水合物法分离技术研究

水合物法分离技术研究*樊拴狮　程宏远　陈光进　郭天民(石油大学流体高压相态及物性研究室,北京102200)　　　,,,。、。　,,,,SeparationtechniquebasedongashydrateformationFanShuanshi,ChengHongyuan,ChenGuangjin,GuoTianmin(HighPressureFluidPhaseBehavior&PropertyResearchLaboratoryofUniversityofPetroleum,Beijing102200)Abstract　Theseparationprocessesbasedonthepropertiesofclathratehydrates,bothforgasseparationsandforwater-containingseparations,arediscussed.Also,theliteratureonthehistoryandprogressofthenewtechnologyarereviewed.Keywords　hydrate,separationtechnology,gasseparation,desalination,watertreatment　　1810,。30,,。,[1,2]。,,。[3]、、[3]、[2]。60[4,5],,80%[6],。90,,。1　-。,(),　*。()。。,vanderWaals。,Ⅰ、ⅡH3。Ⅰ,。Ⅱ,。H(H),。(D-512)3,(T-51262)、(H-51264)(E-51268)Ⅰ、ⅡH。,H(D-435663)。3:ⅠT,ⅡHD。H3D、2D1E,34,S3S2L·34H2O。13,5。·11·　1999192图1　3种水合物晶体结构和相应的笼　　,。,HeH2(0.3nm),Ar、Kr;O2、N2;、、。,、。,(Rmc)0.9,,。,SⅠ51262Rmc=0.939,SⅠ,SⅠSⅡ512Rmc1.08,,SⅡ51264Rmc0.9,SⅡ。,SⅡ(SⅡ51264)。,,SⅡ。,(),(),(),()。,,SⅠSⅡ,。1%,-50%。vanderWaals-Platteeuw,、[1]。1,。,0.5nmSⅠ;,,。,。1　/nmRmcSⅠSⅡ51251262512512640℃/MPaN20.410.8040.7000.8170.61614.30SⅠO20.420.8200.7170.8370.63111.10SⅠCO20.5121.000.8341.020.7691.26SⅠCH40.4360.8550.7440.8680.6552.56SⅠH2S0.4580.8980.7820.9120.6870.093SⅠC2H40.510.9960.8311.0160.7660.55SⅠC2H60.551.080.9391.100.8260.53SⅡC3H80.6281.231.071.250.9430.176SⅡi-C4H100.651.271.111.290.9760.113SⅡn-C4H100.711.391.211.411.07SⅡ　　:,SLOAN[16],。·12·1999192　　　,,85%15%。,,3。850～1050kg/m3。0℃。,、()、、、。,。,,。2图2　水合物法分离过程示意图,。,,。、,,,,。2　,:。、(5),(),;()、、。、,[4,5]。,,。、。,:/,,,,,,,。,SⅡ,(1),0℃0.176MPa,1m371m3,。Huang[6],、80%。。93[7]。Englezos[3],。,,23%26%。Willson[8],。,:①12℃,6.5MPa0.082%;②4℃,5.5MPaCO24%;③4℃,5.0MPaCCl3F。WO8910392,:,,[9]。,,。John[10]。YoonLee--,[11]。、-、--p-T,,,·13·　1999192。,,0.6%,-。,、、、、。3　,、,(、)。,0℃,2.56MPa,。,()。2。Happel[12]1994,,,。CH4-N2,。1,0℃,N214.3MPa,CH42.56MPa,CH4。48%CH4,274.6K,5.7MPaCH482%。82%CH4,CH495%,CH4。、,15%,500μm,。。,,,。,95%。(100%),,,。[13],:5℃,5MPa,,,。,[14]。,,(),[15]。,,。,。、,,。,。,,。1　,,..,1998,18(3):75～822　EnglezosP.IndEngChemRes,1993,32(7):1251～12743　TheProceedingsoftheSecondInternationalConferenceonNatu-ralGasHydrates,Toulouse,19964　US,3085832.19625　SU,865820.19816　HuangCP,FennemaO,PowrieWD.Cryobiology,1966,2:240～2457　CA,93:1914368　WillsonRR,BulotE,CooneyCL.ChemEngCommun,1990,95:47～559　WO,8910392.198910　JohnVT,KommareddiNS,AyyagariMS,etal.NewDirectionsinHydrateTechnology:ApplicationstoBiotechnologyandAd-vancedMaterials.AnnalsoftheNewYorkAcademyofSciences,1994,715:468～48011　YoonJi-Ho,LeeH.ClathratePhaseEquilibriafortheWater-Phe-nol-CarbonDioxideSystem,AIChEJ,1997,43(7):1884～189312　HappelJ,HnatowMA,MeyerH.TheStudyofSeparationof(下转第10页)·14·1999192　、、。,,,,、。4.4　,[11],“”“”,,1800,26,,,,。,,,,。5　①、,,,,,,;、、。,3000～6000,12%;105000～5t/aKCl,,,50%～60%。、、。,,。②,,“”,、、,,,。,,、、、、。1990,,35,(20),,、、,、、,。,、。,,,,、。③,,,,。80,,,、、,,、。1　..:,19772　,..:,19973　.,1997(7):5～84　.,1997(5):25～275　,.,1998(5):3～76　.,1997(9):3～87　.,1998(1):20～258　.,1998(5):16～179　.,1997(2):18～1910　.,1997(1):19～2211　.,1998(2):17～21:1998-10-20(上接第14页)　　NitrogenfromMethanebyHydrateFormationUsingaNovelAp-paratus.AnnalsoftheNewYorkAcademyofSciences,1994,715:412～42413　SU,1648527.198914　US,4424858.198415　US,5660603.199716　SloanED.ClathrateHydratesofNaturalGas.NY:MercelDekkerInc,1990:1998-09-18·10·1999192