用于分布式制氢的甲烷蒸汽重整膜反应器的数值模拟

doi:10.16085/j.issn.1000-6613.2021-1868

摘要/Abstract

摘要：

采用反应-分离集成的膜反应器进行分布式制氢，对简化工艺、降低能耗、提升技术经济性至关重要。本文采用数学模型对甲烷蒸汽重整制氢过程膜反应器进行模拟，系统分析了渗透侧操作策略、反应压力、反应温度、钯基膜性能、催化剂性能对反应器行为的影响；并以1m³/h甲烷最大程度转化为目标进行分布式制氢案例分析，详细比较膜反应器技术与“常规反应器+膜分离”工艺技术。结果表明，膜反应器在反应压力30atm（1atm=101325Pa）、反应温度500℃下操作可实现紧凑设计，比“常规反应器+膜分离”工艺技术具有明显优势，但是亟需研发更佳活性（10倍）的钯基膜和催化剂以实现显著的过程强化。模拟结果可为不同规模分布式制氢膜反应器的操作与设计及进一步的性能强化提供指导。

关键词: 甲烷蒸汽重整, 制氢, 膜反应器, 数学模型, 操作与设计, 过程强化

Abstract:

The membrane reactor system with integrated chemical reaction and membrane separation for distributed hydrogen production is of vital importance to simplify chemical process, lower energy consumption and improve techno-economics. Herein, the mathematical model were adopted to simulate methane steam reforming process in membrane reactor, and thus analyze the effect of operational strategies of permeation side, reaction pressure, reaction temperature, palladium-based membrane performance and activity of catalyst on the behaviors of membrane reactor. Subsequently, case study was conducted with the aim of maximum conversion of 1m³/h CH₄ to compare membrane reactor technology and "conventional reactor + membrane separation" process. The results showed that compact design of membrane reactor under the conditions of 30atm and 500℃ can be achieved and the membrane reactor presented obvious advantages over the process technology of "conventional reactor+membrane separation". However, more active palladium-based membranes and catalysts, particularly 10 times than current performance, were in urgent need for further process intensification. The results can provide fundamental guidelines for the design, operation and further performance intensification of membrane reactor for distributed hydrogen production with various scales.

Key words: methane steam reforming, hydrogen production, membrane reactor, mathematical model, operation and design, process intensification

中图分类号:

TQ032

闫鹏, 程易. 用于分布式制氢的甲烷蒸汽重整膜反应器的数值模拟[J]. 化工进展, 2022, 41(7): 3446-3454.

YAN Peng, CHENG Yi. Numerical simulation of membrane reactor of methane steam reforming for distributed hydrogen production[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3446-3454.

图/表 13

图1 同轴环管式膜反应器的轴切面

表1 催化反应动力学参数

参数	数值
k_I/mol·Pa^0.5·kg^-1·s^-1	3.711×10¹⁷exp(-240100/RT)
k_II/mol·Pa·kg^-1·s^-1	5.431exp(-67130/RT)
k_III/mol·Pa^0.5·kg^-1·s^-1	8.960×10¹⁶exp(-24390/RT)
K_eqI/Pa²	1.198×10²³exp(-26830/RT)
K_eqII	1.767×10^-2exp(4400/T)
K_eqIII/Pa²	K_eqI×K_eqII
K(CH₄)/Pa^-1	6.65×10^-9exp(38280/RT)
K(CO)/Pa^-1	8.23×10^-10exp(70650/RT)
K(H₂)/Pa^-1	6.12×10^-14exp(82900/RT)
K(H₂O)	1.77×10⁵exp(-88680/RT)

表2 膜反应器的设计与操作参数

参数	数值
ε	0.4
ρ_cat/kg·m^-3	800
R₁/mm	6.5
R₂/mm	10.5
K_m(H₂)/mol·m^-2·s^-1·Pa^-0.5	3.96×10^-3
p_per(H₂)/atm	1
F_in(CH₄)/m³·h^-1	1
水碳比	3
T/K	773.15
p_r/atm	30

图2 1173.15K下常规催化反应器的甲烷转化率与一氧化碳选择性

图3 膜反应器在773.15K下的甲烷转化率与选择性

图4 773.15K下常规催化反应器的氢气分压随反应操作压力的变化

图5 反应温度对膜反应器性能的影响（pr=30atm）

图6 反应压力对膜反应器性能的影响（T=773.15K）

图7 钯基膜性能对膜反应器性能的影响（T=773.15K）

图8 催化剂活性对膜反应器性能的影响

图9 案例分析之甲烷转化性能随膜反应器催化床层体积的变化

图10 案例分析之“常规反应器+膜分离”工艺性能随设备体积的变化

图11 案例分析之钯基膜或催化剂性能增强后的膜反应器体积

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