Progress on hydrogen production from catalytic steam reforming of aromatic hydrocarbons

doi:10.16085/j.issn.1000-6613.2021-0452

Abstract

Abstract:

Hydrogen energy as a kind of clean energy has the advantages of environmental friendly, zero pollution and zero carbon emission. The steam reforming of aromatics with vast raw materials has a high hydrogen production per unit volume and shows great application value in tar removal and upgrading, portable hydrogen production, etc. The core of aromatics steam reforming is the development of high performance catalysts. Firstly, the progresses of aromatics reforming kinetics and mechanism were summarized mainly from the aspects of reaction characteristics, reaction network, kinetic model construction, adsorption and dissociation. It was considered that the key to deepening the understanding of kinetic process and mechanism was the integration of thermodynamic theoretical calculations, advanced in-situ characterization technologies and rigorous logical demonstration experiments. Then, various active components, supports and promoters of catalysts for aromatics steam reforming were reviewed according to the classification of supported catalysts components. Based on the nickel-based bimetallic synergy, strong oxygen storage-release capacity of perovskite supporters and acidity regulation of alkaline additives, the development of nickel-based bimetallic supported perovskite catalysts promoted by the alkaline additives was proposed.

Key words: aromatic hydrocarbon, reforming, hydrogen production, catalyst, reaction dynamics and mechanism

摘要：

氢能是一种清洁的二次能源，具有绿色环保、零污染、零碳排放等优点。芳烃蒸汽重整制氢原料来源广、单位体积原料产氢量高，在重油焦油清除升级、便携式移动制氢等领域极具应用价值，其核心在于高性能催化剂的开发。文章首先从芳烃重整反应特性、反应网络、动力学模型构建和吸附解离等方面对其反应动力学及机理进行了概述，认为采用热力学理论计算、先进的原位表征技术和严密的逻辑论证实验等综合手段是加深反应动力学和机理认知的关键；其次，按照催化剂组成分类，评述了不同活性组分、载体及助剂的特点，基于镍基双金属活性组分的协同效应、钙钛矿载体的强储/释氧能力和碱性助剂的酸调控作用，指出碱性助剂改性的负载型镍基双金属钙钛矿催化剂是其发展方向。

关键词: 芳烃, 重整, 制氢, 催化剂, 反应动力学及机理

CLC Number:

TQ116.2

LIU Jiahui, SUN Dao’an, DU Yongmei, LI Chunying, LIU Zhaotie, LYU Jian. Progress on hydrogen production from catalytic steam reforming of aromatic hydrocarbons[J]. Chemical Industry and Engineering Progress, 2021, 40(9): 4782-4790.

刘嘉辉, 孙道安, 杜咏梅, 李春迎, 刘昭铁, 吕剑. 芳烃蒸汽催化重整制氢研究进展[J]. 化工进展, 2021, 40(9): 4782-4790.

Figures/Tables 4

References 50

1	王治斌, 孙来芝, 陈雷, 等. 生物油水蒸气催化重整制氢研究进展[J]. 化工进展, 2021, 40(1): 151-163.
	WANG Z B, ZHANG L Z, CHEN L, et al. Progress in hydrogen production by steam catalytic reforming of bio-oil[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 151-163.
2	乔韦军, 肖国鹏, 张磊, 等. 甲醇水蒸气重整制氢CuO/La_1－_xCe_xCrO₃催化剂[J]. 燃料化学学报, 2021, 49(2): 205-210.
	QIAO Weijun, XIAO Guopeng, ZHANG Lei, et al. Catalytic performance of CuO/La_1－_xCe_xCrO₃ in the steam reforming of methanol[J]. Journal of Fuel Chemistry and Technology, 2021, 49(2): 205-210.
3	刘太楷, 邓春明, 张亚鹏. 电解水制氢发展概况之一: 碱式电解水[J]. 材料研究与应用, 2019, 13(4): 339-346.
	LIU Taikai, DENG Chunming, ZHANG Yapeng. Development of hydrogen generation via water electrolysis Ⅰ‍: Alkaline water electrolysis[J]. Materials Research and Application, 2019, 13(4): 339-346.
4	SARıOĞLAN A. Tar removal on dolomite and steam reforming catalyst: benzene, toluene and xylene reforming[J]. International Journal of Hydrogen Energy, 2012, 37(10): 8133-8142.
5	QIAN K Z, KUMAR A. Catalytic reforming of toluene and naphthalene (model tar) by char supported nickel catalyst[J]. Fuel, 2017, 187: 128-136.
6	GAO N B, WANG X, LI A M, et al. Hydrogen production from catalytic steam reforming of benzene as tar model compound of biomass gasification[J]. Fuel Processing Technology, 2016, 148: 380-387.
7	LU M, XIONG Z H, FANG K J, et al. Steam reforming of toluene over nickel catalysts supported on coal gangue ash[J]. Renewable Energy, 2020, 160: 385-395.
8	JIAO Y, ZHANG J, DU Y M, et al. Hydrogen-rich syngas production by toluene reforming in a microchannel reactor coated with Ni/MgO-Al₂O₃ multifunctional catalysts[J]. Industrial & Engineering Chemistry Research, 2019, 58(43): 19794-19802.
9	TAKISE K, IMORI M, MUKAI D, et al. Effect of catalyst structure on steam reforming of toluene over Ni/La_0.7Sr_0.3AlO_3-_δ catalyst[J]. Applied Catalysis A: General, 2015, 489: 155-161.
10	ZHANG Z H, OU Z L, QIN C L, et al. Roles of alkali/alkaline earth metals in steam reforming of biomass tar for hydrogen production over perovskite supported Ni catalysts[J]. Fuel, 2019, 257: 116032.
11	AHMED T, XIU S N, WANG L J, et al. Investigation of Ni/Fe/Mg zeolite-supported catalysts in steam reforming of tar using simulated-toluene as model compound[J]. Fuel, 2018, 211: 566-571.
12	BAMPENRAT A, MEEYOO V, KITIYANAN B, et al. Naphthalene steam reforming over Mn-doped CeO₂-ZrO₂ supported nickel catalysts[J]. Applied Catalysis A: General, 2010, 373(1/2): 154-159.
13	DU Z Y, ZHANG Z H, XU C, et al. Low-temperature steam reforming of toluene and biomass tar over biochar-supported Ni nanoparticles[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(3): 3111-3119.
14	ZOU X H, CHEN T H, ZHANG P, et al. High catalytic performance of Fe-Ni/palygorskite in the steam reforming of toluene for hydrogen production[J]. Applied Energy, 2018, 226: 827-837.
15	NORINAGA K, SAKURAI Y, SATO R, et al. Numerical simulation of thermal conversion of aromatic hydrocarbons in the presence of hydrogen and steam using a detailed chemical kinetic model[J]. Chemical Engineering Journal, 2011, 178: 282-290.
16	KAISALO N, SIMELL P, LEHTONEN J. Benzene steam reforming kinetics in biomass gasification gas cleaning[J]. Fuel, 2016, 182: 696-703.
17	OH G, PARK S Y, SEO M W, et al. Ni/Ru-Mn/Al₂O₃ catalysts for steam reforming of toluene as model biomass tar[J]. Renewable Energy, 2016, 86: 841-847.
18	LU M, XIONG Z H, FANG K J, et al. Effect of promoters on steam reforming of toluene over a Ni-based catalyst supported on coal gangue ash[J]. ACS Omega, 2020, 5(41): 26335-26346.
19	MEI D H, LEBARBIER V M, ROUSSEAU R, et al. Comparative investigation of benzene steam reforming over spinel supported Rh and Ir catalysts[J]. ACS Catalysis, 2013, 3(6): 1133-1143.
20	GHADAMI YAZDI M, MOUD P H, MARKS K, et al. Naphthalene on Ni(111): experimental and theoretical insights into adsorption, dehydrogenation, and carbon passivation[J]. The Journal of Physical Chemistry C, 2017, 121(40): 22199-22207.
21	DE CASTRO T P, SILVEIRA E B, RABELO-NETO R C, et al. Study of the performance of Pt/Al₂O₃ and Pt/CeO₂/Al₂O₃ catalysts for steam reforming of toluene, methane and mixtures[J]. Catalysis Today, 2018, 299: 251-262.
22	ZHOU S Y, CHEN Z Z, GONG H J, et al. Low-temperature catalytic steam reforming of toluene as a biomass tar model compound over three-dimensional ordered macroporous Ni-Pt/Ce_1-_xZr_xO₂ catalysts[J]. Applied Catalysis A: General, 2020, 607: 117859.
23	MUKAI D, MURAI Y, HIGO T, et al. Effect of Pt addition to Ni/La_0.7Sr_0.3AlO_3-_δ catalyst on steam reforming of toluene for hydrogen production[J]. Applied Catalysis A: General, 2014, 471: 157-164.
24	TAKISE K, HIGO T, MUKAI D, et al. Highly active and stable Co/La_0.7Sr_0.3AlO_3-_δcatalyst for steam reforming of toluene[J]. Catalysis Today, 2016, 265: 111-117.
25	SUGIURA Y, MUKAI D, MURAI Y, et al. Oxidation resistance of Ni/La_0.7Sr_0.3AlO_3-_δcatalyst for steam reforming of model aromatic hydrocarbon[J]. International Journal of Hydrogen Energy, 2013, 38(19): 7822-7829.
26	FURUSAWA T, SAITO K, KORI Y, et al. Steam reforming of naphthalene/benzene with various types of Pt- and Ni-based catalysts for hydrogen production[J]. Fuel, 2013, 103: 111-121.
27	赵效勇, 闫常峰, 张亮. Ni/CeO₂-ZrO₂@SiO₂核壳结构型催化剂对甲苯催化重整研究[J]. 新能源进展, 2017, 5(4): 272-278.
	ZHAO Xiaoyong, YAN Changfeng, ZHANG Liang. Catalytic activity of Ni/CeO₂-ZrO₂@SiO₂ core-shell structure for steam reforming of toluene[J]. Advances in New and Renewable Energy, 2017, 5(4): 272-278.
28	BELBESSAI S, ACHOURI I E, BENYOUSSEF E H, et al. Toluene steam reforming using nickel based catalysts made from mining residues[J]. Catalysis Today, 2021, 365: 111-121.
29	WANG X B, YANG S Q, XU C, et al. Effect of boron doping on the performance of Ni/biochar catalysts for steam reforming of toluene as a tar model compound[J]. Journal of Analytical and Applied Pyrolysis, 2021, 155: 105033.
30	HU S, HE L M, WANG Y, et al. Effects of oxygen species from Fe addition on promoting steam reforming of toluene over Fe-Ni/Al₂O₃ catalysts[J]. International Journal of Hydrogen Energy, 2016, 41(40): 17967-17975.
31	何立模, 胡松, 汪一, 等. 改性镍基催化剂催化甲苯重整与积炭特性研究[J]. 工程热物理学报, 2016, 37(5): 1093-1099.
	HE Limo, HU Song, WANG Yi, et al. Catalytic performance and coke characterization over modified Ni-based catalysts for steam reforming of toluene[J]. Journal of Engineering Thermophysics, 2016, 37(5): 1093-1099.
32	MENG J G, ZHAO Z L, WANG X B, et al. Steam reforming and carbon deposition evaluation of phenol and naphthalene used as tar model compounds over Ni and Fe olivine-supported catalysts[J]. Journal of the Energy Institute, 2019, 92(6): 1765-1778.
33	FERELLA F, STOEHR J, MICHELIS I D, et al. Zirconia and alumina based catalysts for steam reforming of naphthalene[J]. Fuel, 2013, 105: 614-629.
34	陶君, 陆强, 冉泽朋, 等. Ni-CeO₂/γ-Al₂O₃催化甲苯水蒸气重整的实验研究[J]. 可再生能源, 2014, 32(10): 1539-1543.
	TAO Jun, LU Qiang, RAN Zepeng, et al. Experimental research on catalytic steam reforming of toluene using Ni-CeO₂/γ-Al₂O₃ catalysts[J]. Renewable Energy Resources, 2014, 32(10): 1539-1543.
35	HE L M, HU S, JIANG L, et al. Carbon nanotubes formation and its influence on steam reforming of toluene over Ni/Al₂O₃ catalysts: roles of catalyst supports[J]. Fuel Processing Technology, 2018, 176: 7-14.
36	卢雯, 孔猛, 杨琦, 等. 载体对镍基催化剂及其甲苯水蒸气重整性能的影响[J]. 化学反应工程与工艺, 2012, 28(3): 238-243.
	LU Wen, KONG Meng, YANG Qi, et al. Influence of support on catalytic behavior of Ni-based catalysts in steam reforming of toluene[J]. Chemical Reaction Engineering and Technology, 2012, 28(3): 238-243.
37	SILVEIRA E B, RABELO-NETO R C, NORONHA F B. Steam reforming of toluene, methane and mixtures over Ni/ZrO₂ catalysts[J]. Catalysis Today, 2017, 289: 289-301.
38	ABOU RACHED J, HAYEK C EL, DAHDAH E, et al. Ni based catalysts promoted with cerium used in the steam reforming of toluene for hydrogen production[J]. International Journal of Hydrogen Energy, 2017, 42(17): 12829-12840.
39	CLAUDE V, MAHY J G, GEENS J, et al. Synthesis of Ni/γ-Al₂O₃-SiO₂ catalysts with different silicon precursors for the steam toluene reforming[J]. Microporous and Mesoporous Materials, 2019, 284: 304-315.
40	刘晓刚, 魏波, 史芸菲, 等. La_1－_xLi_xMnO₃钙钛矿催化剂同时消除NO和碳烟催化性能[J]. 化工学报, 2020, 71(3): 1053-1059.
	LIU Xiaogang, WEI Bo, SHI Yunfei, et al. Simultaneous removal of NO and soot over La_1－_xLi_xMnO₃ perovskite catalysts[J]. CIESC Journal, 2020, 71(3): 1053-1059.
41	MUKAI D, TOCHIYA S, MURAI Y, et al. Role of support lattice oxygen on steam reforming of toluene for hydrogen production over Ni/La_0.7Sr_0.3AlO_3-_δcatalyst[J]. Applied Catalysis A: General, 2013, 453: 60-70.
42	SEKINE Y, MUKAI D, MURAI Y, et al. Steam reforming of toluene over perovskite-supported Ni catalysts[J]. Applied Catalysis A: General, 2013, 451: 160-167.
43	LIU C L, CHEN D, CAO Y, et al. Catalytic steam reforming of in situ tar from rice husk over MCM-41 supported LaNiO₃ to produce hydrogen rich syngas[J]. Renewable Energy, 2020, 161: 408-418.
44	TANG W, CAO J P, YANG F L, et al. Highly active and stable HF acid modified HZSM-5 supported Ni catalysts for steam reforming of toluene and biomass pyrolysis tar[J]. Energy Conversion and Management, 2020, 212: 112799.
45	BIZKARRA K, BARRIO V L, GARTZIA-RIVERO L, et al. Hydrogen production from a model bio-oil/bio-glycerol mixture through steam reforming using zeolite L supported catalysts[J]. International Journal of Hydrogen Energy, 2019, 44(3): 1492-1504.
46	冉泽朋, 陶君, 陆强, 等. Ni-CeO₂/SBA-15电催化甲苯水蒸气重整的实验研究[J]. 新能源进展, 2014, 2(6): 407-412.
	RAN Zepeng, TAO Jun, LU Qiang, et al. Electric current enhanced catalytic steam reforming of toluene with Ni-CeO₂/SBA-15 catalyst[J]. Advances in New and Renewable Energy, 2014, 2(6): 407-412.
47	HIGO T, SAITO H, OGO S, et al. Promotive effect of Ba addition on the catalytic performance of Ni/LaAlO₃ catalysts for steam reforming of toluene[J]. Applied Catalysis A: General, 2017, 530: 125-131.
48	ASHOK J, KAWI S. Steam reforming of toluene as a biomass tar model compound over CeO₂ promoted Ni/CaO-Al₂O₃ catalytic systems[J]. International Journal of Hydrogen Energy, 2013, 38(32): 13938-13949.
49	BAMPENRAT A, MEEYOO V, KITIYANAN B, et al. Naphthalene steam reforming over Mn-doped CeO₂-ZrO₂ supported nickel catalysts[J]. Applied Catalysis A: General, 2010, 373(1/2): 154-159.
50	HEO D H, LEE R, HWANG J H, et al. The effect of addition of Ca, K and Mn over Ni-based catalyst on steam reforming of toluene as model tar compound[J]. Catalysis Today, 2016, 265: 95-102.

反应物	密度（20℃）/g·cm^－3	理论产氢量/mmol·mL^－1
乙酸	1.050	70.0
二甲醚	0.666	86.7
乙醇	0.789	102.8
正十二烷	0.750	162.9
苯	0.880	169.0
甲苯	0.866	169.2
萘	1.145	214.4

反应物	密度（20℃）/g·cm^－3	理论产氢量/mmol·mL^－1
乙酸	1.050	70.0
二甲醚	0.666	86.7
乙醇	0.789	102.8
正十二烷	0.750	162.9
苯	0.880	169.0
甲苯	0.866	169.2
萘	1.145	214.4

制氢方式	实验室实际产氢量/kg H₂·(kg 原料)^－1	制氢成本/CNY·kg^－1
甲烷重整	0.313	14^①
甲苯重整^②	0.196	20~25^③
碱式电解水	—	40

制氢方式	实验室实际产氢量/kg H₂·(kg 原料)^－1	制氢成本/CNY·kg^－1
甲烷重整	0.313	14^①
甲苯重整^②	0.196	20~25^③
碱式电解水	—	40

反应物	催化剂	反应条件^①	积炭量^②	芳烃转化率/%	H₂收率^③/%	文献
苯	NiO/泡沫陶瓷	750℃，WHSV=5.6h^-1，S/C=2.0	—	85.5	59	［6］
甲苯	Ni/CGA-1d	800℃，WHSV=2.6h^-1，S/C=2.0	0.034g_coke·h·g_cat^－1	91.5	58.2	［7］
甲苯	Ni/MgO-Al₂O₃	650~800℃，WHSV=5.2h^-1，S/C=1.7	2.55~4.86mg·(g C_feed)^－1	95.4	69	［8］
甲苯	Ni/La_0.7Sr_0.3AlO_3-_δ	600℃，WHSV=1.84h^-1，S/C=2.0	9.3mg·g_cat^－1	53.0	49.9	［9］
甲苯	Ni-K/La_0.7Sr_0.3AlO_3-_δ	650℃，WHSV=3.73h^-1，S/C=2.0	7.3mg·g_cat^－1	100	79	［10］
甲苯	Ni-Fe/zeolite	800℃，WHSV=1.0~2.3h^-1，S/C=2.0	—	74	65	［11］
萘	Ni/Ce_0.75Zr_0.25-_xMn_xO₂	700℃，GHSV=20000h^-1，S/C=2.0	(1.1±0.3)mg·g_cat^－1	100（120min）	—	［12］