废弃生物质催化热解制富氢燃气：催化剂性能的影响

李学琴; 刘鹏; 卢岩; 王志伟; 吴幼青; 雷廷宙

doi:10.19906/j.cnki.JFCT.2024011

废弃生物质催化热解制富氢燃气：催化剂性能的影响

doi: 10.19906/j.cnki.JFCT.2024011

李学琴^{1, 2,},
刘鹏^1,,
卢岩^1,,
王志伟^{3, 4},
吴幼青^2,,
雷廷宙^1, ,

1.
常州大学城乡矿山研究院, 江苏常州213164
2.
华东理工大学资源与环境工程学院, 上海 200237
3.
河南工业大学环境工程学院, 河南郑州450001
4.
河南工业大学碳中和研究院, 河南郑州450001

基金项目: 国家重点研发计划（2022YFB4201901）和江苏省碳达峰碳中和科技创新专项资金项目（BE2022426）资助

详细信息

通讯作者:
E-mail: China_newenergy@163.com

中图分类号: TK6
计量
- 文章访问数: 37
- HTML全文浏览量: 15
- PDF下载量: 4
- 被引次数: 0
出版历程
- 收稿日期: 2023-12-25
- 修回日期: 2024-01-31
- 录用日期: 2024-03-20
- 网络出版日期: 2024-03-30

Catalytic pyrolysis of waste biomass to produce hydrogen-rich gas:Influence of catalyst performance

LI Xueqin^{1, 2
,},
LIU Peng^1
,,
LU Yan^1
,,
WANG Zhiwei^{3, 4},
WU Youqing^2
,,
LEI Tingzhou^{1
, ,}

1.
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
2.
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 202162, China
3.
School of Environmental Engineering, Henan University of Technology, Zhengzhou 450001, China
4.
Institute for Carbon Neutrality, Henan University of Technology, Zhengzhou 450001, China

Funds: The project was supported by the National Key Reasearch & Development Program of China (2022YFB4201900) and Carbon reaches peak and carbon neutrality Scientific and technological Innovation of Jiangsu province (BE2022426).

摘要

摘要: 本研究通过超声波辅助过量浸渍法将活性组分镍、助剂铁与HZSM-5分子筛结合来提高富氢燃气的产率；进一步以废弃铝灰与HZSM-5分子筛作为共载体制备铝灰与HZSM-5分子筛符合共载镍-铁催化剂并将其用于强化生物质催化热解产富氢燃气的过程。结果表明，在热解温度700 ℃下，Ni-Fe/HZSM-5可使富氢燃气的产率提高到56.49%（约为230.59 mL/g），氢气产率提高到63.12%，产氢效率提高到0.71%，CO得率增加到65.77 mL/g；足够的Ni-Fe/HZSM-5催化剂量强化了生物质热解的产氢路径，促进了积炭气化反应，起到提高H₂和CO产率的双重作用。不同种类生物质的组成差异导致催化热解的产物分布也不同，Ni-Fe/HZSM-5催化生物质热解气体产率的顺序为PR（74.21%）>WSt（54.71%）>CR（53.5%）>MCh（52.47%）>WSh（52.10%）>CS（46.49%）。HZSM-5和ASA载体间的协同作用强化了CH₄与CO₂的重整过程，抑制了逆水汽变换反应，获得了53.37%和41.56%的气体和焦油产率；并加速了积炭气化反应从而减少了积炭量（0.05g/g），获得了5.07%的半焦产率；Ni-Fe/ASA@HZSM-5具有较好的热裂化能力和脱氧能力，有助于促进HZSM-5催化剂上富氢燃气的生成；为开发高温热解气深度净化与高效利用技术提供理论支撑，有效指导多级催化重整的新型双催化床层的开发。
- HZSM-5 /
- 铝灰 /
- 废弃生物质 /
- 催化热解 /
- 富氢燃气
Abstract: Catalytic pyrolysis of waste biomass is a promising method for the production of hydrogen-rich gas. HZSM-5 carrier is the premise of ensuring the thermal stability and long life of catalytic materials, and plays a mechanical role in bearing the active component nickel（Ni）. At the same time, aluminum ash, as an important waste in the production process of aluminum industry, is mainly composed of Al₂O₃ and a large number of heavy metal oxides such as Na₂O, CaO, MgO, Fe₂O₃ and so on. In this study, aiming at the technical bottleneck problems such as the low performance of traditional HZSM-5 molecular sieve and the difficulty of resource utilization of aluminum ash, the active component nickel (Ni) and promoter iron (Fe) were combined with HZSM-5 molecular sieve by ultrasonic-assisted excessive impregnation to improve the yield of hydrogen-rich gas. Furthermore, waste aluminum ash (ASA) and HZSM-5 molecular sieve were used as co-carriers to prepare aluminum ash co-supported Ni-Fe catalyst with HZSM-5 molecular sieve, and it was used to enhance the process of hydrogen-rich gas production by the catalytic pyrolysis of biomass. The results showed that the heat transfer efficiency decreased with the increase of heating rate during pyrolysis of biomass. After compensation, the apparent kinetic parameters (E and A) of pyrolysis of different biomass were obtained. At the pyrolysis temperature of 700 ℃, Ni-Fe/HZSM-5 catalyst increases the yield of hydrogen-rich gas to 56.49% (about 230.59 mL/g), hydrogen yield to 63.12%, hydrogen production efficiency to 0.71%, and CO yield to 65.77 mL/g. Sufficient amount of Ni-Fe/HZSM-5 catalyst enhanced the pathway of hydrogen production by the catalytic pyrolysis of biomass, promoted the gasification reaction of carbon deposition, and played a dual role in increasing the yield of H₂ and CO. The synergism between HZSM-5 and ASA carriers enhanced the reforming process of CH₄ and CO₂, inhibited the reverse water vapor shift reaction, obtained 53.37% and 41.56% gas and tar yields. At the same time, the gasification reaction of carbon deposition was also accelerated, reduced the char yield to 5.07%, and obtained the carbon deposition of 0.05 g/g. Ni-Fe/ASA@HZSM-5 has good thermal cracking ability and deoxidization ability, which is helpful to promote the formation of hydrogen-rich gas on HZSM-5 as a base catalyst. From the point of view of proximate analysis and chemical composition of biomass, the composition of different kinds of biomass varies greatly, and the product distribution of catalytic pyrolysis also has a great influence. The order of gas yield of pyrolysis of biomass catalyzed by Ni-Fe/HZSM-5 was PR (74.21%)>WSt (54.71%)>CR (53.5%)>MCh (52.47%)>WSh (52.10%)>CS (46.49%)., which provides theoretical support for the development of deep purification and efficient utilization of high temperature pyrolysis gas, and effectively guides the development of a new double catalytic bed for multi-stage catalytic reforming.
- HZSM-5 /
- aluminum ash /
- waste biomass /
- catalytic pyrolysis /
- hydrogen-rich gas

HTML全文

图 1 新鲜催化剂的SEM谱图

Figure 1 SEM spectrum of fresh catalyst

下载: 全尺寸图片幻灯片

图 2 生物质热解反应的装置

Figure 2 Device for the biomass pyrolysis reaction

下载: 全尺寸图片幻灯片

图 3 不同升温速率下玉米秸秆（a）麻栗壳（b）椿木屑（c）核桃壳（d）麦秸秆（e）杨木屑（f）的TG/DTG曲线

Figure 3 TG/DTG curve of CS(a), MCh(b), CR(c), WSh(d), WSt(e), PR(f) at different heating rates

下载: 全尺寸图片幻灯片

图 4 热解温度对产物分布规律的影响（a）三相产物分布（b）气体得率

Figure 4 Effect of pyrolysis temperature on product distribution(a) three-phase product distribution (b) gas yield

下载: 全尺寸图片幻灯片

图 5 催化剂用量对玉米秸秆热解释放气体速率的影响

Figure 5 Effect of catalytic dosage on gas release from pyrolysis of CS

下载: 全尺寸图片幻灯片

图 6 催化剂用量对产物分布的影响（a）气体产率（b）液体产物分布

注：酸类物质（Acid, AC）、酮类物质（Ketones, KE）、醛类物质（Aldehydes, AL）、醇类物质（Alcohol, ALc）、酚类物质（Phenolic, PH）、呋喃类物质（Furan, FU）、酯类物质（Esters, ES）、烷烃类物质（Alkyl hydrocarbons, ALk）、其他（other）

Figure 6 Effect of catalytic dosage on products distribution (a) Gas yield (b) distribution of liquid products

下载: 全尺寸图片幻灯片

图 7 催化剂类型对热解产物分布的影响

Figure 7 Effect of catalyst types on the distribution of pyrolysis products

下载: 全尺寸图片幻灯片

图 8 HZSM-5分子筛的多孔道结构

Figure 8 Porous structure of HZSM-5

下载: 全尺寸图片幻灯片

图 9 催化剂类型对玉米秸秆热解气体产物及氢碳转化率的影响（a）气体产物得率（b）氢、碳得率

Figure 9 Effects of catalyst types on gas products and conversion of H, C (a) gas yield (b) yield of H and C

下载: 全尺寸图片幻灯片

图 10 不同催化剂催化玉米秸秆热解的液体产物分布

Figure 10 Liquid product distribution of CS pyrolysis catalyzed by different catalysts

下载: 全尺寸图片幻灯片

图 11 不同催化剂催化玉米秸秆热解的产物分布规律

Figure 11 Effect of five catalysts on the product distribution of CS pyrolysis

下载: 全尺寸图片幻灯片

图 12 催化生物质热解的产物分布（a）三相产物分布（b）气体产率

Figure 12 Product distribution of catalytic pyrolysis of biomass(a)three-phase product distribution (b) gas yield

下载: 全尺寸图片幻灯片

图 13 催化生物质热解的产物分布规律

Figure 13 Product distribution rules for catalytic pyrolysis of biomass

下载: 全尺寸图片幻灯片

表 1 新鲜催化剂的物理特性及孔道特性

Table 1 Physical properties and pore distribution of fresh catalysts

Fresh catalyst	BET surface area/(m²·g⁻¹)	t-plot micropore area/(m²·g⁻¹)	t-Plot external surface area/(m²·g⁻¹)	Total pore volume/(cm³·g⁻¹)	Pore size /nm
ASA	262.13	−	−	0.44	6.75
HZSM-5	276.21	145.49	130.72	0.23	3.26
Ni/HZSM-5	241.83	155.48	86.35	0.19	3.16
Ni-Fe/HZSM-5	219.50	133.02	84.48	0.17	3.11
Ni-Fe/ASA@HZSM-5	195.90	107.59	88.31	0.16	3.17

下载: 导出CSV

表 2 不同升温速率下玉米秸秆热解反应动力学参数

Table 2 Kinetic parameters of CS pyrolysis under different heating rates

β/(mL·min⁻¹)	CS		MCh		CR
β/(mL·min⁻¹)	E/(kJ·mol⁻¹)	A/min⁻¹	E/(kJ·mol⁻¹)	A/min⁻¹	E/(kJ·mol⁻¹)	A/min⁻¹
10	74.96	1498.02	74.88	1474.39	73.04	1237.76
20	73.21	1253.56	73.50	1290.48	72.27	1150.18
30	72.81	1210.30	74.60	1430.49	72.44	1169.72
40	72.61	1186.40	73.75	1316.83	71.77	1099.88
β/(mL·min⁻¹)	WSh		WSt		PR
β/(mL·min⁻¹)	E/(kJ·mol⁻¹)	A/min⁻¹	E/(kJ·mol⁻¹)	A/min⁻¹	E/(kJ·mol⁻¹)	A/min⁻¹
10	71.33	1059.17	72.48	1178.61	73.89	1341.81
20	71.51	1073.74	72.20	1143.25	72.22	1144.56
30	71.69	1093.54	72.18	1143.54	71.69	1091.38
40	71.95	1119.70	72.48	1179.23	71.63	1084.02

下载: 导出CSV

表 3 生物质热解的反应动力学参数

Table 3 Reaction kinetic parameters of biomass pyrolysis

Sample	E/(kJ·mol⁻¹)	A/min⁻¹	Sample	E/(kJ·mol⁻¹)	A/min⁻¹
CS	73.39	1237.27	WSh	71.62	1061.48
MCh	74.18	1379.27	WSt	72.34	1142.08
CR	72.38	1147.11	PR	72.36	1144.39

下载: 导出CSV

表 4 反应后催化剂的孔道特性

Table 4 Pore characteristics of reacted catalysts

Reacted catalyst	ASA	HZSM-5	Ni/HZSM-5	Ni-Fe/HZSM-5	Ni-Fe/ASA@HZSM-5
BET surface area/(m²·g⁻¹)	48.95	219.99	235.49	214.4	136.12
t-plot micropore area/(m²·g⁻¹)	33.09	157.67	167.17	172.84	104.48
t-plot external surface area/(m²·g⁻¹)	15.86	62.32	68.32	41.56	31.64
Total pore volume/(cm³·g⁻¹)	0.09	0.15	0.18	0.15	0.1
Pore size/nm	7.13	2.75	3.03	2.72	2.94
Average nanoparticle size/nm	122.58	27.27	25.48	27.99	44.08

下载: 导出CSV

参考文献(23)

[1]	SALAMA E S, HWANG J H, ELDALATONY M M, et al. Enhancement of microalgal growth and biocomponent-based transformations for improved biofuel recovery: A review[J]. Bioresour Technol,2018,258:365−375. doi: 10.1016/j.biortech.2018.02.006
[2]	SURIAPPARAO D V, TEJASVI R. A review on role of process parameters on pyrolysis of biomass and plastics: Present scope and future opportunities in conventional and microwave-assisted pyrolysis technologies[J]. Process Saf Environ,2022,162:435−462. doi: 10.1016/j.psep.2022.04.024
[3]	HU X, GHOLIZADEH M. Biomass pyrolysis: A review of the process development and challenges from initial researches up to the commercialisation stage[J]. J Energy Chem,2019,39(12):109−143.
[4]	HUO X, XIAO J, SONG M, et al. Comparison between in-situ and ex-situ catalytic pyrolysis of sawdust for gas production[J]. J Anal Appl Pyrolysis,2018,135:189−198. doi: 10.1016/j.jaap.2018.09.003
[5]	GUPTA S, MONDAL P. Catalytic pyrolysis of pine needles with nickel doped gamma-alumina: Reaction kinetics, mechanism, thermodynamics and products analysis[J]. J Clean Prod,2021,286(1):124930.1−124930.12.
[6]	HERNANDO H, MORENO I, FERMOSO J, et al. Biomass catalytic fast pyrolysis over hierarchical ZSM-5 and Beta zeolites modified with Mg and Zn oxides[J]. Biomass Convers Bior,2017,7(3):289−304. doi: 10.1007/s13399-017-0266-6
[7]	LI Y, NI S, YELLEZUOME D, et al. Deactivation mechanism and regeneration effect of bi-metallic Fe-Ni/ZSM-5 catalyst during biomass catalytic pyrolysis[J]. Fuel,2022,312(15):122924.1−122924.10.
[8]	LI X, LIU P, WU S, et al. Study on the mechanism of syngas production from catalytic pyrolysis of biomass tar by Ni–Fe catalyst in CO₂ atmosphere[J]. Fuel,2022,11(17):126705.
[9]	LI X, LIU P, LEI T, et al. Pyrolysis of biomass Tar model compound with various Ni-based catalysts: Influence of promoters characteristics on hydrogen-rich gas formation[J]. Energy,2022,244(PB):123137.
[10]	LI X, LIU P, CHEN W, et al. Catalytic pyrolysis of toluene as biomass tar model component using Ni/HZSM-5 modified by CeO2 and MgO promoters[J]. J Anal Appl Pyrolysis,2022,162:105436.1−105436.11.
[11]	LI X, Chen Z, LIU P, et al. Feasibility assessment of recycling waste aluminum dross as a basic catalyst for biomass pyrolysis to produce hydrogen-rich gas[J]. Int J Hydrog Energy,2023,48(93):36361−36376. doi: 10.1016/j.ijhydene.2023.06.049
[12]	SINGH S, CHAKRABORTY J P, MONDAL M K. Intrinsic kinetics, thermodynamic parameters and reaction mechanism of non-isothermal degradation of torrefied Acacia nilotica using isoconversional methods[J]. Fuel,2020,259(1):116263.1−116263.15.
[13]	ZHAO B, YANG H, ZHANG H, et al. Study on hydrogen-rich gas production by biomass catalytic pyrolysis assisted with magnetic field[J]. J Anal Appl Pyrolysis,2021,157(Aug):105227.1−105227.10.
[14]	SHARMA P, PANDEY O P, DIWAN P K. Non-isothermal kinetics of pseudo-components of waste biomass[J]. Fuel,2019,253:1149−1161. doi: 10.1016/j.fuel.2019.05.093
[15]	许敏. 生物质热解气化特性分析与试验研究[D]. 天津: 天津大学, 2008. XU MIN. Mechanism and experimental study on biomass gasification and pyrolysis[D]. Tianjin: Tianjin University, 2021.)
[16]	QIN Z, YOU Z, BOZHILOV K N, et al. Dissolution behavior and varied mesoporosity of zeolites by NH4 F etching[J]. Chem Eur J,2022,28(16):e202104339. doi: 10.1002/chem.202104339
[17]	HU Z, HAN J, WEI Y, et al. Dynamic evolution of zeolite framework and metal-zeolite interface[J]. ACS Catal,2022,12(9):5060−5076. doi: 10.1021/acscatal.2c01233
[18]	KOSTYNIUK A, BAJEC D, LIKOZAR B. Catalytic hydrocracking reactions of tetralin as aromatic biomass tar model compound to benzene/toluene/xylenes (BTX) over zeolites under ambient pressure conditions[J]. J Ind Eng Chem,2021,96(1):130−143.
[19]	LI X, LIU P, HUANG S, et al. Study on the mechanism of syngas production from catalytic pyrolysis of biomass tar by Ni–Fe catalyst in CO2 atmosphere[J]. Fuel,2023,335(1):1−12.
[20]	FATHI S, SOHRABI M, FALAMAKI C. Improvement of HZSM-5 performance by alkaline treatments: Comparative catalytic study in the MTG reactions[J]. Fuel,2014,116:529−537. doi: 10.1016/j.fuel.2013.08.036
[21]	TANG W, CAO J, YANG F, 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 Convers Manag,2020,212:112799.1−112799.12.
[22]	MAHINROOSTA M, ALLAHVERDI A. Hazardous aluminum dross characterization and recycling strategies: A critical review[J]. J Environ Manage,2018,223:452−468. doi: 10.1016/j.jenvman.2018.06.068
[23]	孙堂磊. 木质纤维素类生物质定向热解产物分布规律及实验研究[D]. 河南: 河南农业大学, 2021. SUN Tanglei. Product distribution and experimental study of lignocellulosic biomass directional pyrolysis[D]. Henan: Henan Agricultural University, 2021.)