膜分离耦合CO2电催化加氢制甲酸工艺的设计及模拟

doi:10.11949/0438-1157.20210453

摘要/Abstract

摘要：

CO₂对气候影响越来越严重，将其转化为甲酸能够同步实现资源化和碳减排。当前CO₂加氢制甲酸的研究主要在于寻找高性能催化剂，而过程设计对甲酸实现工业化也不可或缺，但是CO₂电催化加氢制甲酸的过程设计尚未见报道。利用主要成分为H₂和CO₂的天然气制氢变压吸附解吸气为原料，设计了气体膜分离耦合CO₂电催化加氢年产3万吨甲酸的工艺，并在Unisim Design流程模拟软件中进行了模拟。随后利用灵敏度分析法对反应器中膜电极面积、阴极电势、H₂膜面积、CO₂膜面积、精馏塔压力和回流比等参数进行优化，在最优方案下甲酸的单位质量成本为6.37 CNY/kg，比传统的Kemiral-Leonard（KL）工艺高31.88%，但是所提出的工艺可以实现减排3.33万吨/年的CO₂，具有重要的环境保护意义。最后通过成本分析，从反应器的寿命、成本和电价三个方面提出三种有效的解决方案，可以将甲酸生产成本降低到传统KL工艺的生产成本。

关键词: 反应器, CO₂电催化, 数学模型, 过程模拟, 优化设计

Abstract:

The impact of CO₂ on the climate is getting more and more serious. Converting it into formic acid can simultaneously realize resource utilization and carbon emission reduction. The current research of CO₂ hydrogenation to formic acid is mainly to find high-performance catalysts, and process design is also indispensable for the industrialization of formic acid, but the process design of CO₂ electrocatalytic hydrogenation to formic acid has not been reported yet. Using natural gas whose main components are H₂ and CO₂ to produce hydrogen pressure swing adsorption desorption gas as raw materials, a process of gas membrane separation coupled with CO₂ electrocatalytic hydrogenation to produce 30000 t of formic acid per year was designed and simulated in Unisim Design process simulation software. Then the sensitivity analysis method was used to optimize the membrane electrode area, cathode potential, H₂ membrane area, CO₂ membrane area, distillation column pressure and reflux ratio. The unit cost of formic acid under the optimal scheme is 6.37 CNY/kg, which is 31.88% higher than the traditional Kemiral-Leonard (KL) process, but the proposed process can reduce 33300 t CO₂ per year, which has important environmental significance. Finally, through cost analysis, three effective solutions are proposed from the three aspects of reactor life, cost and electricity price, which can reduce the production cost of formic acid to that of the traditional KL process.

Key words: reactor, CO₂ electrocatalysis, mathematical modeling, process simulation, optimal design

中图分类号:

TQ 021.6

方远鑫, 肖武, 姜晓滨, 李祥村, 贺高红, 吴雪梅. 膜分离耦合CO₂电催化加氢制甲酸工艺的设计及模拟[J]. 化工学报, 2021, 72(9): 4740-4749.

Yuanxin FANG, Wu XIAO, Xiaobin JIANG, Xiangcun LI, Gaohong HE, Xuemei WU. Process design and simulation of membrane separation coupled with CO₂ electrocatalytic hydrogenation to formic acid[J]. CIESC Journal, 2021, 72(9): 4740-4749.

图/表 16

图1 CO2电催化反应器示意图

Fig.1 The diagram of CO2 electrocatalytic reactor

图2 CO2电催化反应器阴极单流道模型示意图

Fig.2 The diagram of a single-channel model for the cathode of CO2 electrocatalytic reactor

图3 CO2电催化反应器模型与实验值[24]的对比

Fig.3 The comparison of CO2 electrocatalytic reactor models and experimental values[24]

图4 CO2电催化反应器在Unisim Design中单元模块的图标和功能界面

Fig.4 CO2 electrocatalytic reactor unit module icon and function interface in Unisim Design

图5 膜分离耦合CO2电催化加氢制甲酸工艺流程

Fig.5 Membrane separation coupled with CO2 electrocatalytic hydrogenation process for formic acid production

表1 原料气组成

Table 1 Feed gas composition

组成	摩尔分数/%
H₂	45
CO₂	35
CH₄	15
N₂	5

表2 工艺中使用的膜透量数据［32］

Table 2 Membrane permeation data used in the process［32］

膜材料	膜透量/GPU
膜材料	H₂	CO₂	CO	CH₄	N₂
PI	300	20	2	1	1
PEO	85	1000	20	15	15

图6 不同膜电极面积对CO2转化率和选择性的影响

Fig.6 The influence of different membrane electrode area on CO2 conversion and selectivity

图7 阴极电势对CO2转化率和选择性的影响

Fig.7 The influence of cathode potential on CO2 conversion and selectivity

图8 H2膜面积和CO2膜面积对CO2转化率和选择性的影响

Fig.8 The influence of H2 membrane and CO2 membrane area on CO2 conversion and selectivity

图9 加压精馏塔塔顶压力对甲酸回收率和甲酸质量分数的影响

Fig.9 The influence of the pressure at the top of the pressurized distillation column on the recovery rate of formic acid and the mass fraction of formic acid

图10 不同精馏塔中回流比对甲酸质量分数和塔热负荷的影响

Fig.10 The influence of reflux ratio on formic acid mass fraction and tower heat load in different distillation column

表3 关键设备和操作成本

Table 3 Key equipment and operating costs

设备	成本
CO₂电催化反应器	1×10⁴ CNY/m²
H₂膜	1×10⁴ CNY/m²
CO₂膜	0.3×10⁴ CNY/m²
压缩机	0.5×10⁴ CNY/kW
电	0.75 CNY/kWh
循环水	0.19 CNY/t
高压蒸汽	198 CNY/t

表4 公用工程消耗量

Table 4 Utility consumption

类型	消耗量
电能	17217.78 kW
冷却水	201.87 t/h
水蒸气	31.40 kg/h

表5 经济性评估

Table 5 Economic evaluation

项目	数值	折旧年限
98.03%(质量)甲酸产量/(万吨/年)	3.06	—
CO₂消耗量/(万吨/年)	3.33	—
加压精馏塔/(万元/年)	5.5	10年
常压精馏塔/(万元/年)	4	10年
H₂膜组件/(万元/年)	180	5年
CO₂膜组件/(万元/年)	9	5年
压缩机/(万元/年)	184.98	10年
CO₂电催化反应器/(万元/年)	8400	5000 h
CO吸附装置/(万元/年)	144.18	1年
反应器所需电能/(万元/年)	9390.47	—
冷却水/(万元/年)	32.22	—
饱和蒸汽/(万元/年)	2.22	—
压缩机所需电能/(万元/年)	1162.667	—
年度成本/(万元/年)	19505.24	—
单位质量成本/(CNY/kg)	6.37	—

图11 耦合工艺投资和操作成本占比情况

Fig.11 Coupling process investment and operating cost proportion

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膜分离耦合CO₂电催化加氢制甲酸工艺的设计及模拟

Process design and simulation of membrane separation coupled with CO₂ electrocatalytic hydrogenation to formic acid

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