光热驱动的膜分离生物甲烷制氢过程建模与仿真分析

doi:10.11949/0438-1157.20231248

摘要/Abstract

摘要：

光热驱动的甲烷重整制氢技术，是将太阳能转化为燃料的主要技术路径之一。引入聚光集热技术，可实现太阳能的全光谱利用，有效提高太阳能到燃料化学能的转化效率，同时显著降低系统能耗及碳排放。将多孔碳化硅吸热体和La_1-_x Sr _x Co_1-_y Fe _y O_3-_δ 钙钛矿透氧膜结合，提出一种光热驱动的膜反应制氢的设计思路，实现了连续、高效的制氢过程。完成了该反应过程的概念设计，建立考虑辐射-传热-膜分离-反应的数值模型并进行仿真模拟；重点评估了膜表面的温度均匀性，并分析温度对膜内反应及出口产物的影响规律。结果表明，该模型可以有效精准描述概念设计过程。研究成果可为光热驱动的高温膜反应器设计和放大提供理论依据以及初步设计方法。

关键词: 动态建模, 动态仿真, 太阳能, 甲烷部分氧化, 制氢, 透氧膜, 概念设计

Abstract:

Solar-driven methane reforming for hydrogen production is one of the main technological pathways for solar fuels. The introduction of concentrating heat collection technology can realize the full spectrum utilization of solar energy, effectively improve the conversion efficiency of solar energy to fuel chemical energy, and significantly reduce system energy consumption. In this study, a novel design for solar-driven membrane reactor was proposed for hydrogen production by combining porous silicon carbide absorber and La_1-_x Sr _x Co_1-_y Fe _y O_3-_δ perovskite oxygen permeable membrane. The conceptual design of the reaction process was made, and a numerical model considering radiation heat transfer membrane separation reaction was established and simulated. The temperature uniformity of the membrane surface was evaluated, and the influence of temperature on the membrane reaction and outlet products was analyzed. The results demonstrate that this model can effectively and accurately describe the conceptual design process. The findings provide a theoretical basis and initial design approach for the design and scale-up of solar-driven high-temperature membrane reactors.

Key words: dynamic modeling, dynamic simulation, solar energy, methane partial oxidation, hydrogen production, oxygen permeable membrane, conceptual design

中图分类号:

TB 116.2

王沛, 段睿明, 张广儒, 金万勤. 光热驱动的膜分离生物甲烷制氢过程建模与仿真分析[J]. 化工学报, 2024, 75(3): 967-973.

Pei WANG, Ruiming DUAN, Guangru ZHANG, Wanqin JIN. Modeling and simulation analysis of solar driven membrane separation biomethane hydrogen production process[J]. CIESC Journal, 2024, 75(3): 967-973.

图/表 12

图1 光热驱动的透氧膜反应器概念设计

Fig.1 Conceptual design of photothermal driven oxygen permeable membrane reactor

表1 反应器的主要几何尺寸

Table 1 Main geometric dimensions of reactor

参数	数值
反应器直径/mm	70
多孔SiC厚度/mm	50
透氧膜外径/mm	5
透氧膜内径/mm	4
透氧膜长度/mm	45
多孔SiC与透氧膜的距离/mm	5
透氧膜距反应器轴线距离/mm	20

表2 反应动力学参数

Table 2 Parameters of reaction kinetics

参数	公式
正向反应速率常数/(cm/(atm^0.5⋅s))	$k f = 5.90 × 106 e x p - 27291 / T$
逆向反应速率常数/(mol/(cm²⋅s))	$k r = 2.07 × 104 e x p - 29023 / T$
氧空位的扩散系数/(cm²/s)	$D V = 1.58 × 10 - 2 e x p - 8852.5 / T$

表2 反应动力学参数

Table 2 Parameters of reaction kinetics

参数	公式
正向反应速率常数/(cm/(atm^0.5⋅s))	$k f = 5.90 × 106 e x p - 27291 / T$
逆向反应速率常数/(mol/(cm²⋅s))	$k r = 2.07 × 104 e x p - 29023 / T$
氧空位的扩散系数/(cm²/s)	$D V = 1.58 × 10 - 2 e x p - 8852.5 / T$

表3 反应器的边界条件

Table 3 Boundary conditions of reactor

边界条件	数值
入射太阳辐射/W	4924
入口空气压力/atm	1
入口空气流速/(m/s)	1
入口空气温度/℃	28.5
入口空气中O₂质量分数	0.21
入口CH₄压力/atm	1
入口CH₄流速/(m/s)	0.2
入口CH₄温度/℃	20
入口CH₄中O₂质量分数	10^-6

表4 网格独立性验证方案

Table 4 Grid independence test schemes

方案

网格数/个

出口H₂的平均

摩尔分数/%

出口CO的平均

摩尔分数/%

表5 模型准确性验证

Table 5 Accuracy validation of model

温度/℃	$X C H 4$ /%			S_CO/%			H₂/CO
温度/℃	实验	Jin模型	本文模型	实验	Jin模型	本文模型	实验	Jin模型	本文模型
825	97.3	97.2	97.2	97	98.9	97.7	1.69	2	1.66
850	100	99.7	99.4	100	97.9	97.2	1.68	2	1.62
885	96.7	100	99.8	98	97.8	97.2	1.96	2	1.87

表5 模型准确性验证

Table 5 Accuracy validation of model

温度/℃	$X C H 4$ /%			S_CO/%			H₂/CO
温度/℃	实验	Jin模型	本文模型	实验	Jin模型	本文模型	实验	Jin模型	本文模型
825	97.3	97.2	97.2	97	98.9	97.7	1.69	2	1.66
850	100	99.7	99.4	100	97.9	97.2	1.68	2	1.62
885	96.7	100	99.8	98	97.8	97.2	1.96	2	1.87

图2 多孔SiC吸热体热通量分布

Fig.2 Heat flux distribution of porous SiC endothermic material

图3 反应器内流体温度分布

Fig.3 Temperature distribution of fluid in the reactor

图4 靠近/远离反应器轴线侧膜表面温度和氧通量轴向分布

Fig.4 Axial distribution of membrane surface temperature and oxygen flux near and away from the reactor axis

图5 反应物和生成物的摩尔分数分布

Fig.5 Molar fraction distribution of reactants and products

图6 O2摩尔分数分布

Fig.6 Molar fraction distribution of O2

图7 反应器出口各物质的摩尔分数

Fig.7 Molar fraction of species at the outlet of the reactor

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