共电解耦合CO2间接加氢制甲醇工艺集成设计与性能评价

doi:10.11949/0438-1157.20241084

摘要/Abstract

摘要：

针对传统二氧化碳加氢制甲醇单程转化率低的问题，提出了一种新的工艺：共电解耦合CO₂间接加氢制甲醇（Co-SOEC-CO₂tM），该工艺由共电解制取合成气单元、精馏单元以及二氧化碳捕集单元组成。基于工艺全流程模拟数据，进行公用工程电气化改造，并采用元素利用率、能效、CO₂排放、生产成本指标等对新工艺进行技术经济评价，并与传统甲醇合成工艺进行对比分析。结果表明：新工艺的能效最高可达61.76%，远高于其他传统工艺。新工艺的氢元素利用率为70.99%，碳元素利用率为80.84%，CO₂排放可以低至0.197 t/t （MeOH），相比于其他合成甲醇工艺具有明显优势。然而，当前可再生能源电价为0.35 CNY/kWh，新工艺成本较高，随着可再生能源的大力发展，未来电价下降至0.1 CNY/kWh时，新工艺的成本最低可降至1785.16 CNY/t （MeOH），具备良好的经济可行性和优势。

关键词: CO₂制甲醇, 共电解, 固体氧化物电解槽, 电气化, 技术-经济分析

Abstract:

Aiming to address the issue of low one-way conversion in traditional CO₂ hydrogenation to methanol, a new process of indirect hydrogenation of CO₂ to methanol by co-electrolysis coupling is proposed in this paper (Co-SOEC-CO₂tM). The process comprises a CO₂ capture unit, a co-electrolysis unit for syngas production, and a methanol synthesis and distillation unit. Based on the simulation data of the whole process, the utility engineering electrification transformation was carried out, and the technical and economic evaluation of the new process was carried out using element utilization, energy efficiency, CO₂ emissions, production cost indicators, etc., and compared with the traditional methanol synthesis process. The results show that the energy efficiency of the new process is up to 61.76%, which is significantly higher than that of other traditional processes. The hydrogen utilization rate of the new process is 70.99%, the carbon utilization rate is 80.84%, and the CO₂ emission can be as low as 0.197 t/t (MeOH), which is a significant advantage compared to other methanol synthesis processes. However, at the current renewable energy tariff of 0.35 CNY/kWh, the cost of the new process is high. With the vigorous development of renewable energy, when the tariff decreases to 0.1 CNY/kWh in the future, the cost of the new process can be reduced to as low as 1785.16 CNY/t (MeOH), making it economically feasible and advantageous.

Key words: CO₂-to-methanol, co-electrolysis, solid oxide electrolysis cell, electrification, techno-economic analysis

中图分类号:

TQ 09

周怀荣, 伊嘉伟, 曹阿波, 郭奥雪, 王东亮, 杨勇, 杨思宇. 共电解耦合CO₂间接加氢制甲醇工艺集成设计与性能评价[J]. 化工学报, 2025, 76(9): 4586-4600.

Huairong ZHOU, Jiawei YI, Abo CAO, Aoxue GUO, Dongliang WANG, Yong YANG, Siyu YANG. Integrated design and performance evaluation of co-electrolysis coupled CO₂ indirect hydrogenation methanol synthesis process[J]. CIESC Journal, 2025, 76(9): 4586-4600.

图/表 19

图1 Co-SOEC耦合CO2间接加氢制甲醇工艺流程

Fig.1 Flow diagram of Co-SOEC-CO2tM process

图2 Co-SOEC共电解H2O和CO2反应机理

Fig.2 Basic principle of the Co-SOEC technology

表1 反应动力学参数［26］

Table 1 Reaction kinetic parameters［26］

Reaction	k	E_a/(J/(mol·K))
A	4.0638×10^-6 [kmol/(kg_cat·s·Pa)]	11695
B	9.0421×10⁸ [kmol/(kg_cat·s·Pa^1/2)]	112860
C	1.5188×10^-33 [kmol/(kg_cat·s·Pa)]	266010

表2 SOEC系统关键物流模拟结果

Table 2 Critical logistics simulation results of SOEC system

流股	温度/℃	压力/MPa	摩尔流量/ (kmol/h)	摩尔分数/%							质量流量/ (kg/h)
流股	温度/℃	压力/MPa	摩尔流量/ (kmol/h)	H₂O	O₂	H₂	CO₂	N₂	CO	CH₃OH	质量流量/ (kg/h)
1	42.00	0.13	40000	4.20	3.3	0	14.6	77.9	0	0	1202421
2	40.00	0.10	5232	0	0	0	100.00	0	0	0	230266
3	25.00	0.10	13300	100.00	0	0	0	0	0	0	239603
4	40.00	0.10	16537	0	0	68.36	3.49	0	28.15	0	178578
5	230.00	5.00	75444	0.01	0	88.38	2.57	0	8.60	0.44	412260
6	250.00	5.00	65189	0.77	0	85.79	2.21	0	2.84	8.38	412260
7	72.74	0.13	5617	8.77	0	0	0	0	0	91.23	173072
8	64.38	0.10	4732	0.25	0	0	0	0	0	99.75	151270

图3 Co-SOEC共电解单元换热网络

Fig.3 The heat exchanger network of Co-SOEC unit

图4 CO2捕集单元换热网络

Fig.4 The heat exchanger network of CO2 capture unit

图5 甲醇合成与精馏单元换热网络

Fig.5 The heat exchanger network of MSD unit

图6 燃烧单元换热网络

Fig.6 The heat exchanger network of COMB unit

图7 电能平衡结构

Fig.7 Electricity balance structure

图8 Co-SOEC-CO2tM工艺的氢、碳元素流动图

Fig.8 The hydrogen and carbon element flow of the Co-SOEC-CO2tM process

图9 不同甲醇合成工艺的氢、碳元素利用率

Fig.9 Utilization of hydrogen and carbon elements in different methanol synthesis processes

图10 Co-SOEC-CO2tM工艺的能量流动图

Fig.10 Energy flow diagram of Co-SOEC-CO2tM process

图11 甲醇合成工艺的能量利用效率

Fig.11 Energy utilization efficiency of different methanol synthesis processes

表3 CO2间接排放因子

Table 3 Indirect emission factor

CO₂排放	数值
原煤燃烧/(t/MJ)	98
风力发电/(t/MWh)	22000
光伏发电/(t/MWh)	101500
风光耦合发电/(t/MWh)	23300

图12 甲醇合成工艺不同的CO2排放

Fig.12 CO2 emissions of different methanol synthesis processes

图13 甲醇合成不同工艺的生产成本

Fig.13 The production cost of methanol synthesis with different processes

表4 当前场景和未来场景的运营成本

Table 4 Operating costs of the current scenarios and future scenarios

价格	当前	未来
煤/(CNY/t)	550.0	450.0
天然气/(CNY/m³)	1.6	1.40
生物质/(CNY/t)	750.0	600.0
可再生电能/(CNY/kWh)	0.35	0.1
碳税/(CNY/t)	51.0	160.0

图14 当前和未来情景下甲醇合成不同工艺的生产成本

Fig.14 Total production costs of different methanol synthesis processes in current and future situations

图15 不同甲醇合成工艺的相对性能矩阵

Fig.15 Relative performance matrix of methanol synthesis process

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共电解耦合CO₂间接加氢制甲醇工艺集成设计与性能评价

Integrated design and performance evaluation of co-electrolysis coupled CO₂ indirect hydrogenation methanol synthesis process

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