The new methanation process of VESTA

doi:10.16085/j.issn.1000-6613.2019-0763

Abstract

Abstract:

The existing coal-to-SNG process was analyzed, and a new methanation process of VESTA, which was without recycle compressor and adapted to the wide H₂/CO ratio, was introduced. The remarkable feature of VESTA technology was that the temperature of methanation reaction can be controlled by the use of CO₂ in syngas and additional steam without the need for recycle compressors. Before methanation, only sulfides were removed from the feedstock gas and no carbon dioxide was removed, and then carbon dioxide was removed after the methanation reaction. The results of pilot test showed that the H₂/CO ratio in the feed syngas did not affect the quality of the final SNG product. The concentration of CO₂ in crude SNG was as high as 71%. Therefore, medium pressure liquid CO₂ products can be produced at low cost before CO₂ removal. This liquid CO₂ product not only can be pumped to the pulverized coal gasification unit as the transport gas, but also can be used as a by-product to increase the profits of the enterprise and indirectly reduce carbon emissions. Compared with the existing methanation technology with recycle compressors, the new VESTA methanation technology was not only easier to operate, but also improved the stability and safety of operation, and greatly reduce the investment and energy consumption of purification unit, methanation unit and SNG drying unit. Therefore, the use of VESTA methanation technology can effectively improve the market competitiveness of coal-to-SNG.

Key words: syngas methanation, SNG, methanation process, no recycling process, wide H₂/CO ratio

摘要：

分析了现有煤制合成天然气技术主要存在的问题，介绍了新型无循环、适应宽氢碳比的VESTA甲烷化技术。VESTA甲烷化技术的显著特征是利用合成气中的CO₂和外加水蒸汽来控制甲烷化反应温升，不需要操作条件苛刻的循环气压缩机；在甲烷化反应之前对原料气只脱硫、不脱碳，甲烷化反应之后再集中脱碳；经中试试验得出原料气中的H₂/CO比不影响最终的SNG产品指标；甲烷化后的粗SNG产品气中的CO₂体积分数高达71%，因而可在脱碳前低成本联产中压液体CO₂产品。这部分液体CO₂产品除了可用泵增压输送到粉煤气化单元用作输送气体外，还可以直接作为副产品为企业增加收益，并间接降低了碳排放。新型VESTA甲烷化技术与现有带循环压缩机的甲烷化技术相比，不但更容易操控，而且还提高了操作的稳定性和安全性，同时又能极大地降低净化装置、甲烷化装置及SNG干燥装置的投资和能耗。因此，采用VESTA甲烷化技术，能有效地提高煤制合成天然气的市场竞争力。

关键词: 合成气甲烷化, 合成天然气, 甲烷化工艺, 无循环, 宽氢碳比

CLC Number:

TQ 546

Wanfu GONG,Binghai YAN. The new methanation process of VESTA[J]. Chemical Industry and Engineering Progress, 2020, 39(1): 112-118.

宫万福,闫兵海. 新型VESTA甲烷化工艺路线探究[J]. 化工进展, 2020, 39(1): 112-118.

Figures/Tables 5

References 36

1	田志伟, 汪圣甲, 刘庆. 煤制天然气甲烷化工艺技术研究进展[J]. 化学反应工程与工艺, 2017, 33(6): 559-565.
	TIAN Zhiwei, WANG Shengjia, LIU Qing. Research progress of coal to synthetic natural gas methanation process technology[J]. Chemical Reaction Engineering and Technology, 2017, 33(6): 559-565.
2	李安学, 李春启, 左玉帮, 等. 合成气甲烷化工艺技术研究进展[J]. 化工进展, 2015, 34(11): 3898-3905.
	LI Anxue, LI Chunqi, ZUO Yubang, et al. Research development on syngas methanation technology[J]. Chemical Industry and Engineering Progress, 2015, 34(11): 3898-3905.
3	周恩年. 国内外煤制天然气甲烷化技术及工业化现状[J]. 煤化工, 2015, 43(4): 8-11.
	ZHOU Ennian. The domestic and abroad methanation technology for coal-to-SNG and industrialization status[J]. Coal Chemical Industry, 2015, 43(4): 8-11.
4	Jan KOPYSCINSKI, SCHILDHAUER Tilman J, BIOLLAZ Serge M A. Production of synthetic natural gas(SNG) from coal and dry biomass:a technology review from 1950 to 2009[J]. Fuel, 2010, 89: 1763-1783.
5	刘伟. 合成气制天然气甲烷化催化剂的研究进展[J]. 石油化工, 2018, 47(2): 197-202.
	LIU Wei. Process of methanation catalysts for synthetic natural gas[J]. Petrochemical Technology, 2018, 47(2): 197-202.
6	蔺华林, 李克健, 赵利军. 煤制天然气高温甲烷化催化剂研究进展[J]. 化工进展, 2011, 30(8): 1739-1743.
	LIN Hualin, LI Kejian, ZHAO Lijun. Research progress of coal-based high temperature methanation catalyst for synthetic natural gas[J]. Chemical Industry and Engineering Progress, 2011, 30(8): 1739-1743.
7	王志忠, 何忠, 常瑜. CO甲烷化Ni基催化剂研究进展[J]. 天然气化工(C1化学与化工), 2013, 38: 90-94.
	WANG Zhizhong, HE Zhong, CHANG Yu. Progress in Ni-based catalysts for CO methanation[J]. Natural Gas Chemical Industry, 2013, 38: 90-94.
8	李楠, 侯蕾, 杜霞茹, 等. 合成天然气Ni基甲烷化催化剂的研究进展[J]. 天然气化工(C1化学与化工), 2015, 40: 76-81.
	LI Nan, HOU Lei, DU Xiaru, et al. Research progress in Ni-based methanation catalysts for synthesis of natural gas[J].Natural Gas Chemical Industry, 2015, 40: 76-81.
9	王玮涵, 李振花, 王保伟, 等. 耐硫甲烷化反应的研究进展[J]. 化工学报, 2015, 66(9): 3357-3366.
	WANG Weihan, LI Zhenhua, WANG Baowei, et al. Recent advances in sulfur-resistant methanation[J]. CIESC Journal, 2015, 66(9): 3357-3366.
10	SEHESTED J, DAHL S, JACOBSEN J. Methanation of CO over nickel: mechanism and kinetics at high H₂/CO ratios[J]. J. Phys. Chem. B, 2004, 109(6): 2432-2438.
11	李泽军, 张新波, 何洋, 等. 一种煤制合成天然气的甲烷化工艺: 201110268668.0[P]. 2012-01-25.
	LI Zejun, ZHANG Xinbo, HE Yang, et al. A methanation process for synthetic natural gas from coal: CN201110268668.0[P]. 2012-01-25.
12	易竖棚, 李泽军, 郭雄, 等. 一种带循环的多级甲烷化兰炭尾气制天然气方法: 201210265715.0[P]. 2012-11-14.
	YI Shupeng, LI Zejun, GUO Xiong, et al. A method of producing natural gas from tail gas of blue carbon furnace with circulation and multi-stage methanation: CN201210265715.0[P]. 2012-11-14.
13	李泽军, 张新波, 侯建国, 等. 一种煤制合成天然气的甲烷化工艺: 201510098878.8[P]. 2015-07-08.
	LI Zejun, ZHANG Xinbo, HOU Jianguo, et al. A methanation process for synthetic natural gas from coal: CN201510098878.8[P]. 2015-07-08.
14	李春启, 刘永健, 邱波, 等. 生产合成天然气的方法、装置及其产物天然气: 201010149218.5[P]. 2010-08-25.
	LI Chunqi, LIU Yongjian, QIU Bo, et al. Method and devices for producing synthetic natural gas and SNG product: CN201010149218.5[P]. 2010-08-25.
15	李安学, 李春启, 左玉帮, 等. 生产合成天然气的方法及装置: 201410424970.4[P]. 2016-03-02.
	LI Anxue, LI Chunqi, ZUO Yubang, et al. Method and devices for producing synthetic natural gas: CN201410424970.4[P]. 2016-03-02.
16	李安学, 李春启, 左玉帮, 等. 一种生产代用天然气的方法及装置: 201510137677.4[P]. 2016-11-23.
	LI Anxue, LI Chunqi, ZUO Yubang, et al. A method and device for producing substitute natural gas: CN201510137677.4[P]. 2016-11-23.
17	王树东, 王胜, 李德伏, 等. 一种合成气制天然气的工艺: 201210029444.9[P]. 2013-08-14.
	WANG Shudong, WANG Sheng, LI Defu, et al. A process for producing natural gas from synthetic gas: CN201210029444.9[P]. 2013-08-14.
18	王树东, 白晓波, 苏宏久, 等. 一种用于煤制天然气的合成气甲烷化工艺: 201510014927.5[P]. 2016-08-10.
	WANG Shudong, BAI Xiaobo, SU Hongjiu, et al. A syngas methanation process for coal to natural gas: CN201510014927.5[P]. 2016-08-10.
19	宫万福, 闫兵海, 吕建宁,等. 一种合成气单次通过制天然气的节能装置及工艺: 201611052527.4[P]. 2018-06-01.
	GONG Wanfu, YAN Binghai, Jianning LÜ, et al. Energy-saving device and process for producing natural gas by single-pass process of synthetic gas: CN201611052527.4[P]. 2018-06-01.
20	宫万福, 闫兵海, 吕建宁,等. 一种有效回收低品位余热的甲烷化工艺: 201710800839.7[P]. 2017-12-01.
	GONG Wanfu, YAN Binghai, Jianning LÜ, et al. A methanation process for effectively recovering low grade waste heat: CN201710800839.7[P]. 2017-12-01.
21	闫兵海, 宫万福, 侯宁, 等. 一种一次通过甲烷化工艺: 201811569586.8[P]. 2019-04-09.
	YAN Binghai, GONG Wanfu, HOU Ning, et al. A single-pass methanation process: CN201811569586.8[P]. 2019-04-09.
22	闫兵海, 侯宁, 宫万福, 等. 一种兰炭炉尾气精脱硫及绝热甲烷化工艺: 201811569588.7[P]. 2019-04-09.
	YAN Binghai, HOU Ning, GONG Wanfu, et al. A fine desulfurization of tail gas from blue carbon furnace and adiabatic methanation process: CN201811569588.7[P]. 2019-04-09.
23	闫兵海, 宫万福, 吕建宁, 等. 一种兰炭炉尾气精脱硫及等温甲烷化工艺: 201811569599.5[P]. 2019-04-12.
	YAN Binghai, GONG Wanfu, Jianning LÜ, et al. A fine desulfurization of tail gas from blue carbon furnace and isothermal methanation process: 201811569599.5[P]. 2019-04-12.
24	闫兵海, 宫万福, 吕建宁, 等. 一种一次通过甲烷化工艺: 201811569597.6[P]. 2019-04-09.
	YAN Binghai, GONG Wanfu, Jianning LÜ, et al. A single-pass methanation process: CN201811569597.6[P]. 2019-04-09.
25	JENSEN J H, POULSEN J M, ANDERSEN N U. From coal to clean energy[J]. Nitrogen+Syngas, 2011, 310: 36-37.
26	吴迪. 煤制替代天然气(SNG)甲烷合成工艺研究与开发[J]. 石油化工设计, 2017, 34(1): 3.
	WU Di. Research and development of methanation process for coal to substitute natural gas(SNG)[J]. Petrochemical Design, 2017, 34(1): 3.
27	赵立军, 蔺华林. 甲烷化历史与甲烷化机理研究[J]. 神华科技, 2010, 8(5): 80-84.
	ZHAO Lijun, LIN Hualin. Methanation history and catalytic mechanisms[J]. Shenhua Science and Technology, 2010, 8(5): 80-84.
28	史建公, 刘志坚, 刘春生. 二氧化碳甲烷化研究进展[J]. 中外能源, 2018, 23(10): 71-73.
	SHI Jiangong, LIU Zhijian, LIU Chunsheng. Research progress in methanation of carbon dioxide[J]. Sino-Global Energy, 2018, 23(10): 71-73.
29	PEEBLES D E, GOODMAN D W, WHITE J M. Methanation of carbon dioxide on nickel(100) and the effects of surface modifiers[J]. The Journal of Physical Chemistry, 1983, 87(22): 4378-4387.
30	MAATMAN R, HIEMSTR S. A kinetic study of the methanation of CO₂ over nickel-alumina[J]. Journal of Catalysis, 1980, 62(2):349-356.
31	CHOE S J, KANG H J, KIM S J, et al. Adsorbed carbon formation and carbon hydrogenation for CO₂ methanation on the Ni(111) surface: ASED-MO study[J]. Bulletin of the Korean Chemical Society, 2005, 26(11): 1682-1688.
32	宫万福, 侯宁, 吕建宁, 等. 一种用于煤基合成天然气装置的气体净化方法: 201610061575.3[P]. 2017-08-04.
	GONG Wanfu, HOU Ning, Jianning LÜ, et al. A gas purification method for coal-based synthesis natural gas plant: CN201610061575.3[P]. 2017-08-04.
33	宫万福, 闫兵海, 吕建宁, 等. 一种利用低温甲醇洗工序联产高浓度液体CO₂的方法: 201610791573.X[P]. 2017-02-15.
	GONG Wanfu, YAN Binghai, Jianning LÜ, et al. A method for co-producing high concentration liquid CO₂ by Rectisol process: CN201610791573.>X[P]. 2017-02-15.
34	宫万福, 吕建宁, 闫兵海, 等. 一种制备高纯度液体二氧化碳的节能型装置和方法: 201610785689.2[P]. 2017-02-22.
	GONG Wanfu, Jianning LÜ, YAN Binghai, et al. Energy-saving device and method for producing high-purity liquid CO₂: CN201610785689.2[P]. 2017-02-22.
35	刘光启, 马连湘, 项曙光. 化学化工物性数据手册·无机卷[M]. 增订版. 北京: 化学工业出版社, 2013.
	LIU Guangqi, MA Lianxiang, XIANG Shuguang. Manual of chemical property data (inorganic part)[M]. Beijing: Chemical Industry Press, 2013.
36	宫万福, 侯宁, 葛秀文, 等. 一种用于粉煤气化合成气制天然气的节能工艺: 201710686596.9[P]. 2017-10-13.
	GONG Wanfu, HOU Ning, GE Xiuwen, et al. An energy-saving process for producing natural gas by synthetic gas from pulverized coal gasification: CN201710686596.9[P]. 2017-10-13.

H₂/CO比	原料气体积分数/%
H₂/CO比	H₂	CO	CO₂	N₂+Ar
2.5	46.81	18.74	33.71	0.74
3.2	48.40	15.13	35.70	0.77
3.9	49.45	12.67	37.03	0.85
4.6	50.23	10.91	38.00	0.86
5.3	50.82	9.58	38.74	0.86

H₂/CO比	原料气体积分数/%
H₂/CO比	H₂	CO	CO₂	N₂+Ar
2.5	46.81	18.74	33.71	0.74
3.2	48.40	15.13	35.70	0.77
3.9	49.45	12.67	37.03	0.85
4.6	50.23	10.91	38.00	0.86
5.3	50.82	9.58	38.74	0.86

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