不同CO2捕集技术的CO2耦合绿氢制甲醇工艺研究

doi:10.11949/0438-1157.20220778

摘要/Abstract

摘要：

大量的化石燃料燃烧导致温室气体排放增加，全球气候变暖。世界各国以全球协约的方式减排CO₂，我国也由此提出“碳达峰·碳中和”目标。CO₂捕集以及转化制液体燃料和化学品是双碳目标下行之有效的碳减排措施之一，不仅可以实现CO₂的资源化利用，同时也缓解了国家能源安全问题。本文以燃煤电厂烟气CO₂捕集和CO₂合成甲醇为研究对象，分析了基于四种不同CO₂捕集技术的CO₂耦合绿氢制甲醇工艺。对四种不同CO₂捕集技术的CO₂制甲醇工艺进行了严格的稳态建模和模拟，分析和比较了不同CO₂捕集技术情景下的CO₂制甲醇工艺的技术和经济性能。结果表明，MEA、PCS、DMC和GMS情景的单位甲醇能耗分别是7.81、5.48、5.91和4.66 GJ/ t CH₃OH，GMS情景的单位能耗最低，其次是PCS情景，但随着更高效相变吸收剂的开发，PCS情景的单位甲醇产品的能耗将降低至2.29~2.58 GJ/t CH₃OH。四种情景的总生产成本分别是4314、4204、4279和4367 CNY/ t CH₃OH，PCS情景的成本最低，更具有经济优势。综合分析表明PCS情景的性能表现最好，为可用于燃煤电厂最佳的碳捕集技术，为CO₂高效合成燃料化学品提供方向，缓解化石燃料短缺和环境污染问题。

关键词: CO₂捕集, CO₂制甲醇, 模拟, 过程系统, 技术-经济分析

Abstract:

The burning of large amounts of fossil fuels has led to a rise in greenhouse gas emissions and global warming. The world has proposed a global agreement to reduce CO₂ emissions, and China has proposed the goal of “carbon peaking and carbon neutrality”. CO₂ capture and conversion to liquid fuels and chemicals are one of the effective carbon reduction measures under the carbon peaking and carbon neutrality targets, which not only can realize the resource utilization of CO₂, but also alleviate the national energy security problem. In this paper, we analyze the CO₂ to methanol process coupling green hydrogen, which is based on four different CO₂ capture technologies, taking CO₂ capture from flue gas of coal-fired power generation and CO₂ to methanol as the research objects. Rigorous steady-state modeling and simulation of the CO₂-to-methanol process with four different CO₂ capture technologies are carried out, and compare the technical-economic performance of the CO₂-to-methanol process under different cases of CO₂ capture technologies. The results show that the energy consumption per unit of methanol is 7.81, 5.48, 5.91 and 4.66 GJ/t CH₃OH for the MEA case, PCS case, DMC case and GMS case, respectively. And the GMS case has the lowest energy consumption, followed by the PCS case, but with the development of more efficient phase change solvents, the energy consumption will be reduced to 2.29—2.58 GJ/ t CH₃OH for the PCS case. The total production costs of the four cases are 4314, 4204, 4279 and 4367 CNY/ t CH₃OH, respectively, and the PCS case has the lowest cost and is more economically competitive. The comprehensive analysis shows that the PCS case has the best performance and can be used as the best carbon capture technology for coal-fired power plants, providing directions for efficient CO₂ synthesis of fuel chemicals to alleviate fossil fuel shortage and environmental pollution problems.

Key words: CO₂ capture, CO₂-to-methanol, simulation, process systems, techno-economic analysis

中图分类号:

X 773

季东, 王健, 王可, 李婧玮, 孟文亮, 杨勇, 李贵贤, 王东亮, 周怀荣. 不同CO₂捕集技术的CO₂耦合绿氢制甲醇工艺研究[J]. 化工学报, 2022, 73(10): 4565-4575.

Dong JI, Jian WANG, Ke WANG, Jingwei LI, Wenliang MENG, Yong YANG, Guixian LI, Dongliang WANG, Huairong ZHOU. Process research of methanol production by CO₂ coupled green hydrogen with different CO₂ capture technologies[J]. CIESC Journal, 2022, 73(10): 4565-4575.

图/表 16

表1 燃煤电厂烟气的工况参数

Table 1 The specifications of the flue gas

参数	数值
CO₂/%(mol)	14.6
N₂/%(mol)	77.9
O₂/%(mol)	3.3
H₂O/%(mol)	4.2
烟气流量/(kmol/h)	40000
烟气进料温度/℃	42
烟气进料压力/bar	1.09

图1 不同二氧化碳捕集技术的CTM工艺方案

Fig.1 The CTM process with different CO2 capture technologies

表2 不同二氧化碳捕集技术的CTM工艺建模和模拟过程的关键参数

Table 2 Key parameters for modeling and simulation of CTM process with four different CO2 capture technologies

过程单元	关键参数	数值
CO₂捕集
MEA^[14]	吸收温度	42℃
	解吸温度	120℃
	MEA 消耗	465 t/h
	CO₂ 捕集率	90%
PCS^[15]	吸收温度	42℃
	解吸温度	110℃
	贫相体积分数	41.2%
	CO₂ 捕集率	90%
DMC^[16]	吸收温度	30℃
	吸收压力	3 MPa
	闪蒸压力	5/1 MPa
	CO₂ 捕集率	90%
GMS^[17]	CO₂/N₂选择性（一级膜）	49
	CO₂渗透速率（一级膜）	2000 GPU
	CO₂/N₂选择性（二级膜）	140
	CO₂渗透速率（二级膜）	700 GPU
	渗透压力	0.6 MPa
	CO₂ 捕集率	90%
CO₂转化
MS^[18]	反应温度	250℃
	反应压力	5 MPa
MD^[18]	进料温度	77℃
	操作压力	0.1 MPa
	塔板数	33
	回流比	2.3
	甲醇回收率	99.5%
	甲醇质量分数	99.9%

图2 MEA捕集CO2工艺流程简图

Fig.2 Simplified simulation flowsheet of the MEA technology

表3 方程中的参数k和E

Table 3 The parameters k and E in the equations

反应	k	E/(cal/mol)
（1）	3.02×10¹⁴	9855.8
（2）	1.33×10¹⁷	13249.0
（1）的可逆反应	5.52×10²³	16518.0
（2）的可逆反应	6.63×10¹⁶	25656.0

表4 平衡常数的各项参数

Table 4 The parameters of equilibrium constants

反应	A	B	C
（3）	132.899	-13446	-22.4773
（4）	231.465	-12092	-35.4819
（5）	2.8898	-3635.09	0

图3 PCS捕集CO2工艺流程简图

Fig.3 Simplified simulation flowsheet of the PCS technology

图4 DMC捕集CO2工艺流程简图

Fig.4 Simplified simulation flowsheet of the DMC technology

图5 GMS捕集CO2工艺流程简图

Fig.5 Simplified simulation flowsheet of the GMS technology

图6 甲醇合成过程工艺流程简图

Fig.6 Simplified simulation flowsheet of the methanol synthesis process

表5 CTM过程主要能量消耗

Table 5 Main energy consumption of CTM process

CTM过程	天然气消耗/(t/h)	电力消耗/MWh
C_MEATM	34.72	11.63
C_PCSTM	23.85	13.15
C_DMCTM	16.14	107.80
C_GMSTM	16.12	51.75

表6 主要单元设备投资数据汇总

Table 6 Summary of investment data for main equipment components

单元	基准	S_ref	sf	f	$E I j r e f$ / (10⁶ CNY)
MEA^[16]	CO₂产量	2771.2 t/h	0.67	0.65	206.55
PCS^[28]	CO₂产量	62.26 t/h	0.67	0.65	87.14
DMC^[16]	CO₂产量	2771.2 t/h	0.67	0.65	244.45
GMS^[17]	CO₂产量	423.36 t/h	0.67	0.65	387.8
MS^[29]	合成气进料量	10.81 kmol/s	0.67	0.65	142.8
MD^[29]	甲醇进料量	3.66 kg/s	0.67	0.65	12.04

表6 主要单元设备投资数据汇总

Table 6 Summary of investment data for main equipment components

单元	基准	S_ref	sf	f	$E I j r e f$ / (10⁶ CNY)
MEA^[16]	CO₂产量	2771.2 t/h	0.67	0.65	206.55
PCS^[28]	CO₂产量	62.26 t/h	0.67	0.65	87.14
DMC^[16]	CO₂产量	2771.2 t/h	0.67	0.65	244.45
GMS^[17]	CO₂产量	423.36 t/h	0.67	0.65	387.8
MS^[29]	合成气进料量	10.81 kmol/s	0.67	0.65	142.8
MD^[29]	甲醇进料量	3.66 kg/s	0.67	0.65	12.04

表7 关键参数的模拟结果与文献的比较

Table 7 Comparison of the simulated and reported results of key parameters

过程单元	关键参数	数值	文献值
CO₂捕集
MEA^[14]	MEA补充/(kg/t(CO₂))	1.52	1.50
	MEA循环量/(t/h)	463	—
	贫相CO₂负载/(mol/mol)	0.25	0.20
	再生能耗/(MJ/kg CO₂)	4.02	4.00
	CO₂捕集量（CC unit）/(t/h)	231.26	—
	CO₂捕集纯度/%	99.5	99.5
PCS^[15]	贫相体积分数/%	41.2	43.6
	溶剂循环速率/(kg/h)	4.52×10⁶	4.50×10⁶
	再生能耗/(MJ/kg CO₂)	2.42	2.40
	CO₂捕集量（CC unit）/(t/h)	231.26	—
	CO₂捕集纯度/%	99.5	99.5
DMC^[16]	溶剂损失/(kg/h)	953	946
	电力/MW	635	629
	DMC循环量/(t/h)	976.5	—
	再生能耗/(MJ/kg CO₂)	2.7	—
	CO₂捕集量（CC unit）/(t/h)	231.26	—
	CO₂捕集纯度/%	99.5	99.5
GMS^[17]	总膜面积/(10⁶ m²)	0.72	0.70
	一级膜渗透测气体流率/(mol/s)	9475	9240
	二级膜渗透测气体流率/(mol/s)	8750	8625
	再生能耗/(MJ/kg CO₂)	1.72	1.70
	CO₂捕集量（CC unit）/(t/h)	231.26	—
	CO₂捕集纯度/%	99.5	99.5
CO₂转化
MS单元^[18]	单位甲醇CO₂消耗/(t/(t MeOH)	1.44	1.46
	单位甲醇H₂消耗/(t/t MeOH)	0.194	0.199
	反应器出口流率/(t/h)	472.8	467.6
	反应器出口甲醇组成/%	12.4	12.0
MD单元^[18]	精馏塔塔顶质量流率/(t/h)	55.4	55.1
	甲醇质量分数/%	99.90	99.96
	甲醇产量/(t/h)	161.4	—

图7 不同CO2捕集技术的CTM工艺能耗

Fig.7 Energy consumption of CTM process with different CO2 capture technologies

图8 不同CO2捕集技术的CTM工艺总资本投资

Fig.8 Total capital investment of CTM process with different CO2 capture technologies

图9 不同CO2捕集技术的CTM工艺总生产成本

Fig.9 Total production cost of CTM process with different CO2 capture technologies

参考文献 33

1	IEA. Global Energy Review: CO₂ Emissions in 2021[R]. Paris: IEA, 2021.
2	Jung S H, Kim H, Kang Y, et al. Analysis of Korea's green technology policy and investment trends for the realization of carbon neutrality: focusing on CCUS technology[J]. Processes, 2022, 10(3): 501.
3	黄宏, 杨思宇. 一种低能耗捕集CO₂煤基甲醇和电力联产过程设计[J]. 化工学报, 2017, 68(10): 3860-3869.
	Huang H, Yang S Y. Design of a coal based methanol and power polygeneration process with low energy consumption for CO₂ capture[J]. CIESC Journal, 2017, 68(10): 3860-3869.
4	Papadopoulos A I, Tzirakis F, Tsivintzelis I, et al. Phase-change solvents and processes for postcombustion CO₂ capture: a detailed review[J]. Industrial & Engineering Chemistry Research, 2019, 58(13): 5088-5111.
5	王涛, 刘飞, 方梦祥, 等. 两相吸收剂捕集二氧化碳技术研究进展[J]. 中国电机工程学报, 2021, 41(4): 1186-1196.
	Wang T, Liu F, Fang M X, et al. Research progress in biphasic solvent for CO₂ capture technology[J]. Proceedings of the CSEE, 2021, 41(4): 1186-1196.
6	Tang Z G, Li H W, Fei W Y, et al. Performance evaluation of a novel CO₂ absorbent: dimethyl carbonate[J]. International Journal of Greenhouse Gas Control, 2016, 44: 140-151.
7	Lee S, Binns M, Kim J K. Automated process design and optimization of membrane-based CO₂ capture for a coal-based power plant[J]. Journal of Membrane Science, 2018, 563: 820-834.
8	Kim S H, Kim J K, Yeo J G, et al. Comparative feasibility study of CO₂ capture in hollowfiber membrane processes based on process models and heat exchanger analysis[J]. Chemical Engineering Research and Design, 2017, 117: 659-669.
9	Olah G A. Beyond oil and gas: the methanol economy[J]. Angewandte Chemie International Edition, 2005, 44(18): 2636-2639.
10	王靖, 康丽霞, 刘永忠. 化工系统消纳可再生能源的电-氢协调储能系统优化设计[J]. 化工学报, 2020, 71(3): 1131-1142.
	Wang J, Kang L X, Liu Y Z. Optimal design of electricity-hydrogen energy storage systems for renewable energy penetrating into chemical process systems[J]. CIESC Journal, 2020, 71(3): 1131-1142.
11	Ravikumar D, Keoleian G, Miller S. The environmental opportunity cost of using renewable energy for carbon capture and utilization for methanol production[J]. Applied Energy, 2020, 279: 115770.
12	王集杰, 韩哲, 陈思宇, 等. 太阳燃料甲醇合成[J]. 化工进展, 2022, 41(3): 1309-1317.
	Wang J J, Han Z, Chen S Y, et al. Liquid sunshine methanol[J]. Chemical Industry and Engineering Progress, 2022, 41(3): 1309-1317.
13	Lee B, Lee H, Lim D, et al. Renewable methanol synthesis from renewable H₂ and captured CO₂: how can power-to-liquid technology be economically feasible? [J]. Applied Energy, 2020, 279: 115827.
14	Li B H, Zhang N, Smith R. Simulation and analysis of CO₂ capture process with aqueous monoethanolamine solution[J]. Applied Energy, 2016, 161: 707-717.
15	Wang R J, Liu S S, Wang L D, et al. Superior energy-saving splitter in monoethanolamine-based biphasic solvents for CO₂ capture from coal-fired flue gas[J]. Applied Energy, 2019, 242: 302-310.
16	Zhou W J, Zhu B, Chen D J, et al. Technoeconomic assessment of China's indirect coal liquefaction projects with different CO₂ capture alternatives[J]. Energy, 2011, 36(11): 6559-6566.
17	Xu J Y, Wang Z, Qiao Z H, et al. Post-combustion CO₂ capture with membrane process: practical membrane performance and appropriate pressure[J]. Journal of Membrane Science, 2019, 581: 195-213.
18	Pérez-Fortes M, Schöneberger J C, Boulamanti A, et al. Methanol synthesis using captured CO₂ as raw material: techno-economic and environmental assessment[J]. Applied Energy, 2016, 161: 718-732.
19	Amirkhosrow M, Nemati Lay E. Simulation model evaluation of desorber column in CO₂ capture process by MEA scrubbing: a rigorous rate-based model for kinetic model and mass transfer correlations analysis[J]. Fuel Processing Technology, 2020, 203: 106390.
20	Zhang W D, Jin X H, Tu W W, et al. Development of MEA-based CO₂ phase change absorbent[J]. Applied Energy, 2017, 195: 316-323.
21	Ren L X, Chang F L, Kang D Y, et al. Hybrid membrane process for post-combustion CO₂ capture from coal-fired power plant[J]. Journal of Membrane Science, 2020, 603: 118001.
22	孟文亮, 李贵贤, 周怀荣, 等. 绿氢重构的粉煤气化煤制甲醇近零碳排放工艺研究[J]. 化工学报, 2022, 73(4): 1714-1723.
	Meng W L, Li G X, Zhou H R, et al. A novel coal to methanol process with near zero CO₂ emission by pulverized coal gasification integrated green hydrogen[J]. CIESC Journal, 2022, 73(4): 1714-1723.
23	An X, Zuo Y Z, Zhang Q, et al. Methanol synthesis from CO₂ hydrogenation with a Cu/Zn/Al/Zr fibrous catalyst[J]. Chinese Journal of Chemical Engineering, 2009, 17(1): 88-94.
24	Kiss A A, Pragt J J, Vos H J, et al. Novel efficient process for methanol synthesis by CO₂ hydrogenation[J]. Chemical Engineering Journal, 2016, 284: 260-269.
25	Lim H W, Park M J, Kang S H, et al. Modeling of the kinetics for methanol synthesis using Cu/ZnO/Al₂O₃/ZrO₂ catalyst: influence of carbon dioxide during hydrogenation[J]. Industrial & Engineering Chemistry Research, 2009, 48(23): 10448-10455.
26	Chen J J, Qian Y, Yang S Y. Conceptual design and techno-economic analysis of a coal to methanol and ethylene glycol cogeneration process with low carbon emission and high efficiency[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(13): 5229-5239.
27	Xiang D, Yang S Y, Liu X, et al. Techno-economic performance of the coal-to-olefins process with CCS[J]. Chemical Engineering Journal, 2014, 240: 45-54.
28	Askmar J, Carbol J. Carbon dioxide capture using phase changing solvents — a comparison with state-of-the-art MEA technologies[D]. Gothenburg, Sweden: Chalmers University of Technology, 2017.
29	He C, Feng X. Evaluation indicators for energy-chemical systems with multi-feed and multi-product[J]. Energy, 2012, 43(1): 344-354.
30	Ma Y Q, Liao Y T, Su Y, et al. Comparative investigation of different CO₂ capture technologies for coal to ethylene glycol process[J]. Processes, 2021, 9(2): 207.
31	杨庆, 许思敏, 张大伟, 等. 石油与煤路线制乙二醇过程的技术经济分析[J]. 化工学报, 2020, 71(5): 2164-2172.
	Yang Q, Xu S M, Zhang D W, et al. Techno-economic analysis of oil and coal to ethylene glycol processes[J]. CIESC Journal, 2020, 71(5): 2164-2172.
32	Zhang J F, Qiao Y, Wang W Z, et al. Development of an energy-efficient CO₂ capture process using thermomorphic biphasic solvents[J]. Energy Procedia, 2013, 37: 1254-1261.
33	Chen Z B, Jing G H, Lv B H, et al. An efficient solid-liquid biphasic solvent for CO₂ capture: crystalline powder product and low heat duty[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(38): 14493-14503.

[1]	叶展羽, 山訸, 徐震原. 用于太阳能蒸发的折纸式蒸发器性能仿真[J]. 化工学报, 2023, 74(S1): 132-140.
[2]	张龙, 宋孟杰, 邵苛苛, 张旋, 沈俊, 高润淼, 甄泽康, 江正勇. 管翅式换热器迎风侧翅片末端霜层生长模拟研究[J]. 化工学报, 2023, 74(S1): 179-182.
[3]	张义飞, 刘舫辰, 张双星, 杜文静. 超临界二氧化碳用印刷电路板式换热器性能分析[J]. 化工学报, 2023, 74(S1): 183-190.
[4]	王志国, 薛孟, 董芋双, 张田震, 秦晓凯, 韩强. 基于裂隙粗糙性表征方法的地热岩体热流耦合数值模拟与分析[J]. 化工学报, 2023, 74(S1): 223-234.
[5]	宋嘉豪, 王文. 斯特林发动机与高温热管耦合运行特性研究[J]. 化工学报, 2023, 74(S1): 287-294.
[6]	张思雨, 殷勇高, 贾鹏琦, 叶威. 双U型地埋管群跨季节蓄热特性研究[J]. 化工学报, 2023, 74(S1): 295-301.
[7]	陈哲文, 魏俊杰, 张玉明. 超临界水煤气化耦合SOFC发电系统集成及其能量转化机制[J]. 化工学报, 2023, 74(9): 3888-3902.
[8]	宋明昊, 赵霏, 刘淑晴, 李国选, 杨声, 雷志刚. 离子液体脱除模拟油中挥发酚的多尺度模拟与研究[J]. 化工学报, 2023, 74(9): 3654-3664.
[9]	胡建波, 刘洪超, 胡齐, 黄美英, 宋先雨, 赵双良. 有机笼跨细胞膜易位行为的分子动力学模拟研究[J]. 化工学报, 2023, 74(9): 3756-3765.
[10]	赵佳佳, 田世祥, 李鹏, 谢洪高. SiO₂-H₂O纳米流体强化煤尘润湿性的微观机理研究[J]. 化工学报, 2023, 74(9): 3931-3945.
[11]	何松, 刘乔迈, 谢广烁, 王斯民, 肖娟. 高浓度水煤浆管道气膜减阻两相流模拟及代理辅助优化[J]. 化工学报, 2023, 74(9): 3766-3774.
[12]	刘远超, 关斌, 钟建斌, 徐一帆, 蒋旭浩, 李耑. 单层XSe₂（X=Zr/Hf）的热电输运特性研究[J]. 化工学报, 2023, 74(9): 3968-3978.
[13]	汪林正, 陆俞冰, 张睿智, 罗永浩. 基于分子动力学模拟的VOCs热氧化特性分析[J]. 化工学报, 2023, 74(8): 3242-3255.
[14]	邢雷, 苗春雨, 蒋明虎, 赵立新, 李新亚. 井下微型气液旋流分离器优化设计与性能分析[J]. 化工学报, 2023, 74(8): 3394-3406.
[15]	曾如宾, 沈中杰, 梁钦锋, 许建良, 代正华, 刘海峰. 基于分子动力学模拟的Fe₂O₃纳米颗粒烧结机制研究[J]. 化工学报, 2023, 74(8): 3353-3365.

不同CO₂捕集技术的CO₂耦合绿氢制甲醇工艺研究

Process research of methanol production by CO₂ coupled green hydrogen with different CO₂ capture technologies

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 16

参考文献 33

相关文章 15

编辑推荐

Metrics

本文评价