低浓度煤层气分离提纯的研究进展
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摘要
综述了应用于低浓度煤层气分离的主要方法,包括低温精馏法、吸附分离法、膜分离法和水合物法,探讨了各种方法在不同工艺条件下的分离效果,分析了它们的优缺点。文中总结了每种方法需要解决与突破的关键性问题:低温精馏法获得的甲烷浓度高,但在处理含氧煤层气时首先要脱氧;吸附分离的关键技术在于吸附剂的选择,吸附剂决定了该方法的经济效益与难易程度;对于膜法分离,影响煤层气分离效果的主要因素在于膜材料的选择及制膜工艺;对于水合物法,寻找制备具有较高分离效率的添加剂是关键。最后指出,多种方法结合、多级分离的分离方法是未来研究发展方向。
This paper reviewed the methods of methane(CH4) separation and purification from coal-bed methane(CBM),including low-temperature distillation,adsorption,membrane separation and gas hydrate separation.By the analysis of the advantages and the disadvantages of these methods,the separation efficiencies under different technical conditions were compared and discussed.Key issues needed to be solved for each method were summarized.For the low-temperature distillation method,de-oxidation is necessarily conducted for the oxygen-containing CBM.The selection of the adsorbent is the key for the adsorption method because the adsorbent determines the economy benefit directly.As for the membrane separation,the separation is affected by the selection of the membrane materials and membrane-making technology.For the hydrated-based CH4 separation,a good additive is crucial to promote the hydrate formation and enhance the CH4 separation efficiency.Finally,the separation of multi-methods or the separation by multi-stage processes is proposed for the future development of CBM separation.
This paper reviewed the methods of methane(CH4) separation and purification from coal-bed methane(CBM),including low-temperature distillation,adsorption,membrane separation and gas hydrate separation.By the analysis of the advantages and the disadvantages of these methods,the separation efficiencies under different technical conditions were compared and discussed.Key issues needed to be solved for each method were summarized.For the low-temperature distillation method,de-oxidation is necessarily conducted for the oxygen-containing CBM.The selection of the adsorbent is the key for the adsorption method because the adsorbent determines the economy benefit directly.As for the membrane separation,the separation is affected by the selection of the membrane materials and membrane-making technology.For the hydrated-based CH4 separation,a good additive is crucial to promote the hydrate formation and enhance the CH4 separation efficiency.Finally,the separation of multi-methods or the separation by multi-stage processes is proposed for the future development of CBM separation.
引文
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[19]Bhadra S J,Farooq S.Separation of methane-nitrogen mixture bypressure swing adsorption for natural gas upgrading[J].Industral&Engineering Chemistry Research,2011,50:14030-14045.
[20]Cavenati S,Grande C A,Rodrigues A E.Separation of CH4/CO2/N2mixtures by layered pressure swing adsorption for upgrade of naturalgas[J].Chemical Engineering Science,2006,61(12):3885-3892.
[21]Utaki T.Development of coal mine methane concentration technologyfor reduction of greenhouse gas emissions[J].Science China:Technological Sciences,2010,53(1):28-32.
[22]Yang X,Liu Y S,Li Y L,et al.Low concentration coal minemethane concentrated by vacuum pressure swing adsorption[C]//Changsha:2010 International Conference on Digital Manufacturing&Automation,2010.
[23]Mollmer J,Lange M,Moller A,et al.Pure and mixed gas adsorptionof CH4and N2on the metal-organic framework Basolite(R)A100 anda novel copper-based 1,2,4-triazolyl isophthalate MOF[J].Journal ofMaterials Chemistry,2012,22(20):10274-10286.
[24]杨雄,刘应书,李永玲,等.基于活性炭的真空变压吸附提浓煤层气甲烷的实验研究[J].煤炭学报,2010,35(6):987-991.
[25]章川泉,林文胜,顾安忠,等.CH4/N2混合气体在CMS上的低温吸附分离实验研究[J].低温与超导,2008,36(5):9-12.
[26]席芳,林文胜,顾安忠.CH4/N2混合气在炭分子筛上的变压吸附分离[J].煤炭学报,2011,6(6):1032-1035.
[27]刘聪敏.吸附法浓缩煤层气甲烷研究[D].天津:天津大学,2010.
[28]Li P Y,Tezel F H.Pure and binary adsorption of methane andnitrogen by silicalite[J].Journal of Chemical and Engineering Data,2009,54(10):8-15.
[29]Mulgundmath V P,Tezel F H,Hou F,et al.Binary adsorptionbehaviour of methane and nitrogen gases[J].Journal of PorousMaterials,2012,19(40):455-464.
[30]赵国峰,刘欣梅,代晓东,等.煤矿瓦斯气中低浓度CH4吸附富集研究[J].工业催化,2007,15(8):44-49.
[31]张晓环.低浓度甲烷的吸附研究[D].上海:华东理工大学,2012.
[32]向广艳,潘红艳,张煜,等.含氧煤层气分离提纯技术的研究进展[J].贵州化工,2012,37(2):1-9.
[33]孟翠翠,牟文荷,罗新荣.膜法分离净化煤层气的基础研究[J].能源技术与管理,2009(5):53-55.
[34]Powell C E,Qiao G G.Polymeric CO2/N2gas separation membranesfor the capture of carbon dioxide power plant flue gases[J].Journal ofMembrane Science,2006,279(1-2):1-49.
[35]Saimani S,Dal-Cin M M,Kumar A.Separation performance ofasymmetric membranes based on PEGDa/PEI semi-interpenetratingpolymer network in pure and binary gas mixtures of CO2,N2 andCH4[J].Journal of Membrane Science,2010,362(1-2):353-359.
[36]Lokhandwala K A,Pinnau I,He Z J,et al.Membrane separation ofnitrogen from natural gas:A case study from membrane synthesis tocommercial deployment[J].Journal of Membrane Technology andResearch,2010,346(2):270-279.
[37]Liu B,Smit B.Comparative molecular simulation study of CO2/N2and CH4/N2 separation in zeolites and metal-organic frameworks[J].American Chemical Society,2009,25(10):5918-5926.
[38]Gilani N,Daryan J T,Rashidi A,et al.Separation ofmethane–nitrogen mixtures using synthesis vertically aligned carbonnanotube membranes[J].Applied Surface Science,2012,258(10):4819-4825.
[39]Van den Bergh J,Zhu W,Gascon J,et al.Separation and permeationcharacteristics of a DD3R zeolite membrane[J].Journal of MembraneScience,2008,316(1-2):35-45.
[40]王树立,郑志,徐晓瑞.含氧煤层气膜分离数学模型的建立与应用[J].天然气化工,2010,35(6):59-63.
[41]郑志.含氧煤层气膜法分离提纯的理论研究[J].化学工业与工程,2010,27(6):510-515.
[42]牟文荷,罗新荣,孟翠翠.炭膜用于煤矿瓦斯提纯的新技术构想[J].能源技术与管理,2009(3):98-100.
[43]刘东华.孔狭缝及孔网络模型在炭膜气体分离中的应用[D].大连:大连理工大学,2007.
[44]徐晓瑞,王树立,李恩田,等.管输煤层气净化的膜组件[J].化工机械,2011,38(3):273-275.
[45]Zhong D L,Ye Y,Yang C.Equilibrium conditions for semiclathratehydrates formed in the CH4+N2+O2+tetra-n-butyl ammoniumbromide systems[J].Journal of Chemical and Engineering Data,2011,56(6):2899-2903.
[46]Zhong D L,Englezos P.Methane separation from coal mine methanegas by tetra-n-butyl ammonium bromide semiclathrate hydrateformation[J].Energy&Fuels,2012,26(4):2098-2106.
[47]Sun Q,Guo X Q,Liu AX,et al.Experimental study on the separationof CH4 and N2 via hydrate formation in TBAB solution[J].Industrial&Engineering Chemistry Research,2011,50(4):2284-2288.
[48]Zhang B Y,Wu Q.Thermodynamic promotion of tetrahydrofuran onmethane separation from low-concentration coal mine methane basedon hydrate[J].Energy&Fuels,2010,24(4):2530-2535.
[49]Zhang B Y,Cheng Y P,Wu Q.Sponge effect on coal mine methaneseparation based on clathrate hydrate method[J].Chinese Journal ofChemical Engineering,2011,19(4):610-614.
[50]Li X S,Cai J,Chen Z Y,et al.Hydrate-based methane separationfrom the drainage coal-bedmethane with tetrahydrofuran solution inthe presence of sodium dodecyl sulfate[J].Energy&Fuels,2012,26(2):1144-1151.
[51]赵建忠,赵阳升,石定贤.THF溶液水合物技术提纯含氧煤层气的实验[J].煤炭学报,2008,33(12):1419-1424.
[52]吴强,张保勇,孙登林,等.利用水合原理分离矿井瓦斯实验[J].煤炭学报,2009,34(3):361-365.
[53]吴强,朱玉梅,张保勇.低浓度瓦斯气体水合分离工程中十二烷基硫酸钠和高岭土的影响[J].化工学报,2009,60(5):1193-1198.
[2]毛庆国,陈贵峰,谢华,等.中国煤层气利用途径[J].洁净煤技术,2009,15(4):14-16.
[3]马晓钟.煤矿瓦斯综合利用技术的探索与实践[J].中国煤层气,2007,4(3):28-31.
[4]王长元,王正辉,陈孝通.低浓度煤层气变压吸附浓缩技术研究现状[J].矿业安全与环保,2008,35(6):70-72.
[5]杨江峰,赵强,于秋红,等.煤层气回收及CH4/N2分离PSA材料的研究进展[J].化工进展,2011,30(4):793-801.
[6]郭东.低浓度煤层气资源利用现状及效益分析[J].中国煤层气,2008,5(3):41-46.
[7]Pahade R F,Saunders J B,Maloney J J.Process for separatingmethane and nitrogen:US,4592767[P].1986-06-03.
[8]陶鹏万,王晓东,黄建彬.低温法浓缩煤层气中的甲烷[J].天然气化工,2005,30(4):43-46.
[9]西南化工研究设计院.煤层气低温分离提浓甲烷工艺:中国,1718680A[P].2006-01-11.
[10]杨克剑.含氧煤层气的分离与液化[J].中国煤层气,2007,4(4):20-22.
[11]孙恒,朱鸿梅,舒丹.一种低浓度煤层气低温液化分馏工艺的模拟与分析[J].低温技术,2009,37(8):21-23.
[12]肖露,任小坤,张武,等.低浓度煤层气含氧液化冷箱的研制[J].矿业安全与环保,2011,38(5):19-21.
[13]季中敏,范庆虎,刘晓东.适合于低浓度煤层气的低温液化精馏浓缩的工艺流程模拟与分析[J].煤炭技术,2010,29(6):11-13.
[14]范庆虎.含氮氧煤层气液化装置中关键技术的研究[D].哈尔滨:哈尔滨工业大学,2011.
[15]上海交通大学.含氧煤层气的液化精馏方法:中国,101922849A[P].2010-12-22.
[16]吴剑锋,孙兆虎,公茂琼.从含氧煤层气中安全分离提纯甲烷的工艺方法[J].天然气工业,2009,29(2):113-116.
[17]Delgado J A,Uguina M A,Sotelo J L,et al.Modelling of thefixed-bed adsorption of methane/nitrogen mixtures on silicalitepellets[J].Separation and Purification Technology,2006,50(2):192-203.
[18]Grande C A,Cavenat S,Da Silva F A,et al.Carbon molecular sievesfor hydrocarbon separations by adsorption[J].Industrial&Engineering Chemistry Research,2005,44(18):7218-7227.
[19]Bhadra S J,Farooq S.Separation of methane-nitrogen mixture bypressure swing adsorption for natural gas upgrading[J].Industral&Engineering Chemistry Research,2011,50:14030-14045.
[20]Cavenati S,Grande C A,Rodrigues A E.Separation of CH4/CO2/N2mixtures by layered pressure swing adsorption for upgrade of naturalgas[J].Chemical Engineering Science,2006,61(12):3885-3892.
[21]Utaki T.Development of coal mine methane concentration technologyfor reduction of greenhouse gas emissions[J].Science China:Technological Sciences,2010,53(1):28-32.
[22]Yang X,Liu Y S,Li Y L,et al.Low concentration coal minemethane concentrated by vacuum pressure swing adsorption[C]//Changsha:2010 International Conference on Digital Manufacturing&Automation,2010.
[23]Mollmer J,Lange M,Moller A,et al.Pure and mixed gas adsorptionof CH4and N2on the metal-organic framework Basolite(R)A100 anda novel copper-based 1,2,4-triazolyl isophthalate MOF[J].Journal ofMaterials Chemistry,2012,22(20):10274-10286.
[24]杨雄,刘应书,李永玲,等.基于活性炭的真空变压吸附提浓煤层气甲烷的实验研究[J].煤炭学报,2010,35(6):987-991.
[25]章川泉,林文胜,顾安忠,等.CH4/N2混合气体在CMS上的低温吸附分离实验研究[J].低温与超导,2008,36(5):9-12.
[26]席芳,林文胜,顾安忠.CH4/N2混合气在炭分子筛上的变压吸附分离[J].煤炭学报,2011,6(6):1032-1035.
[27]刘聪敏.吸附法浓缩煤层气甲烷研究[D].天津:天津大学,2010.
[28]Li P Y,Tezel F H.Pure and binary adsorption of methane andnitrogen by silicalite[J].Journal of Chemical and Engineering Data,2009,54(10):8-15.
[29]Mulgundmath V P,Tezel F H,Hou F,et al.Binary adsorptionbehaviour of methane and nitrogen gases[J].Journal of PorousMaterials,2012,19(40):455-464.
[30]赵国峰,刘欣梅,代晓东,等.煤矿瓦斯气中低浓度CH4吸附富集研究[J].工业催化,2007,15(8):44-49.
[31]张晓环.低浓度甲烷的吸附研究[D].上海:华东理工大学,2012.
[32]向广艳,潘红艳,张煜,等.含氧煤层气分离提纯技术的研究进展[J].贵州化工,2012,37(2):1-9.
[33]孟翠翠,牟文荷,罗新荣.膜法分离净化煤层气的基础研究[J].能源技术与管理,2009(5):53-55.
[34]Powell C E,Qiao G G.Polymeric CO2/N2gas separation membranesfor the capture of carbon dioxide power plant flue gases[J].Journal ofMembrane Science,2006,279(1-2):1-49.
[35]Saimani S,Dal-Cin M M,Kumar A.Separation performance ofasymmetric membranes based on PEGDa/PEI semi-interpenetratingpolymer network in pure and binary gas mixtures of CO2,N2 andCH4[J].Journal of Membrane Science,2010,362(1-2):353-359.
[36]Lokhandwala K A,Pinnau I,He Z J,et al.Membrane separation ofnitrogen from natural gas:A case study from membrane synthesis tocommercial deployment[J].Journal of Membrane Technology andResearch,2010,346(2):270-279.
[37]Liu B,Smit B.Comparative molecular simulation study of CO2/N2and CH4/N2 separation in zeolites and metal-organic frameworks[J].American Chemical Society,2009,25(10):5918-5926.
[38]Gilani N,Daryan J T,Rashidi A,et al.Separation ofmethane–nitrogen mixtures using synthesis vertically aligned carbonnanotube membranes[J].Applied Surface Science,2012,258(10):4819-4825.
[39]Van den Bergh J,Zhu W,Gascon J,et al.Separation and permeationcharacteristics of a DD3R zeolite membrane[J].Journal of MembraneScience,2008,316(1-2):35-45.
[40]王树立,郑志,徐晓瑞.含氧煤层气膜分离数学模型的建立与应用[J].天然气化工,2010,35(6):59-63.
[41]郑志.含氧煤层气膜法分离提纯的理论研究[J].化学工业与工程,2010,27(6):510-515.
[42]牟文荷,罗新荣,孟翠翠.炭膜用于煤矿瓦斯提纯的新技术构想[J].能源技术与管理,2009(3):98-100.
[43]刘东华.孔狭缝及孔网络模型在炭膜气体分离中的应用[D].大连:大连理工大学,2007.
[44]徐晓瑞,王树立,李恩田,等.管输煤层气净化的膜组件[J].化工机械,2011,38(3):273-275.
[45]Zhong D L,Ye Y,Yang C.Equilibrium conditions for semiclathratehydrates formed in the CH4+N2+O2+tetra-n-butyl ammoniumbromide systems[J].Journal of Chemical and Engineering Data,2011,56(6):2899-2903.
[46]Zhong D L,Englezos P.Methane separation from coal mine methanegas by tetra-n-butyl ammonium bromide semiclathrate hydrateformation[J].Energy&Fuels,2012,26(4):2098-2106.
[47]Sun Q,Guo X Q,Liu AX,et al.Experimental study on the separationof CH4 and N2 via hydrate formation in TBAB solution[J].Industrial&Engineering Chemistry Research,2011,50(4):2284-2288.
[48]Zhang B Y,Wu Q.Thermodynamic promotion of tetrahydrofuran onmethane separation from low-concentration coal mine methane basedon hydrate[J].Energy&Fuels,2010,24(4):2530-2535.
[49]Zhang B Y,Cheng Y P,Wu Q.Sponge effect on coal mine methaneseparation based on clathrate hydrate method[J].Chinese Journal ofChemical Engineering,2011,19(4):610-614.
[50]Li X S,Cai J,Chen Z Y,et al.Hydrate-based methane separationfrom the drainage coal-bedmethane with tetrahydrofuran solution inthe presence of sodium dodecyl sulfate[J].Energy&Fuels,2012,26(2):1144-1151.
[51]赵建忠,赵阳升,石定贤.THF溶液水合物技术提纯含氧煤层气的实验[J].煤炭学报,2008,33(12):1419-1424.
[52]吴强,张保勇,孙登林,等.利用水合原理分离矿井瓦斯实验[J].煤炭学报,2009,34(3):361-365.
[53]吴强,朱玉梅,张保勇.低浓度瓦斯气体水合分离工程中十二烷基硫酸钠和高岭土的影响[J].化工学报,2009,60(5):1193-1198.