绿氢重构的粉煤气化煤制甲醇近零碳排放工艺研究

doi:10.11949/0438-1157.20211584

化工学报 ›› 2022, Vol. 73 ›› Issue (4): 1714-1723.DOI: 10.11949/0438-1157.20211584

绿氢重构的粉煤气化煤制甲醇近零碳排放工艺研究

孟文亮^1,²(),李贵贤^1,²(),周怀荣^1,²,李婧玮^1,²,王健^1,²,王可^1,²,范学英³,王东亮^1,²()

^1.兰州理工大学石油化工学院，甘肃兰州 730050
^2.甘肃省低碳能源化工重点实验室，甘肃兰州 730050
^3.中国石油兰州石化公司自动化研究院，甘肃兰州 730060

收稿日期:2021-11-09 修回日期:2021-12-22 出版日期:2022-04-05 发布日期:2022-04-25
通讯作者: 李贵贤,王东亮
作者简介:孟文亮（1996—），男，博士研究生，mengwla@163.com
基金资助:
甘肃省科技重大专项(19ZD2GD001);甘肃省高等学校产业支撑计划项目(2020C-06)

A novel coal to methanol process with near zero CO₂ emission by pulverized coal gasification integrated green hydrogen

Wenliang MENG^1,²(),Guixian LI^1,²(),Huairong ZHOU^1,²,Jingwei LI^1,²,Jian WANG^1,²,Ke WANG^1,²,Xueying FAN³,Dongliang WANG^1,²()

^1.School of Petrochemical Engineering, Lanzhou University of Technology, Lanzhou 730050, Gansu, China
^2.Key Laboratory of Low Carbon Energy and Chemical Engineering of Gansu Province, Lanzhou 730050, Gansu, China
^3.Automation Institute, PetroChina Lanzhou Petrochemical Company, Lanzhou 730060, Gansu, China

Received:2021-11-09 Revised:2021-12-22 Online:2022-04-05 Published:2022-04-25
Contact: Guixian LI,Dongliang WANG

摘要/Abstract

摘要：

在“碳达峰、碳中和”的背景下，传统煤制甲醇工艺存在CO₂排放强度大、能耗高等问题成为制约煤制甲醇工艺发展的瓶颈问题。本研究基于外源性的绿氢，重构粉煤气化煤制甲醇工艺，省掉了空分单元、变换单元，开发了短流程低温甲醇洗单元，提出了粉煤气化集成绿氢的近零碳排放煤制甲醇新工艺。从碳元素利用率、CO₂排放、成本分析等角度对新工艺进行了评价。结果表明，与传统煤制甲醇工艺相比，新工艺碳元素利用率从41.50%提高到95.77%，CO₂直接排放量由1.939降低至0.035 t·(t MeOH)^-1，通过分析H₂价格与碳税对产品成本的影响发现，当氢气价格和碳税分别为10.36 CNY·(kg H₂)^-1和223.3 CNY·(t CO₂)^-1时，两种工艺的产品成本相当。新工艺不仅减少了煤制甲醇过程碳排放，而且可以提高可再生能源就地消纳能力，具有良好的应用前景。

关键词: 煤制甲醇, 绿氢, 二氧化碳, 过程集成, 过程系统, 优化设计

Abstract:

In the context of “Emission peak, Carbon neutrality”, high CO₂ emission intensity, and low carbon utilization efficiency greatly restrict the development of the coal to methanol(CTM) process. A novel CTM process is proposed in the paper,which is near zero carbon emission by pulverized coal gasification integrated green hydrogen. In this case, the air separator and water-gas shift units can be eliminated, and acid gas removal unit also can be simplified. The key parameters are analyzed on the basis of established model of the two processes. The advantages of novel process are manifested in detail in comparison with the CTM process. The results show that the carbon utilization rate of the CTM process and the novel process are 41.50% and 95.77%, and the CO₂ direct emission intensity is decreased from 1.939 to 0.035 t·(t MeOH)^-1. An analysis of the impact of hydrogen prices and carbon taxes on product costs reveals that when the hydrogen price and carbon tax are 10.36 CNY·(kg H₂)^-1 and 223.3 CNY·(t CO₂)^-1, the production cost of two processes is equal. The new technology not only reduces carbon emissions from the CTM process, but also improves the on-site absorption capacity of renewable energy, which has good application prospects.

Key words: coal to methanol, green hydrogen, carbon dioxide, process integration, process systems, optimal design

中图分类号:

TQ 536.9

孟文亮, 李贵贤, 周怀荣, 李婧玮, 王健, 王可, 范学英, 王东亮. 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.

Wenliang MENG, Guixian LI, Huairong ZHOU, Jingwei LI, Jian WANG, Ke WANG, Xueying FAN, Dongliang WANG. 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.

图/表 13

参考文献 30

1	Yang Q C, Li X F, Yang Q, et al. Opportunities for CO₂ utilization in coal to green fuel process: optimal design and performance evaluation[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(3): 1329-1342.
2	Chen Q Q, Lv M, Gu Y, et al. Hybrid energy system for a coal-based chemical industry[J]. Joule, 2018, 2(4): 607-620.
3	Hosseini S E, Wahid M A. Hydrogen production from renewable and sustainable energy resources: promising green energy carrier for clean development[J]. Renewable and Sustainable Energy Reviews, 2016, 57: 850-866.
4	唐志永, 孙予罕, 江绵恒. 低碳复合能源系统——中国未来能源的解决方案和发展模式? [J].中国科学, 2013, 43(1): 116-124.
	Tang Z Y, Sun Y H, Jiang M H. Low-carbon hybrid energy systems: future energy solutions and development models in China?[J]. Scientia sinica Chimica 43(1): 116-124.
5	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.
6	Chen J J, Yang S Y, Qian Y. A novel path for carbon-rich resource utilization with lower emission and higher efficiency: an integrated process of coal gasification and coking to methanol production[J]. Energy, 2019, 177: 304-318.
7	Zhang J P, Li Z W, Zhang Z H, et al. Techno-economic analysis of integrating a CO₂ hydrogenation-to-methanol unit with a coal-to-methanol process for CO₂ reduction[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(49): 18062-18070.
8	刘硕士, 杨思宇, 顾竞芳, 等. 气煤联供实现资源高效利用和碳减排技术进展[J]. 化工进展, 2019, 38(1): 664-671.
	Liu S S, Yang S Y, Gu J F, et al. Review on coal and gas co-feed processes for better resource use and lower carbon emission[J]. Chemical Industry and Engineering Progress, 2019, 38(1): 664-671.
9	Qin Z, Zhai G F, Wu X M, et al. Carbon footprint evaluation of coal-to-methanol chain with the hierarchical attribution management and life cycle assessment[J]. Energy Conversion and Management, 2016, 124: 168-179.
10	金涌, 周禹成, 胡山鹰. 低碳理念指导的煤化工产业发展探讨[J]. 化工学报, 2012, 63(1): 3-8.
	Jin Y, Zhou Y C, Hu S Y. Discussion on development of coal chemical industry using low-carbon concept[J]. CIESC Journal, 2012, 63(1): 3-8.
11	Qin Z, Bhattacharya S, Tang K, et al. Effects of gasification condition on the overall performance of methanol-electricity polygeneration system[J]. Energy Conversion and Management, 2019, 184: 362-373.
12	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.
13	Wang D L, Meng W L, Zhou H R, et al. Green hydrogen coupling with CO₂ utilization of coal-to-methanol for high methanol productivity and low CO₂ emission[J]. Energy, 2021, 231: 120970.
14	东赫, 刘金昌, 解强, 等. 典型气流床煤气化炉气化过程的建模[J]. 化工进展, 2016, 35(8): 2426-2431.
	Dong H, Liu J C, Xie Q, et al. Modeling of coal gasification reaction in typical entrained-flow coal gasifiers[J]. Chemical Industry and Engineering Progress, 2016, 35(8): 2426-2431.
15	Qin S Y, Chang S Y, Yao Q. Modeling, thermodynamic and techno-economic analysis of coal-to-liquids process with different entrained flow coal gasifiers[J]. Applied Energy, 2018, 229: 413-432.
16	Park N, Park M J, Ha K S, et al. Modeling and analysis of a methanol synthesis process using a mixed reforming reactor: perspective on methanol production and CO₂ utilization[J]. Fuel, 2014, 129: 163-172.
17	Bussche K M V, Froment G F. A steady-state kinetic model for methanol synthesis and the water gas shift reaction on a commercial Cu/ZnO/Al₂O₃ catalyst[J]. Journal of Catalysis, 1996, 161(1): 1-10.
18	Cui C T, Sun J S, Li X G. A hybrid design combining double-effect thermal integration and heat pump to the methanol distillation process for improving energy efficiency[J]. Chemical Engineering and Processing: Process Intensification, 2017, 119: 81-92.
19	Liu X, Yang S Y, Hu Z G, et al. Simulation and assessment of an integrated acid gas removal process with higher CO₂ capture rate[J]. Computers & Chemical Engineering, 2015, 83: 48-57.
20	Sun L, Smith R. Rectisol wash process simulation and analysis[J]. Journal of Cleaner Production, 2013, 39: 321-328.
21	赵鹏飞, 李水弟, 王立志. 低温甲醇洗技术及其在煤化工中的应用[J]. 化工进展, 2012, 31(11): 2442-2448.
	Zhao P F, Li S D, Wang L Z. Rectisol technology and its application in coal chemical industry[J]. Chemical Industry and Engineering Progress, 2012, 31(11): 2442-2448.
22	贾欣, 赵文星, 王建成, 等. 低温甲醇洗吸收塔产出液再生过程模拟研究[J]. 天然气化工(C1化学与化工), 2019, 44(3): 65-70.
	Jia X, Zhao W X, Wang J C, et al. Regeneration process simulation of the output fluid from rectisol absorber[J]. Natural Gas Chemical Industry, 2019, 44(3): 65-70.
23	Yang Q C, Zhang J L, Chu G Y, et al. Optimal design, thermodynamic and economic analysis of coal to ethylene glycol processes integrated with various methane reforming technologies for CO₂ reduction[J]. Energy Conversion and Management, 2021, 244: 114538.
24	Yang Q C, Zhu S, Yang Q, et al. Comparative techno-economic analysis of oil-based and coal-based ethylene glycol processes[J]. Energy Conversion and Management, 2019, 198: 111814.
25	Yi Q, Wu G S, Gong M H, et al. A feasibility study for CO₂ recycle assistance with coke oven gas to synthetic natural gas[J]. Applied Energy, 2017, 193: 149-161.
26	Zhang D Q, Duan R H, Li H W, et al. Optimal design, thermodynamic, cost and CO₂ emission analyses of coal-to-methanol process integrated with chemical looping air separation and hydrogen technology[J]. Energy, 2020, 203: 117876.
27	Li M X, Zhuang Y, Zhang L, et al. Conceptual design and techno-economic analysis for a coal-to-SNG/methanol polygeneration process in series and parallel reactors with integration of waste heat recovery[J]. Energy Conversion and Management, 2020, 214: 112890.
28	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.
29	Xiang D, Li P, Yuan X Y, et al. Highly efficient carbon utilization of coal-to-methanol process integrated with chemical looping hydrogen and air separation technology: process modeling and parameter optimization[J]. Journal of Cleaner Production, 2020, 258: 120910.
30	王科, 刘永艳. 2020 年中国碳市场回顾与展望[J]. 北京理工大学学报(社会科学版), 2020, 22(2): 10-19.
	Wang K, Liu Y Y. China's carbon market: reviews and prospects for 2020[J]. Journal of Beijing Institute of Technology (Social Sciences Edition), 2020, 22(2): 10-19.

传统煤制甲醇工艺		近零碳排放的煤制甲醇新工艺
煤气化单元		煤气化单元
气化温度/℃	1554	气化温度/℃	1554
气化压力/MPa	8.8	气化压力/MPa	8.8
煤转化率/%	＞99	煤转化率/%	＞99
水煤气变换单元		电解水制氢单元
高/低变温度/℃	350/220	工作效率/%	70~90
压力/MPa	3	工作压力/MPa	3.2
蒸汽/CO摩尔比	0.94	能耗/(kWh·m^-3)	3.8~5.0
低温甲醇洗单元		短流程的低温甲醇洗单元
H₂S移除率/%(mol)	100	H₂S移除率/%(mol)	100
CO₂移除率/%(mol)	96	CO₂移除率/%(mol)	30
甲醇合成单元		甲醇合成单元
催化剂	Cu/ZnO/Al₂O₃	催化剂	Cu/ZnO/Al₂O₃
未反应气循环比/%	99	未反应气循环比/%	99
温度/℃	240	温度/℃	250
压力/MPa	8	压力/MPa	8
甲醇精馏单元		甲醇精馏单元
甲醇回收率/%(mol)	99.9	甲醇回收率/%(mol)	99.9
精甲醇纯度/%(mass)	99.9	精甲醇纯度/%(mass)	99.9

传统煤制甲醇工艺		近零碳排放的煤制甲醇新工艺
煤气化单元		煤气化单元
气化温度/℃	1554	气化温度/℃	1554
气化压力/MPa	8.8	气化压力/MPa	8.8
煤转化率/%	＞99	煤转化率/%	＞99
水煤气变换单元		电解水制氢单元
高/低变温度/℃	350/220	工作效率/%	70~90
压力/MPa	3	工作压力/MPa	3.2
蒸汽/CO摩尔比	0.94	能耗/(kWh·m^-3)	3.8~5.0
低温甲醇洗单元		短流程的低温甲醇洗单元
H₂S移除率/%(mol)	100	H₂S移除率/%(mol)	100
CO₂移除率/%(mol)	96	CO₂移除率/%(mol)	30
甲醇合成单元		甲醇合成单元
催化剂	Cu/ZnO/Al₂O₃	催化剂	Cu/ZnO/Al₂O₃
未反应气循环比/%	99	未反应气循环比/%	99
温度/℃	240	温度/℃	250
压力/MPa	8	压力/MPa	8
甲醇精馏单元		甲醇精馏单元
甲醇回收率/%(mol)	99.9	甲醇回收率/%(mol)	99.9
精甲醇纯度/%(mass)	99.9	精甲醇纯度/%(mass)	99.9

流股	温度/℃	压力/MPa	摩尔分数/%								摩尔流量/ (kmol·h^-1)	质量流量/ (kg·h^-1)
流股	温度/℃	压力/MPa	N₂	O₂	H₂O	CO	CO₂	H₂S	H₂	CH₃OH	摩尔流量/ (kmol·h^-1)	质量流量/ (kg·h^-1)
1	25	0.1	N/A	N/A	N/A	N/A	N/A	N/A	N/A	N/A		100000
2	210	4	0.58	0	6.51	62.65	4.03	0.1	26.13	0	9841.63	208608
3	90	4	0.44	0	0.24	20.69	30.75	0.08	47.8	0	12798	262163
4	30	0.2	6.31	0	0	0.31	93.2	0	0.17	0.01	3240.81	138965
5	30	2.8	0.63	0	0	29.38	1.84	0	68.15	0	8965.75	94945
6	41	0.1	0	0	5.06	0	0.14	0	0	94.8	2904.73	91055
7	67	0.1	0	0	0.18	0	0	0	0	99.82	2755.83	88117.89

流股	温度/℃	压力/MPa	摩尔分数/%								摩尔流量/ (kmol·h^-1)	质量流量/ (kg·h^-1)
流股	温度/℃	压力/MPa	N₂	O₂	H₂O	CO	CO₂	H₂S	H₂	CH₃OH	摩尔流量/ (kmol·h^-1)	质量流量/ (kg·h^-1)
1	25	0.1	N/A	N/A	N/A	N/A	N/A	N/A	N/A	N/A		100000
2	210	4	0.58	0	6.51	62.65	4.03	0.1	26.13	0	9841.63	208608
3	90	4	0.44	0	0.24	20.69	30.75	0.08	47.8	0	12798	262163
4	30	0.2	6.31	0	0	0.31	93.2	0	0.17	0.01	3240.81	138965
5	30	2.8	0.63	0	0	29.38	1.84	0	68.15	0	8965.75	94945
6	41	0.1	0	0	5.06	0	0.14	0	0	94.8	2904.73	91055
7	67	0.1	0	0	0.18	0	0	0	0	99.82	2755.83	88117.89

流股	温度/℃	压力/MPa	摩尔分数/%								摩尔流量/ (kmol·h^-1)	质量流量/ (kg·h^-1)
流股	温度/℃	压力/MPa	N₂	O₂	H₂O	CO	CO₂	H₂S	H₂	CH₃OH	摩尔流量/ (kmol·h^-1)	质量流量/ (kg·h^-1)
1	25	0.1	N/A	N/A	N/A	N/A	N/A	N/A	N/A	N/A		100000
2	86	3.2	0	100	0	0	0	0	0	0	2343.75	75000
3	210	4	0.26	0	6.53	62.85	4.04	0.01	26.21	0	9841.63	208614
4	30	2.8	0.29	0	0	68.15	3.11	0	28.44	0	9062.82	191368
5	86	3.2	0	0	0	0	0	0	100	0	11396.03	22792
6	41	0.1	0	0	3.75	0	0.13	0	0	96.12	6620.84	208758
7	67	0.1	0	0	0.18	0	0	0	0	99.82	6368.89	203646

绿氢重构的粉煤气化煤制甲醇近零碳排放工艺研究

A novel coal to methanol process with near zero CO₂ emission by pulverized coal gasification integrated green hydrogen

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参考文献 30

相关文章 15

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工艺	能耗/(MJ·(kg MeOH))^-1
工艺	AS	CG	WGS	AGR	SAGR	MS	MD
传统煤制甲醇工艺	4.2	-3.0	-1.9	5.5	—	-1.6	2.5
近零碳排放的煤制甲醇新工艺	—	-1.3	—	—	0.8	-1.6	2.4

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绿氢重构的粉煤气化煤制甲醇近零碳排放工艺研究

A novel coal to methanol process with near zero CO2 emission by pulverized coal gasification integrated green hydrogen

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A novel coal to methanol process with near zero CO₂ emission by pulverized coal gasification integrated green hydrogen