Process simulations and multi-ion coupled transport mechanism for hydrogen-driven electrochemical CO2 capture system

doi:10.11949/0438-1157.20250657

Abstract

Abstract:

Hydrogen-driven electrochemical carbon capture systems (HECCS) have been widely attracted attention due to their low energy consumption and high selectivity. Establishing a quantitative relationship between the multiple ions coupled transport mechanisms in HECCS and operating parameters such as current density, capture concentration, and temperature is the key to elucidating the underlying carbon capture mechanisms. Based on the Maxwell-Stefan diffusion equation, this paper establishes a mass transfer-electric field coupled multiphysics model for the carbon capture process in the HECCS system, taking into account multi-ion coupling transport. The results show that the proposed model can effectively simulate the multiple ions transport in the HECCS system. By analyzing the coupled behaviors of pH distribution, electrolyte potential, and the transport of OH^-, $H C O 3 -$ and $C O 3 2 -$ ions within the membrane electrode assembly, the rate-limiting steps under different operating conditions are identified. The influences of various operational parameters and key controlling factors on CO₂ capture flux and faradaic efficiency are determined, clarifying the mechanisms by which operating conditions affect carbon capture performance. This work provides a theoretical and computational foundation for the performance improvement and optimal design of electrochemical CO₂ capture system.

Key words: CO₂capture, hydrogen, ion diffusion, mathematical modeling, rate controlling step

摘要：

氢气驱动的电化学CO₂捕集系统（hydrogen-driven electrochemical carbon capture system，HECCS）因低能耗和高选择性等特性受到广泛关注。HECCS中多离子耦合传输与电流密度、捕集浓度及温度等操作参数的定量关联是厘清其捕碳机制的关键。基于Maxwell-Stefan扩散方程，建立了HECCS系统捕碳过程中考虑多离子耦合传输的传质-电场耦合多物理场模型。研究表明，所建立模型可以有效地模拟HECCS系统中的多离子传输过程。通过对膜电极内pH分布、电解质电势及OH^-、 $H C O 3 -$ 和 $C O 3 2 -$ 传输过程耦合特性的分析，厘清了不同操作参数下捕碳性能的速率限制步骤，获得了操作参数和关键控制因素对HECCS捕集通量和电子效率的影响规律。研究可为电化学CO₂捕集系统的性能提升和优化设计提供理论分析和计算依据。

关键词: CO₂捕集, 氢气, 离子扩散, 数学模拟, 速率限制步骤

CLC Number:

TQ 021.8

Yibai LI, Shichang LIU, Jing WANG, Yongzhong LIU. Process simulations and multi-ion coupled transport mechanism for hydrogen-driven electrochemical CO₂ capture system[J]. CIESC Journal, 2025, 76(11): 5951-5964.

李一白, 刘世昌, 王靖, 刘永忠. 氢气驱动电化学CO₂捕集系统的过程模拟与多离子耦合传输机制[J]. 化工学报, 2025, 76(11): 5951-5964.

Figures/Tables 10

Fig.1 Schematic diagram of a hydrogen-driven electrochemical CO₂ capture system

Table 1 The geometrical parameters and operating conditions used in the model

几何参数	数值	操作条件	数值
$L A G D L$ , $L C G D L$ /μm	200	$p$ /Pa	101325
$L A N$ , $L C A$ /μm	5	$y H 2 O$	0.7
$L M$ /μm	40	$x C O 2$	0.2

Table 1 The geometrical parameters and operating conditions used in the model

几何参数	数值	操作条件	数值
$L A G D L$ , $L C G D L$ /μm	200	$p$ /Pa	101325
$L A N$ , $L C A$ /μm	5	$y H 2 O$	0.7
$L M$ /μm	40	$x C O 2$	0.2

Table 2 Additional parameters used in the model

参数符号	值	公式编号	文献
常数
$R$ /(J/(mol∙K))	8.31	(15)(19)(20)(22)~(26)(29)(30)(33)(34)(36)(37)
$F$ /(C/mol)	96485	(18)(22)(25)(26)(29)(30)(33)~(38)
材料物性
$ρ M$ /(kg/m³)	1000	(8)
$ρ W$ /(kg/m³)	1000	(12)(13)
IEC/(mol/kg)	3	(8)(13)
$σ e f f$ /(S/m)	100	(40)	[32]
$ε G D L, g$	0.4	(47)
$τ G D L$	5	(47)
扩散系数
$D O H -$ / (m²/s)	$5.3 × 10 - 9$	(29)	[30]
$δ$	1.35	(29)	[30]
$D C O 2$ /(m²/s)	$2.74 × 10 - 4 T 1.59 / (e 102.1 T p)$	(47)	[33]
电化学反应
$α A N, H O R$	0.5	(34)
$α C A, H O R$	0.5	(34)
$α A N, O R R$	1	(35)
$i 0, H O R$ /(A/m²)	$5 × 106$	(34)	[34]
$i 0, O O R$ /(A/m²)	1	(35)	[34]
化学反应
$K a 1$ /(m³/mol)	$10 13.8845 - 0.03763 T - 3072.590 T - 1 + 1.4273 × 10 - 5 T 2 / K W$	(3)	[35]
$K a 2$ /(m³/mol)	$10 17.4200 - 0.05797 T - 4080.582 T - 1 + 3.6045 × 10 - 5 T 2 / K W$	(4)	[35]
$k 1$ /(m³/(mol∙s))	$7.0 × 10 - 7$	(5)	[26]
$k - 1$ /s^-1	26	(5)	[26]
$k 2$ /(m³/(mol∙s))	11	(6)	[26]
$k - 2$ / s^-1	$3.2 × 10 - 4$	(6)	[26]
$K C O 2$ /(mol/(m³∙Pa))	$34 e 2400 1 / T - 1 / 298 / p$	(41)	[27]
修正因子
$φ 0$	5.6	(43)
$k 0$	0.0195	(44)
$Δ H a b s$ /(J/mol)	$103$	(44)

Table 2 Additional parameters used in the model

参数符号	值	公式编号	文献
常数
$R$ /(J/(mol∙K))	8.31	(15)(19)(20)(22)~(26)(29)(30)(33)(34)(36)(37)
$F$ /(C/mol)	96485	(18)(22)(25)(26)(29)(30)(33)~(38)
材料物性
$ρ M$ /(kg/m³)	1000	(8)
$ρ W$ /(kg/m³)	1000	(12)(13)
IEC/(mol/kg)	3	(8)(13)
$σ e f f$ /(S/m)	100	(40)	[32]
$ε G D L, g$	0.4	(47)
$τ G D L$	5	(47)
扩散系数
$D O H -$ / (m²/s)	$5.3 × 10 - 9$	(29)	[30]
$δ$	1.35	(29)	[30]
$D C O 2$ /(m²/s)	$2.74 × 10 - 4 T 1.59 / (e 102.1 T p)$	(47)	[33]
电化学反应
$α A N, H O R$	0.5	(34)
$α C A, H O R$	0.5	(34)
$α A N, O R R$	1	(35)
$i 0, H O R$ /(A/m²)	$5 × 106$	(34)	[34]
$i 0, O O R$ /(A/m²)	1	(35)	[34]
化学反应
$K a 1$ /(m³/mol)	$10 13.8845 - 0.03763 T - 3072.590 T - 1 + 1.4273 × 10 - 5 T 2 / K W$	(3)	[35]
$K a 2$ /(m³/mol)	$10 17.4200 - 0.05797 T - 4080.582 T - 1 + 3.6045 × 10 - 5 T 2 / K W$	(4)	[35]
$k 1$ /(m³/(mol∙s))	$7.0 × 10 - 7$	(5)	[26]
$k - 1$ /s^-1	26	(5)	[26]
$k 2$ /(m³/(mol∙s))	11	(6)	[26]
$k - 2$ / s^-1	$3.2 × 10 - 4$	(6)	[26]
$K C O 2$ /(mol/(m³∙Pa))	$34 e 2400 1 / T - 1 / 298 / p$	(41)	[27]
修正因子
$φ 0$	5.6	(43)
$k 0$	0.0195	(44)
$Δ H a b s$ /(J/mol)	$103$	(44)

Fig.2 Comparisons between the simulated data and experimental data from reference[14] under variation of CO₂ capture flux with current density

Fig.3 Distribution of pH and electrolyte potential within the membrane electrode under different current densities (40℃, CO2 concentration 0.04%)

Fig.4 Proportion of ionic conduction current within the membrane electrode under different current densities (40℃, CO2 concentration 0.04%)

Fig.5 Comparison of CO₂ fluxes driven by gradients of pH and electrolyte potential ϕl under different current densities

Fig.6 Characteristics of electronic efficiency and proportion of current conducted by ions within the membrane electrode under different CO2 capture concentration

Fig.7 Variation of CO2 capture flux with current density under different temperature

Fig.8 Variation of electronic efficiency with current density under different temperature (CO2 capture concentration of 0.2%)

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Process simulations and multi-ion coupled transport mechanism for hydrogen-driven electrochemical CO₂ capture system

氢气驱动电化学CO₂捕集系统的过程模拟与多离子耦合传输机制

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