Hydrogen production performance and reaction kinetics of biomass gasification enhanced by calcined carbide slag

doi:10.11949/0438-1157.20250623

Abstract

Abstract:

Calcium-cycled biomass chemical chaining gasification (CaL-BCLG) technology uses CaO-based absorbents to capture CO₂ in situ, achieving the synergistic goals of high-purity H₂ production and carbon emission reduction. It holds great promise in the clean energy sector. However, the sintering-induced deactivation of sorbents during high-temperature cycling remains a major barrier to industrial application. In this study, a series of inert oxide-doped sorbents were synthesized via a wet-mixing and calcination method, using calcined carbide slag (CCS) as the CaO precursor. Comprehensive characterization, large-sample thermogravimetric analysis, and CaL-BCLG platform tests were employed to investigate the effects of dopant type on the physicochemical properties and CO₂ adsorption performance of the sorbents. The effect of doping modification on biomass cyclic H₂ production and gasification kinetics was also systematically evaluated. The results showed that CCS exhibited a relatively high initial carbonation conversion, but suffered significant performance degradation due to sintering. Among all samples, the CCS-Si2 sorbent (mass ratio CCS∶SiO₂ = 98∶2) demonstrated the best performance, with an average maximum CO₂ uptake of 0.32 g·g_sor^-1 and a peak carbonation conversion of 47.44% after 20 cycles. The hydrogen production efficiency of biomass gasification was jointly influenced by the CO₂ capture capacity of the sorbent and the diffusion efficiency of syngas within it. When the CaO-to-carbon molar ratio (CaO/C) is below 1.0 or the steam-to-biomass mass ratio (S/B) is below 30, increasing the sorbent and steam inputs could promote the gasification reaction. However, exceeding these thresholds might hinder syngas diffusion and disrupt the temperature stability within the reactor, leading to adverse effects. Under typical conditions (temperature 650℃, CaO/C = 1.0, S/B = 30), the CCS-Si2 sorbent delivered a H₂ yield of 357 ml·g $b i o - 1$ after 10 cycles, with a CO₂ yield of only 91 ml·g $b i o - 1$ , significantly outperforming both pure CaO and unmodified CCS. This study provides theoretical insights into the resource utilization of waste carbide slag and the development of efficient and stable sorbents for CaL-BCLG hydrogen production processes.

Key words: biomass, chemical looping gasification, sorbent, hydrogen production, CO₂ adsorption, kinetic model

摘要：

钙循环生物质化学链气化（CaL-BCLG）技术通过CaO基吸收剂原位捕集CO₂以实现高纯H₂制取与碳减排的协同目标，在清洁能源领域具有广阔前景。但吸附剂在高温循环中的烧结失活问题严重制约其工业化应用。以煅烧电石渣（CCS）为CaO前体，采用湿混-煅烧法制备了一系列掺杂惰性氧化物的改性吸附剂。结合XRD SEM、BET、STA等表征手段、大样品量热重装置及CaL-BCLG平台，系统研究了掺杂剂类型对吸附剂物化特性和CO₂吸附性能的影响，并评估了掺杂改性对生物质循环制氢能力和气化动力学行为的作用机制。结果表明，CCS在初始反应中具有较高的碳酸化转化率，但烧结导致其性能显著下降。CCS-Si2吸附剂（CCS∶SiO₂=98∶2）在20次循环反应中展现出最优性能，平均最大CO₂吸附量和碳酸化转化率分别达到0.32 g·g $s o r - 1$ 和47.44%。生物质气化制氢效率受吸附剂CO₂捕集能力和合成气在吸附剂内部的扩散效率共同影响。当CaO与碳元素摩尔比（CaO/C）<1.0或蒸汽与生物质质量比（S/B）<30时，增加吸附剂和蒸汽添加量可促进气化反应；超过该阈值则会抑制合成气扩散并破坏反应器内温度场稳定性，产生负效应。在典型工况下（温度650℃，CaO/C=1.0，S/B=30），CCS-Si2吸附剂经10次循环后的H₂产率达357 ml·g $b i o - 1$ ，CO₂产率仅为91 ml·g $b i o - 1$ ，显著优于纯CaO和未改性CCS。研究可为电石渣的资源化利用及CaL-BCLG工艺中吸附剂的高效稳定设计提供理论支撑。

关键词: 生物质, 化学链气化, 吸附剂, 制氢, CO₂吸附, 动力学模型

CLC Number:

TK 6

Li ZOU, Li MA, Pengyu ZHANG, Gaoming WEI, Ruizhi GUO, Qinxin ZHAO. Hydrogen production performance and reaction kinetics of biomass gasification enhanced by calcined carbide slag[J]. CIESC Journal, 2025, 76(11): 6040-6057.

邹立, 马砺, 张鹏宇, 魏高明, 郭睿智, 赵钦新. 煅烧电石渣强化生物质气化制氢特性及其反应动力学研究[J]. 化工学报, 2025, 76(11): 6040-6057.

Figures/Tables 25

Fig.1 Schematic diagram of calcium cycle-biomass chemical looping gasification for H2 production technology

Table 1 Compositional analysis results of corn cob sample

样品

工业分析/%

（质量，空气干燥基）

元素分析/%

（质量，空气干燥基)

Table 2 Compositional analysis results of calcined carbide slag

主要成分	质量分数/%
CaO	85.50
SiO₂	7.48
Al₂O₃	3.90
MgO	2.37
Fe₂O₃	0.21
SO₃	0.54

Table 3 Properties related to calcium carbonate and inert oxide precursors

样品	分子式	相对分子质量	纯度/%
碳酸钙	CaCO₃	100.09	99.0
硝酸铝	Al(NO₃)₃·9H₂O	375.13	99.0
醋酸镁	Mg(CH₃COO)₂·9H₂O	214.40	99.0
正硅酸四乙酯	C₈H₂₀O₄Si	208.33	98.0

Fig.2 Preparation process of modified sorbent

Fig.3 Schematic diagram of a large sample size thermogravimetric device

Fig.4 Schematic diagram of a calcium cycle-biomass chemical looping gasification system

Table 4 Common kinetic mechanism functions for solid-phase pyrolysis gasification reactions

序号	机理函数	积分形式G(α)	微分形式f(α)
扩散模型
1	一维扩散，1D	$α 2$	$1 / 2 α - 1$
2	二维扩散-Valensi，2D-V	$α + (1 - α) l n (1 - α)$	$- l n (1 - α) - 1$
3	二维扩散-Jander，n=1/2，2D-J	$1 - (1 - α) 1 / 2 1 / 2$	$4 (1 - α) 1 / 2 1 - (1 - α) 1 / 2 1 / 2$
4	三维扩散-Jander，n=2，3D-J	$1 - (1 - α) 1 / 3 2$	$3 / 2 (1 - α) 2 / 3 1 - (1 - α) 1 / 3 - 1$
5	三维扩散-Zhuravlev Leskin Tempelman，3D-ZLT	$(1 - α) - 1 / 3 - 1 2$	$3 / 2 (1 - α) 4 / 3 (1 - α) - 1 / 3 - 1 - 1$
6	三维扩散-Ginstling Broushtsin，3D-GB	$1 - 2 / 3 α - 1 - α 2 / 3$	$3 / 2 (1 - α) - 1 / 3 - 1 - 1$
速率方程模型
7	Avrami Erofeev，n=1/2，AE2	$- l n 1 - α 1 / 2$	$2 1 - α - l n 1 - α 1 / 2$
8	Avrami Erofeev，n=1/3，AE3	$- l n 1 - α 1 / 3$	$3 1 - α - l n 1 - α 2 / 3$
9	Avrami Erofeev，n=1/4，AE4	$- l n 1 - α 1 / 4$	$4 1 - α - l n 1 - α 3 / 4$
反应级数模型
10	反应级数，n=2，RO2	$1 - 1 - α 2$	$1 / 2 1 - α - 1$
11	反应级数，n=3，RO3	$1 - 1 - α 3$	$1 / 3 1 - α - 2$
12	化学反应，CR	$1 - α - 1 - 1$	$2 1 - α 3 / 2$
几何收缩模型
13	收缩圆柱体，n=2，CA2	$2 1 - 1 - α 1 / 2$	$1 - α 1 / 2$
14	收缩球状，n=3，3D-CV3	$3 1 - 1 - α 1 / 3$	$1 - α 2 / 3$
指数幂模型
15	一级指数幂，n=1，EP1	$l n α$	$α$
16	二级指数幂，n=2，EP2	$l n α 2$	$1 / 2 α$
幂函数模型
17	n=1/2, MP2	$α 1 / 2$	$2 α 1 / 2$
18	n=1/3, MP3	$α 1 / 3$	$3 α 2 / 3$

Table 4 Common kinetic mechanism functions for solid-phase pyrolysis gasification reactions

序号	机理函数	积分形式G(α)	微分形式f(α)
扩散模型
1	一维扩散，1D	$α 2$	$1 / 2 α - 1$
2	二维扩散-Valensi，2D-V	$α + (1 - α) l n (1 - α)$	$- l n (1 - α) - 1$
3	二维扩散-Jander，n=1/2，2D-J	$1 - (1 - α) 1 / 2 1 / 2$	$4 (1 - α) 1 / 2 1 - (1 - α) 1 / 2 1 / 2$
4	三维扩散-Jander，n=2，3D-J	$1 - (1 - α) 1 / 3 2$	$3 / 2 (1 - α) 2 / 3 1 - (1 - α) 1 / 3 - 1$
5	三维扩散-Zhuravlev Leskin Tempelman，3D-ZLT	$(1 - α) - 1 / 3 - 1 2$	$3 / 2 (1 - α) 4 / 3 (1 - α) - 1 / 3 - 1 - 1$
6	三维扩散-Ginstling Broushtsin，3D-GB	$1 - 2 / 3 α - 1 - α 2 / 3$	$3 / 2 (1 - α) - 1 / 3 - 1 - 1$
速率方程模型
7	Avrami Erofeev，n=1/2，AE2	$- l n 1 - α 1 / 2$	$2 1 - α - l n 1 - α 1 / 2$
8	Avrami Erofeev，n=1/3，AE3	$- l n 1 - α 1 / 3$	$3 1 - α - l n 1 - α 2 / 3$
9	Avrami Erofeev，n=1/4，AE4	$- l n 1 - α 1 / 4$	$4 1 - α - l n 1 - α 3 / 4$
反应级数模型
10	反应级数，n=2，RO2	$1 - 1 - α 2$	$1 / 2 1 - α - 1$
11	反应级数，n=3，RO3	$1 - 1 - α 3$	$1 / 3 1 - α - 2$
12	化学反应，CR	$1 - α - 1 - 1$	$2 1 - α 3 / 2$
几何收缩模型
13	收缩圆柱体，n=2，CA2	$2 1 - 1 - α 1 / 2$	$1 - α 1 / 2$
14	收缩球状，n=3，3D-CV3	$3 1 - 1 - α 1 / 3$	$1 - α 2 / 3$
指数幂模型
15	一级指数幂，n=1，EP1	$l n α$	$α$
16	二级指数幂，n=2，EP2	$l n α 2$	$1 / 2 α$
幂函数模型
17	n=1/2, MP2	$α 1 / 2$	$2 α 1 / 2$
18	n=1/3, MP3	$α 1 / 3$	$3 α 2 / 3$

Fig.5 XRD spectra of modified adsorbents

Fig.6 Apparent morphology and energy spectra of modified sorbents

Fig.7 Melting points and Taman temperatures of CaO, CaCO3 and inert oxides

Table 5 BET test results for sorbents

样品	比表面积/（m²·g^-1）	总孔容/（cm³·g^-1）	平均孔径/nm
CaO	11.58	0.049	16.81
CCS	10.69	0.044	15.93
CCS-Al2	8.32	0.034	13.25
CCS-Mg2	9.35	0.032	13.90
CCS-Si2	10.35	0.036	13.90

Fig.8 BET test curves of sorbents

Fig.9 CO2 cyclic sorption characteristic parameters of sorbents

Fig.10 Average sorption characteristic parameters of modified sorbents over 20 carbonation/calcination reaction cycles

Fig.11 Comparison of the apparent morphology of sorbents before and after reaction: (a) before reaction; (b) after reaction

Fig.12 Thermogravimetric results of biomass isothermal gasification under different CaO/C conditions

Fig.13 Thermogravimetric results of biomass isothermal gasification under different S/B conditions

Fig.14 Thermogravimetric results of biomass isothermal gasification under different gasification temperature conditions

Fig.15 Thermogravimetric results of biomass isothermal gasification under different sorbent types

Fig.16 Linear fitting results of the mechanism function for the biomass isothermal gasification process

Table 6 Optimal mechanism function and apparent activation energy for the biomass isothermal gasification process

序号	吸附剂	CaO/C	蒸汽流量/(g·min^-1)	最佳机理函数		E_a/(kJ·mol^-1)
序号	吸附剂	CaO/C	蒸汽流量/(g·min^-1)	阶段Ⅰ	阶段Ⅱ	阶段Ⅰ	阶段Ⅱ
1	CCS	0	1.0	2D-J	1D	12.18	55.06
2	CCS	0.5	1.0	2D-J	CA2	12.99	52.12
3	CCS	1.0	1.0	2D-J	CA2	15.84	78.66
4	CCS	1.5	1.0	2D-J	CA2	21.83	85.40
5	CCS	1.0	0	2D-J	CA2	16.60	73.03
6	CCS	1.0	1.5	2D-J	CA2	15.53	46.99
7	CCS	1.0	2.0	2D-J	CA2	15.25	38.18
8	纯CaO	1.0	1.0	2D-J	CA2	15.98	76.44
9	CCS-Si2	1.0	1.0	2D-J	CA2	17.27	86.02

Fig.17 Calculation process for gasification kinetics

Fig. 18 Test results of cyclic H2 production in the presence of different sorbents

Table 7 Comparison of the results of this study with those of other studies

吸附剂	生物质	气化工况	循环次数	H₂产率/(ml· $g b i o - 1$ )	CO₂产率/(ml· $g b i o - 1$ )	文献
Ca₂Fe₂O₅-CaO	松木	850℃, 60 min, S/B = 5	1	593	505	[31]
NiO/Al₂O₃-煅烧白云石	玉米秸秆	650℃, 40 min, S/B = 2, CaO/C = 0.6	1	341	65	[32]
Al₂O₃-CaO	污泥	650℃, 100 min, S/B = 10, CaO/C = 1.0	1	329	31	[33]
CeO₂/Ca₁₂Al₁₄O₃₃-CaO	甘蔗渣	650℃, 40 min, S/B = 12, CaO/C = 1.0	10	130	15	[34]
SiO₂-煅烧电石渣	玉米芯	650℃, 15 min, S/B = 30, CaO/C = 1.0	10	381	78	本研究

Table 7 Comparison of the results of this study with those of other studies

吸附剂	生物质	气化工况	循环次数	H₂产率/(ml· $g b i o - 1$ )	CO₂产率/(ml· $g b i o - 1$ )	文献
Ca₂Fe₂O₅-CaO	松木	850℃, 60 min, S/B = 5	1	593	505	[31]
NiO/Al₂O₃-煅烧白云石	玉米秸秆	650℃, 40 min, S/B = 2, CaO/C = 0.6	1	341	65	[32]
Al₂O₃-CaO	污泥	650℃, 100 min, S/B = 10, CaO/C = 1.0	1	329	31	[33]
CeO₂/Ca₁₂Al₁₄O₃₃-CaO	甘蔗渣	650℃, 40 min, S/B = 12, CaO/C = 1.0	10	130	15	[34]
SiO₂-煅烧电石渣	玉米芯	650℃, 15 min, S/B = 30, CaO/C = 1.0	10	381	78	本研究

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