel [J]. Appl. Catal., 2005, 57B: 211
10	Nishiguchi T, Oka K, Matsumoto T, et al. Durability of WO₃/ZrO₂-CuO/CeO₂ catalysts for steam reforming of dimethyl ether [J]. Appl. Catal., 2006, 301A(1) : 66
11	Faungnawakij K, Kikuchi R, Shimoda N, et al. Effect of thermal treatment on activity and durability of CuFe₂O₄-Al₂O₃ composite catalysts for steam reforming of dimethyl ether [J]. Angew. Chem. Int. Ed., 2008, 47: 9314 doi: 10.1002/anie.200802809 pmid: 18979476
12	Deng X Q, Yang T T, Zhang Q, et al. A monolith CuNiFe/γ-Al₂O₃/Al catalyst for steam reforming of dimethyl ether and applied in a microreactor [J]. Int. J. Hydrog. Energy, 2019, 44(5): 2417
13	Kim D, Park G, Choi B, et al. Reaction characteristics of dimethyl ether (DME) steam reforming catalysts for hydrogen production [J]. Int. J. Hydrog. Energy, 2017, 42(49): 29210
14	Shimoda N, Faungnawakij K, Kikuchi R, et al. Degradation and regeneration of copper-iron spinel and zeolite composite catalysts in steam reforming of dimethyl ether [J]. Appl. Catal., 2010, 378A: 234
15	Sheng Q T, Niu Y X, Shen J, et al. Influence of modification methods on porosity, acidity and catalytic properties of HZSM-5 zeolite in dehydration ethanol to ethylene [J]. Acta Pet. Sin. (Pet. Process. Sect.), 2017, 33(2): 242
15	盛清涛, 牛艳霞, 申峻等. 改性方法对HZSM-5分子筛孔结构、酸性质及乙醇脱水制乙烯催化性能的影响 [J]. 石油学报(石油加工), 2017, 33(2): 242
16	Wei Z H, Xia T F, Liu M H, et al. Alkaline modification of ZSM-5 catalysts for methanol aromatization: The effect of the alkaline concentration [J]. Front. Chem. Sci. Eng., 2015, 9(4): 450 doi: 10.1007/s11705-015-1542-2
17	Ahmadpour J, Taghizadeh M. Selective production of propylene from methanol over high-silica mesoporous ZSM-5 zeolites treated with NaOH and NaOH/tetrapropylammonium hydroxide [J]. C. R. Chim., 2015, 18: 834
18	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
19	Sadowska K, Góra-Marek K, Drozdek M, et al. Desilication of highly siliceous zeolite ZSM-5 with NaOH and NaOH/tetrabutylamine hydroxide [J]. Microporous Mesoporous Mater., 2013, 168: 195
20	Wang Y G, Gui J Z, Zhang X T, et al. Synthesis and characterization of nanosized ZSM-5 zeolite [J]. Chin. J. Spectrosc. Lab., 2005, 22(2): 225
20	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
21	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
22	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
23	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
24	Dumitriu D, Bârjega R, Frunza L, et al. BiO _x clusters occluded in a ZSM-5 matrix: preparation, characterization, and catalytic behavior in liquid-phase oxidation of hydrocarbons [J]. J. Catal., 2003, 219: 337
25	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
26	Wang Q, Cui Z M, Cao C Y, et al. 0.3 Å makes the difference: dramatic changes in methanol-to-olefin activities between H-ZSM-12 and H-ZSM-22 zeolites [J]. J. Phys. Chem. C, 2011, 115: 24987
27	Luo H X, Zhao Y H, Zhang J K, et al. Oxide-pillared montmorillonite supported Cu catalyst for production of hydrogen via steam reforming of dimethyl ether [J]. Chin. J. Mater. Res., 2024， 38 (11): 872
27	罗洪旭, 赵永华, 张家慷等. 双功能催化剂(Cu-Co/X-MMT)的制备和性能 [J]. 材料研究学报, 2024， 38 (11): 872 doi: 10.11901/1005.3093.2023.493
28	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., 2006, 304A: 40

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