1、A Referencenumbe r ISO14687:1999 (E) INTERNATIONAL STANDARD ISO 14687 Firstedition 19990301 HydrogenfuelProductspecification CarburanthydrogneSpcificationdeproduitISO14687:1999(E) ISO1999 Allrightsreserved.Unlessotherwisespecified,nopartofthispublicationmaybereproducedorutilizedinanyformorbyan ymean
2、s,electronic ormechanical,includingphotocopyingandmicrofilm,withoutpermissioninwritingfromthepublisher. InternationalOrganizationforStandardization Casepostale56 CH1211Genve20 Switzerland Internet isoiso.ch PrintedinSwitzerland ii Contents 1Scope 1 2Termsanddefinitions .1 3Requirements. 1 3.1Classif
3、ication. 1 3.2Applications . .2 3.3Limitingcharacteristics. .2 4Qualityverification. 2 4.1Qualitytests 2 4.2Productionqualificationtests . 2 4.2.1Generalrequirements. .2 4.2.2Analyticalrequirementsoftheproductionqualificationtests 2 4.3Lotacceptancetests . .4 4.3.1Applicability 4 4.3.2Lotdefinitions
4、 4 4.3.3Numberofsamplesperlot .4 5Sampling. 4 5.1Samplesize 4 5.2Gaseoussamples .4 5.3Liquidsamples(vapourized) .5 6Testmethods. .5 6.1Parametersofanalysis. 5 6.2Hydrogenassayforpurity .5 6.3Hydrogenassayfor parahydrogen 6ISO ISO14687:1999(E) iii 6.4Watercontent 6 6.5Totalhydrocarboncontent 6 6.6Oxy
5、gencontent. 6 6.7Argon,nitrogen,neonandheliumcontents 7 6.8Carbondioxidecontent. . 7 6.9Carbonmonoxidecontent . 7 6.10Mercuryvapourcontent . 8 6.11Totalsulfurcontent 8 6.12Permanentparticulates 8 7Safetyanddetection. . 8 7.1Safety . 8 7.2Detection 8 Bibliography 9ISO14687:1999(E) ISO iv Foreword ISO
6、(theInternationalOrganizationforStandardization)isaworldwidefederationofnationalstandardsbodies(ISO memberbodies).TheworkofpreparingInternationalStandardsisnormallycarriedoutthroughISOtechnical committees.Eachmemberbodyinterestedinasubjectforwhichatechnicalcommitteehasbeenestablishedhas therighttobe
7、representedonthatcommittee.Internationalorganizations,governmentalandnongovernmental,in liaisonwithISO,alsotakepartinthework.ISOcollaboratescloselywiththeInternationalElectrotechnical Commission(IEC)onallmattersofelectrotechnicalstandardization. InternationalStandardsaredraftedinaccordancewiththerul
8、esgivenintheISO/IECDirectives,Part3. DraftInternationalStandardsadoptedbythetechnicalcommitteesarecirculatedtothememberbodiesforvoting. PublicationasanInternationalStandardrequiresapprovalbyatleast75%ofthememberbodiescastingavote. ThisdocumentwaspreparedbyTechnicalCommitteeISO/TC197, Hydrogentechnol
9、ogies .INTERNATIONALSTANDARD ISO ISO14687:1999(E) 1 HydrogenfuelProductspecification 1Scope ThisInternationalStandardspecifiesthequalitycharacteristicsofhydrogenfuelinordertoassureuniformityofthe hydrogenproductasproducedanddistributedforutilizationinvehicular,applianceorotherfuellingapplications. T
10、hisInternationalStandardappliestoallmodesoftransportationandhydrogenfuellingapplications(ground,water, airandspace). 2 Termsanddefinitions ForthepurposesofthisInternationalStandard,thefollowingtermsanddefinitionsapply. 2.1 gaseoushydrogen GH 2 hydrogenthathasbeenproducedtogaseousform,andbroughttoess
11、entiallyambientconditionsasanequilibrium mixtureof orthohydrogenand parahydrogen,purifiedtoaminimummolefractionof98% NOTE Thegaseousformisproducedtypicallybyanynumberofmethods,includingpetrochemical,thermochemical,solar, electrolyticorbiologicalprocesses. 2.2 liquidhydrogen LH 2 hydrogenthathasbeenl
12、iquefied,i.e.broughttoaliquidstate(para) NOTE Liquefactionmaybecarriedoutbyeitherchillingandcompressionorothermeanssuchasthemagnetocaloric effect. 2.3 slushhydrogen SLH 2 hydrogenthatisamixtureofsolidandLH 2 attheeutectic(triplepoint)temperature 3Requirements 3.1Classification Hydrogenfuelshallbecla
13、ssifiedaccordingtothefollowingtypesandgradedesignations: a) TypeI(gradesA,B,andC): Gaseoushydrogen b)Type II: Liquid hydrogen c)Type III: Slush hydrogenISO14687:1999(E) ISO 2 3.2Applications Thefollowinginformationcharacterizesrepresentativeapplicationsofeachtypeandgradeofhydrogenfuel.Itis notedthat
14、suppliers(especiallyliquidtransporters)commonlytransporthydrogenofahigherqualitythansome usersmayrequire.The“lower”gradesAandBentaillessstringentrequirements,whichmaybemoresuitablefor “captive”systemssuchasvehiclefleets/commonfilloronsitehydrogenproduction/use,suchasinindustrial complexes. TypeI,gra
15、deA internalcombustionengines/fuelcellsfortransportation;residential/commercialappliances; TypeI,gradeB industrialfuel,forusee.g.inpowergenerationorasaheatenergysource; TypeI,gradeC aircraftandspacevehiclegroundsupportsystems; TypeII aircraftandspacevehicleonboardpropulsionandelectricalenergyrequire
16、ments;landvehicles; TypeIII aircraftandspacevehicleonboardpropulsion. 3.3Limiting characteristics TheDirectoryofLimitingCharacteristics,outlinedinTable1,specifiestherequirementsapplicabletoeachtypeand gradeofhydrogenfuel.Ablankindicatesnomaximumlimitingcharacteristic.Theabsenceofamaximumlimiting cha
17、racteristicinalistedqualityleveldoesnotimplythatthecomponentisorisnotpresent,butmerelyindicatesthat thetestneednotbeperformedforcompliancewiththisInternationalStandard. 4Quality verification 4.1Quality tests Thesuppliershallassure,bystandardpractice,theverificationofthequalitylevelofhydrogen.Thesamp
18、lingand controlproceduresdescribedin4.3.1and4.3.2andinclauses5and6maybeapplied.Othercontrolprocedures notlistedinthisInternationalStandardareacceptableifagreeduponbetweenthesupplierandthecustomer. 4.2 Productionqualificationtests 4.2.1General requirements Productionqualificationtestsareasingleanalys
19、isoraseriesofanalysesthatshallbeperformedontheproductto assurethereliabilityoftheproductionfacilitytosupplyhydrogenoftherequiredqualitylevel.Thisproduction qualificationmaybeachievedbyverifyingtheanalyticalrecordsofproductfromthesupplier,or,ifrequired,by performinganalysesofrepresentativesamplesofth
20、eproductfromthefacilityatappropriateintervalsasagreed betweenthesupplierandthecustomer.Productionqualificationtestsmaybeperformedbythesupplierorbya laboratoryagreeduponbetweenthesupplierandthecustomer. 4.2.2 Analyticalrequirementsoftheproductionqualificationtests Theanalyticalrequirementsfortheprodu
21、ctionqualificationtestsshallincludethedeterminationofalllimiting characteristicsofhydrogen.ISO ISO14687:1999(E) 3 Table1Directoryoflimitingcharacteristics Dimensionsinmicromolespermoleunlessotherwisestated Subclause Characteristics TypeI TypeII TypeIII (assay) GradeA GradeB GradeC 6.2 Hydrogenpurity
22、 (minimummolefraction, %) 98,0 99,90 99,995 99,995 99,995 6.3 Para hydrogen (minimummolefraction, %) NS NS NS 95,0 95,0 Impurities (maximumcontent) Totalgases 50 50 6.4 Water(cm 3 /m 3 ) NC a NC bb 6.5 Totalhydrocarbon 100 NC bb 6.6 Oxygen a 100 cc 6.7 Argon ac c 6.7 Nitrogen a 400 bb 6.7 Helium 39
23、39 6.8 CO 2 dd 6.9 CO 1 dd 6.10 Mercury 0,004 6.11 Sulfur 2,0 10 6.12 Permanentparticulates feee Density e NOTE1 NS:Notspecified NOTE2 NC:Nottobecondensed a Combinedwater,oxygen,nitrogenandargon:max.1900 m mol/mol. b Combinednitrogen,waterandhydrocarbon:max.9 m mol/mol. c Combinedoxygenandargon:max.
24、1 m mol/mol. d TotalCO 2 andCO:max.1 m mol/mol. e Tobeagreedbetweensupplierandcustomer. f Thehydrogenshallnotcontaindust,sand,dirt,gums,oils,orothersubstancesinanamountsufficienttodamagethe fuellingstationequipmentorthevehicle(engine)beingfuelled.ISO14687:1999(E) ISO 4 4.3 Lotacceptancetests 4.3.1Ap
25、plicability Lotacceptancetestsareanalysesthatshallbeperformedonthehydrogeninthedeliverycontainer,orasample thereof,whichisrepresentativeofthelot. 4.3.2Lot definitions Oneofthefollowingdefinitionsofthelotshallbeused: a) nospecificquantity,oranyquantityofhydrogenagreeduponbetweenthesupplierandthecusto
26、mer; b) allofthehydrogensupplied,orcontainersfilled,duringthecontractperiod; c) allofthehydrogensupplied,orcontainersfilled,duringacalendarmonth; d) allofthehydrogensupplied,orcontainersfilled,duringsevenconsecutivedays; e) allofthehydrogensupplied,orcontainersfilled,duringaconsecutive24hperiod; f)
27、allofthehydrogensupplied,orcontainersfilled,duringonecontinuousshift; g) allofthehydrogensuppliedinoneshipment; h) allofthehydrogensuppliedinonedeliverycontainer; i) allofthehydrogeninthecontainer(s)filledononemanifoldatthesametime. 4.3.3 Numberofsamplesperlot Thenumberofsamplesperlotshallbeinaccord
28、ancewithoneofthefollowing: a) onesampleperlot; b) anynumberofsamplesagreeduponbythesupplierandthecustomer. 5Sampling 5.1Sample size Thequantityofhydrogeninasinglesamplecontainershallbesufficienttoperformtheanalysesforthelimiting characteristics.Ifasinglesampledoesnotcontainasufficientquantityofhydro
29、gentoperformalloftheanalyses requiredtoassessthequalitylevel,additionalsamplesfromthesamelotshallbetakenundersimilarconditions. 5.2Gaseous samples Gaseoussamplesshallberepresentativeofthehydrogensupply.Samplesshallbeobtainedusingoneofthe followingprocedures. a) Fillthesamplecontaineranddeliveryconta
30、inersatthesametime,onthesamemanifoldandinthesame manner. b) Withdrawasamplefromthesupplycontainerthroughasuitableconnectionintothesamplecontainer.No regulatorshallbeusedbetweenthesupplyandthesamplecontainers(asuitablepurgevalvemaybeused). Forsafetyreasons,thesamplecontainerandsamplingsystemshallhave
31、aratedservicepressureatleast equaltothepressureinthesupplycontainer.ISO ISO14687:1999(E) 5 c) Connectthecontainerbeingsampleddirectlytotheanalyticalequipmentusingsuitablepressureregulationto preventoverpressurizingthisequipment. d) Selectarepresentativecontainerfromthecontainersfilledinthelot. 5.3 L
32、iquidsamples(vaporized) Vaporizedliquidsamplesshallberepresentativeoftheliquidhydrogensupply.Samplesshallbeobtainedusingone ofthefollowingprocedures: a) byvaporizing,inthesamplingline,liquidhydrogenfromthesupplycontainer; b) byflowingliquidhydrogenfromthesupplycontainerintoorthroughasuitablecontaine
33、rinwhicha representativesampleiscollectedandthenvaporized. 6Test methods 6.1 Parametersofanalysis Theparametersforanalyticaltechniquescontainedinthisclauseare: a) molefraction,expressedasapercentage(%); b) numberofcubiccentimetrespercubicmetre(cm 3 /m 3 )wateronly; NOTE1 Contentsin6.1a)andb)represen
34、t10 -6 . c) numberofmicromolespermole( m mol/mol). Totalhydrocarboncontent“asmethane”forthepurposeofthisInternationalStandardisdefinedasthesingle carbonatomequivalent. Calibrationgasstandardswhichcontaintheapplicablegaseouscomponentsmaybeneededtocalibratethe analyticalinstrumentsusedtodeterminetheli
35、mitingcharacteristicsofhydrogen. Ifrequiredbythecustomer,theaccuracyofthemeasuringequipmentusedinpreparingthesestandardsshallbe traceabletoanestablishedinstituteforstandards. Analyticalequipmentshallbeoperatedinaccordancewiththemanufacturersinstructions. AnalyticalmethodsnotlistedinthisInternational
36、Standardareacceptableifagreeduponbetweensupplierand customer. 6.2 Hydrogenassayforpurity Thehydrogenconcentrationshallbedeterminedbyoneofthefollowingprocedures. a)Useathermalconductivityanalyserwhichmeasurestheaggregateimpuritieswhichhavethermal conductivitiesdifferentfromhydrogen.Theanalysershallbe
37、calibratedatappropriateintervalsusingcalibration gasstandards.Therangeoftheanalysershallbenogreaterthantentimesthedifferencebetweenthe specifiedminimumhydrogenconcentration,inpercent,and100%.Thusfora99,5%minimumhydrogen concentration,theanalysershallhaveamaximumrangeof5%impurityorfrom95%to100%hydrog
38、en. b) Useavolumetricormanometricgasanalysisapparatus. c) Determinetheamountofaggregateimpuritiesusingthemethodsinthefollowingsubclausesofthis InternationalStandard.Thehydrogenconcentrationisthevalueobtainedwhenthisamount,expressedas percentmolefraction,issubtractedfrom100%. d) Useanysuitablechromat
39、ographicsystemwhicheffectivelyquantifiesspecificimpuritiessee6.7a).ISO14687:1999(E) ISO 6 6.3 Hydrogenassayfor parahydrogen Parahydrogen(percentminimumbalance orthohydrogen)shallbedeterminedusingthermalconductivitytypein streamanalysersinstalledinthesuppliersproductionsystemandshallbecalibratedinteg
40、rallybytheappropriate useoftemperaturecontrolledcatalystbeds. NOTE Industrialusersofhydrogentypicallydonotrequirelotanalysisfor paracontent.Thetestmaybeperformedas agreeduponbetweenthesupplierandthecustomer. 6.4Water content Thewatercontentshallbedeterminedusingoneofthefollowingprocedures. a) Suppor
41、tthehydrogencylinderinaninvertedposition(valveatthebottom)for5min.Thenopenthecylinder valveslightlywhilethecylinderremainsinverted,andventthehydrogenwithabarelyaudibleflowintoanopen, drycontainerfor1min. Thecylinderanditscontentshallbeabove0C.Thisprocedureshallnotbeusedforhydrogenfuelotherthan TypeI
42、,gradesAandB.Thisproceduredetectscondensedhydrocarbons(oil)aswellaswater. NOTE Arapidflowmaycauseanywatertodisperseandnotcollectinthecontainer. b) Useanelectrolytichygrometerhavinganindicatorgraduatedincubiccentimetrespercubicmetreonarange whichisnogreaterthantentimesthespecifiedmaximumwatercontent.
43、Recombinationofoxygenwith hydrogencanoccur,producingafalsehighreading;refertoinstrumentmanufacturersinstructionsforproper analyticaltechnique. NOTE Recombinationofoxygenwithhydrogencanoccur,producingafalsehighreading.Refertoinstrument manufacturersinstructionsforproperanalyticaltechnique. c) Useadewpointanalyserinwhichthetemperatureofaviewedsurfaceismeasuredatthetimemoisturefirst beginstoform. d) Useapiezoelectric(e.g.vibratingquar
