氮气/二氧化碳的吸附分离
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摘要
大气温室效应和地球变暖是21世纪人类亟待解决的重大环境问题。目前,人类在能源系统中产生大量CO2(通常以N2和CO2混合气的方式存在)并直接排放是导致上述问题的主要原因。因此从环境保护和节约能源角度考虑,在全球范围内对排放的氮气/二氧化碳混合气进行回收和利用是非常必要的。
本文选择高沸点的N-甲基二乙醇胺(MDEA)作为涂渍液,用不同浓度的涂渍液对粗孔微球硅胶进行预处理,并分别进行了氮气/二氧化碳混合气的穿透和脱附再生实验研究。
首先在0.1MPa压力下,对涂渍不同浓度MDEA的硅胶分离氮气/二氧化碳混合气的性能进行了研究,确定最佳MDEA涂渍浓度为35%。然后,在35%MDEA涂渍浓度下,通过变化吸附压力,确定最佳吸附压力为0.4MPa。
本文同时对两种吸附剂再生方式(冲洗脱附再生和真空脱附再生)进行了对比。发现以冲洗方式对吸附剂进行再生时,在C/C0=0.5(C0为原料气中CO2浓度)时再生成本系数都接近0.4,如此大的再生成本表明本实验中的吸附剂不适宜采用冲洗脱附再生的方法再生,应采用真空脱附再生的方法进行再生。而通过对真空脱附再生方法的研究,发现出口尾气中CO2含量平均为60%,远远高于原料气中CO2含量11.95%,约浓缩了5倍。
所以,综合分离效果和脱附效果来看,以粗孔微球硅胶为担体涂渍35% MDEA的吸附剂效果最好。此吸附剂在操作压力为0.4MPa,再生方式为真空脱附再生时,可将氮气/二氧化碳混合气中的CO2浓度富集5倍左右。
Greenhouse effect is the great environmental problem that human have to solve in the 21st century. Nowadays, the direct emission of CO2(generally existing in the mixture of N2 and CO2) is considered as the root cause. Therefore, capture of greenhouse gases is so necessary from the view of environmental protection and energy saving.
In this paper, we choose MDEA with high boiling point to modify the surface of silica gel and carry out the adsorption and desorption experiments for the mixture of N2 and CO2 respectively to find out the best MDEA coating ratio(35%MDEA coating) and adsorption pressure(0.4MPa).
At the same time, we contrast two regeneration methods. For purging, when C/C0 (C0 is the CO2 concentration of feeding gas) equals to 0.5, the regeneration cost coefficient comes up to 0.4, which is so great as not to be the ideal choice. For vacuuming, the CO2 concentration of exhaust gas averages to 60%, which concentration is about five times higher than the feeding gas.
In conclusion, the silica gel coated 35% MDEA and operated under 0.4 MPa pressure will be the ideal choice for separation of the mixture of N2 and CO2 and the CO2 concentration in vacuuming can be enriched by almost five times.
本文选择高沸点的N-甲基二乙醇胺(MDEA)作为涂渍液,用不同浓度的涂渍液对粗孔微球硅胶进行预处理,并分别进行了氮气/二氧化碳混合气的穿透和脱附再生实验研究。
首先在0.1MPa压力下,对涂渍不同浓度MDEA的硅胶分离氮气/二氧化碳混合气的性能进行了研究,确定最佳MDEA涂渍浓度为35%。然后,在35%MDEA涂渍浓度下,通过变化吸附压力,确定最佳吸附压力为0.4MPa。
本文同时对两种吸附剂再生方式(冲洗脱附再生和真空脱附再生)进行了对比。发现以冲洗方式对吸附剂进行再生时,在C/C0=0.5(C0为原料气中CO2浓度)时再生成本系数都接近0.4,如此大的再生成本表明本实验中的吸附剂不适宜采用冲洗脱附再生的方法再生,应采用真空脱附再生的方法进行再生。而通过对真空脱附再生方法的研究,发现出口尾气中CO2含量平均为60%,远远高于原料气中CO2含量11.95%,约浓缩了5倍。
所以,综合分离效果和脱附效果来看,以粗孔微球硅胶为担体涂渍35% MDEA的吸附剂效果最好。此吸附剂在操作压力为0.4MPa,再生方式为真空脱附再生时,可将氮气/二氧化碳混合气中的CO2浓度富集5倍左右。
Greenhouse effect is the great environmental problem that human have to solve in the 21st century. Nowadays, the direct emission of CO2(generally existing in the mixture of N2 and CO2) is considered as the root cause. Therefore, capture of greenhouse gases is so necessary from the view of environmental protection and energy saving.
In this paper, we choose MDEA with high boiling point to modify the surface of silica gel and carry out the adsorption and desorption experiments for the mixture of N2 and CO2 respectively to find out the best MDEA coating ratio(35%MDEA coating) and adsorption pressure(0.4MPa).
At the same time, we contrast two regeneration methods. For purging, when C/C0 (C0 is the CO2 concentration of feeding gas) equals to 0.5, the regeneration cost coefficient comes up to 0.4, which is so great as not to be the ideal choice. For vacuuming, the CO2 concentration of exhaust gas averages to 60%, which concentration is about five times higher than the feeding gas.
In conclusion, the silica gel coated 35% MDEA and operated under 0.4 MPa pressure will be the ideal choice for separation of the mixture of N2 and CO2 and the CO2 concentration in vacuuming can be enriched by almost five times.
引文
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[3] 闫志勇,张虹,CO2排放导致的地球温升问题及基本技术对策[J],环境科学进展,1999,7(6):175-181
[4] 吴克明,黄松荣,温室气体CO2的分离回收及其资源化[J],武汉科技大学学报(自然科学版),2001,24(4):365-369
[5] 代斌,宫为民,张秀玲等,等离子体催化二氧化碳转化的研究进展[J],化学进展,2002,14(3):225-230
[6] ISLAMMR, CHAKMA A, Storage and utilization of CO2 in petroleum reservoirs, A simulation study [J], Energy Conversion and Management, 1993, 34(9-11) : 1205-1212
[7] 李天成,冯霞,李鑫刚,二氧化碳处理技术现状及其发展趋势,化学工业与工程,2002,4(2):191-196
[8] 周患清,CO2的分离回收工艺[J],湖北化工,1992,4:34-38
[9] 黄肖容,隋贤栋,张学斌,用梯度硅藻土膜分离CO2/N2混合气[J],天然气化工,2002,27:9-13
[10] 秦向东,温铁,金美芳,脱除与浓缩二氧化碳的膜分离技术[J],膜科学与技术,1998,18(6):7-13
[11] 甄寒菲,王志,李保安等,用于分离CO2的高分子膜[J],高分子材料科学与工程,1999,15(6):29-31
[12] VOROBER A V,KHIM TO, Recent advance in CO2 separation [J], Technol 1985, 19(4) : 544
[13] 苏金才,邱介山,炭纤维基复合吸附材料的制备及其气体分离性能研究[J],炭素技术,2001,114(3):1-4
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[17] 郑彤,李邦民,王金渠,多孔陶瓷载体上Y型分子筛膜的气体渗透性能[J],化工装备技术,2003,24(4):14-16
[18] 沙广燕,朱英华,梁长海等,炭-炭复合膜制备的探索研究[J],炭素,2002,111(3):41-43
[19] 夏明珠,严莲荷,雷武等,二氧化碳的分离回收技术与综合利用,现代化工,1999,19(5):46-48
[20] 魏玺,陈健,变压吸附分离技术及其在粉末冶金行业中的应用,化工进展,2002,21(3):209-213
[21] Cheng Tung Chou, Chao Yuh Chen,Carbon dioxide recovery by vacuum swing adsorption, Separation and Purification Technology, 2004, 39 : 51-65
[22] 杨云,变压吸附分离技术的研究进展,广西化工,1999,28(1):26-29
[23] 梁其煜,李式模,邵皓平,变压吸附技术的发展[J],低温工程,1997(5),7-11
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[25] R.Kumar, W.C.Kratz, D.E.Guro, et al, Gas mixture fractionation to produce two high purity products by pressure swing adsorption, Separation Science and Technology, 1992, 27(4) : 509-522
[26] S.Sircar, Pressure Swing dsorption, Ind.Eng.Chen.Res., 2002(41), 1389-1393
[27] 宁平,唐晓龙,易红宏,变压吸附工艺的研究与进展,云南化工,2003,30(3):28-31
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