新型雙子表面活性劑在硫化氫與二氧化碳鹽水溶液對碳鋼的緩蝕的性能

1、新型雙子表面活性劑在H?S和CO?鹽水溶液中對碳鋼的緩蝕性能1 IntroductionThecoaabnudeffectsdtheacidCO«ndHSanctr-ban$teelcanx)siailuve<lw<y$been<majorcancantothe0$didaxideoilin±utries.duetothepotentialIxreattceqtqniienB(eg,pumps,vibes.pq)es).Miibtantiecampouiid$tlutcaxfroLreduceorpreventgctiawbetween<meulai

2、xditsEmnmdingsTheuseofiihibiiarsiingeiural<morecoi-efifectiremethodforprotectiaxagainstcoarosixiAandhencekthemostwidelyvisedmetlwd.Dfferexxtfrooacoawattinulmxftcuitsgemmijurfacttixuirecomposedoftwohydrophilichudgrovesandtwohydrophobicchans.$epantedbyretd<ndflexible<rom«ti£arahplut

3、x$p«ctn.Duetcthespecialchemicalmutiweofdie“campontnU.Hlusbeendemoovtntedtlutthenovelnufactuttsaremoreefficititf<trednesxufacetension<ndfamn<miceIlesdunccawavtiaiulsnfactArtsaivllweabwaitiulmicelhcauexxtntxm(CMCJ.*Inrecentyem.gemnusurfactensbecamethefocusafJtudy.mostofthetvilabhhtenntre

4、.gsnau$uxfactaxilshivebeenstudiedscazroaoaimlxbUcnfarcuboiisteelnlxydrodilancacidwdsuRlnmc<cidsolitiaiis.'ThestudiedgeiainimfacteiBwerebasedontnazole.mldasolineqiuter-nuytiELiaaiuknn$<1LSduffbseetc.TheseworksshowedtlMtheywereexcellaucarrosiaiihhibian.Howeverfluluicostofreactu也<ndlaiprod

5、uctiaicycleslunitttxtiru«iipnctktlThe<imofthisworkwastoprepeetiwvelsaiesofgonininnfacttittsconfininghydroxylgr哪vduchhavegoodwaterjohibiliry.edalsoh«vefluadvurugesafewyprochuticai«ndn«pens>ecort.Andduircorrosionhlubitxmperfarmcuefa*c«rbansteelixbrausohttiaicant«mnc

6、HSandCOpsesweremiditdbygnvmetriceltctrodxmic<1poUnsitiaimdelectrodxankilnnpeduuespectrosccpy(EE).Inddmon.thetdsocrptionmodelafthesecampouiulsailcubairteelftcewwalsoirwertietted.2 ExperimentalMaterialpreparationThecompo$liansoftheas&essive$olttioiwot58$6g6H0.124glNtSO,.<id0.04g.LNtF.whkhw&l

7、t;Jimu-htedsohuiaiiafprodiicedwaternigwfieldhChinA.Analytic<1gradedimktlsnddistiDedw<terwereusedhisohuionprep<ntiaiL360steeljptemmIujthechemicalcoxnpositians(m“$fraction):C0.16%Si045%Mi1.60.P0025%.S0.015KV006%.Nb0D5KTiO04%.<ndFebhxueSynthesisofgeminisurfactantsThegeminisurftcunbweresyxxf

8、iusEtdnthreertepsFirstly,oneoftheinlemediite$waspreparedbyreacUonbe-twemteiticy<mmesvdxhhavedffereixtcaibanraunbenaflangchainalkyl(10.12.14.16)wAepkhlarohydrm«t*molarratioaf1:5far4he35-40C.Secondly,theothernuer-medntewas$yixtlusizedbyreactiaiiafhydrochhrx4ndtaturyAmieswhichdsoluvedifferentCA

9、ibonHum(10.12.14.16)«tamohrratioaf1:1usmguetane<$sobeiitFLnalV.thetwontennedutBSweremseedwillaiaolareio11Aivltlienretctedat40-45*Cfar5h.Alltheusedduakdswereuulytxallypureexcepttertwryurniuswliidiwerehdustrialproductsfixan.FexiaiigCliaakals.Ltd.Thedumualrtructure$afdxprepared91aiusuifoctants&

10、#187;-30H-ju(1=12.14.16.18)andwwiiitT<bh1.Theirdumicalrtructmtswerecoirfimedbyinfraredjpectrojcopy.2.1 WeightlossmethodC.HWMOI2.KMJ2TbblStnicurw,hnniisyvn”dmttoolhrwohufthegwAiiisurhatnuCamfitMiadMuIcvwWbfmvheEyanbolCH,111C<HwfCH.-CHCH.hICJIXOI6>3CH46OHCIS-3OH4S?orlossmeexits,rectuicuhi*L36

11、0$teel爭電"mens(50mm<10mmx3mm)weremeduiucallypdidudwih240.400.600.and1000gradesoftinaypaper,cleuudwuhabsoluteethuwLdegreasedwihxetane<ndfiulVdnidndrytir.After穴acamtefy,threep/mlkleci-mensweresninenedntittertsohttxniwillarwithoutaddi-tiaiafdiffereitcoxuemratiaiuofthegeminijuiftctutts.Aftertl

12、uLflusohttiaiiw<spxirpdwilllupurityNfar1hillar-dtiwdeoxypnrtefirn.ThenHS«ndCOweitntroducedinto*heghssbottlefar1htccardntoAflownteaf20«nd10mlmmrespect>ely.pHvahuofsolutionw«sabout43atiooaateiaperiture.Tlute$t<ba<limiafgnviaetrxmeasurementswas72h.Theexperimeiuswereccriedout&

13、lt;t(60±1)C.oxrosionrate(九)wascalailxtedfromthefolloweqiu-ticci:gr)(1)vdvei'eAw*theavertsintfiflo財(illg)ofthi'ee$pecimeiv5isthetotal<re<(hem)cffluspecintn.<idfisthemnaer-sicntme(inh).7/ttlithec<knittedcanosmxrate,nhibitiaiiefficiency(y)of<coxrosxmnilublarw<$defmedbythe

14、followingexpression:<.»(1-*A>100%(2)hertk<ndKire.respeetvely.thecaxrosDnnte$ofsteelMhandwithoutthe<dditxnafHufactcxtssohxtxxn.2ZElectrochemicaltechnique?orelectrodumx<1me<$uiui4caiveiUiaiulglns$cellof250mLwiflxtlxreeelectrodeswwvised.Thewarkhgelec-troieintlufonnafdscattframL36

15、0rttelwnl«nutmof0.35anwasembeddedwillepoxyexceptthewoxicn<wface.Thesamplewaspohdwdwttltdifferentgptoneryp<pato1000gnd£$cleiudwifixebsolmeethylalcohol,tee-tare.<idfiruDydnedidryar.AplAtununeketrode<nda$tmtedabmelelectrode(SCE)wereusecLrejpectively.as<uxibuywdreferexueelectrod

16、es.PotentDdyxumxpohn2itiaacliveswereobtainedbyclunkingthepotauul«xtoan«tM<lVfrom200to令200inVwtmsopencrcuitpotential(OCP)wUhtjcmieeof05inV-s.ZlectToduinicalimpeduuejpectroscopy(EIS)wajine<-dinafrtquexuyr<x<tfrom64kHzto10mHzwih<10mVwivea$theexcitation<ciulntqp«cimutpot

17、entia】Beforeeochnm.atmelUervtlofabout15mmw«sgenforthe$y$tontoattoi<stetdysute.Themunwandwere«u-tandxtllyrecardtdbyusniccoanpxxtei'pcrogru".KC>datawereuugdbyine<ii$ofZSiupwinsoftwnre.Pateitiody-lunicpohnsitiaix<ndEISwerecondncttdusingCS350(VJu-hwiContesthvtnunsitsCompan

18、y.China).2 Resultsanddiscussion3.1WeightIossmeasurements3onx)sianmesofcaibaiisteelmtuabsenceandpresaiceofdifferentcanceim*<tiaxuofgenininnfct«ntsmbrine$ohitiancanummgHSmdC0watdetenuinedbyweittlossmettwd<t60C.rejpecti»ely.TleresulBtrelrtedmTable2.ItcmbechnifnotiedfromTabk2tlutgemini$u

19、rf<ct®tts12-3OH-12nd14-3OH-14cwpreventcaibansteelfromcar-rosiniefficientlynbrhesohtioncaniuuifHS<ndCOThen-mhibmoiiefficiencies(IEs)werehitterthm95%ctthecaueiHrauaiiof35mgL.TheTinkmgofHifarthefourgemiuJwActrnis<sfoltows:14.3OH14>D-30H-D>lfi.3OH-16>18-3OH-ISaccardnActoinlubiiane

20、fficiency.There<remanyfactorsrffectithecaxrosanmlubiianptrfar-muueoflhegearnusuf<ctnnB.Oneofthesefactorsisthelengftiofdkylduin.WhenthelengUtofalkylisrelAtvelydxarter.thecompoundwillluve<betterw«tersohbilMywhichmakesfluadscaptiaixsoenur.However,if血c<rbcaduinaf<lkylkoverla<th.tu

21、sp«cebafiQeeffectwillbepredamiuxxt<idpoorwatersohibiltywillhindertheadsaxptiaiprocessanthemetak.cansequeitQythecoho$diinihbniaiiofAnftctent立decreased.Hegtsytlwuttdut4e«baxptioaeffxieiuyofgemhi$urf<ctextsinatuedwifliureweaffludumlenefliduetothtmcreaseofekctraiuceffectaf<lkylduinThe

22、caiToswnmhibmancfthreeSduflf-basecatxnucgsnmiJVirftctcUs(10S10.12-S-12.<nd14-S-14)ontheurban$teelcanosmiinhydroditorr<cxlwasmiked<sfollowing:14- S-14>12-S-D>10-S-10.-Thecom)sioiiinhibiianperfarm<iutafpiaininnfactuts(10-240.12-2-12.14-2-14)mhy-drodUazic<cidwere匕omemuredcidsmihrre

23、sultswereob-taiudbyAclwunza/.Tb2Cerr»$nrttatfmiUrteolIEv*besf»rv»r»u$c»ncentr«thisurHants«t<0*Cfiefrtmwiffitl«ssrementsgfiigmi<g.L1航aiyibbnk01(MM-I2JOM-I2IOOMDCJO200OS2I313SOIMU*99SOOO«O«SSIOOOlMIII4JOH-I4IOiri丸0420004)1命4*350?MW"eOIMWXgIO

24、OOOSM咄40I6JOM-UIOrsiuS29220I7HM2I)SOIMM)«幾so00572aUIOOO0«SIMOII8JOH-ISIO0SB42).IJ20Ml41l«3S)1的“soO34U<792IOOO34S2040Vif1Ptekr«T«ti«rervmeIinhretA<«lwtc»nt«hHj«ndCOj«t60*Cwthrwthut4rfferentgenviisurhatntstthoc*nc«ntmi«H>135mf-L

25、SwriKtiMt.wiV»!*%(oSCEl(mV*«!a：3(mV*dev'|bUik-731I2OSIGIOO-I2.K)H2-S37141101437的63I4-MM-I4-5252OIS7.4I7I*29I6-30H-U-67912967.41079>JOIS.J0M4S-7032"72.10Tbb3Efectrechmmlp«rtm«tentwinedft>mpihrizttbnmmsurementsftretritn$teolnbno“hitbnontwinhgHStn4C0,«t60Cwithtrw

26、ithout4iffeiwitfeminisurftawnu«tth«c»nc«itr«t»ntf35mf-L btonAc 12-XJH-1214-3OH-14 16-3OH16 183OH-16¥flYQ10*10*訶伸1011(f101Frequency/kteThtrejxihsmTitleJalsoshowflutmhibitianefficiencynvcm$eswiltmiureaseintheadditivecooiueitti'itjoiiofgemi-iuHrfActmBwhenthegemmis

27、urf"tartscancextntmtislow-erun35xxigL.Abovethstoneentntian.howevernunts-ing(aiuattntiaiidoesnoteffectinlubitiaiiefficiencyagnifi-centiy.Aiggertiixgflut<saturatedadsaiptioaiofsvrftctoiumoleculesatcubansteelAufacek<dneved.32PotentiodynamicpolarizationmeasurementsF.ldwwjtlxpohnataxiauvesofcu

28、bansteelntonesohniaixcanunxingHSmidCO<t60*Cwilwvttarwilitlusynthesizedgemhi$uxf«cuittsattheoptimumtancentratianaf35L.Vihttsafusocutedehctroclmicalp<mnetei5Aldicorrosionpottittwl(fippurattTrfelsbpei(#andA),conosiaiicurrentdensity(i.)«ndnhi)iianefficiency(fJfar<11Anfactetbwerectkukl

29、ed<ndhneditTible3.TheQiliibiiaiiefficienciesaredefinedw)*100%(3)whereicdf<recanosiniaurentdenstiesindiesohttxnAwillendwilwxitnnfqctinB.respectizeiy.detenainedbySwNewtmiftttincnwe<kpohiizttiaiizoii£af血cnve$.hvpectiaiiafTable3ndFi.lreveals4ut(i)thevaluesofJihifttowardmoreposttyepoteittwl

30、uxdthevaliesofi.dterttsesduiplyrfter<ddigtlugsnnusurfutdmdx«tinc血uhibnbgeffectofthegemnusurftcvmB.(ii)compelledwiththeblank(withoutnUibxtarLlhev«liesafTfelslopts(fi<ndfi)becamehrger.gemi-nisufdctants<remixedtypeiiubitersvdixhpreferQOltyre-tardtheanodicprocessofcoarosion.tin(iii)ni

31、s<pp<rentfigtheremitstinttheIE$offlugeminiAtrftctaiUstestedbypoteitbodyiumicpohnsstiaiimethoddecreasemthefollowingorder14.3OH-14>12-3OH-1>16-3OH.16>1S-3OH-1&wiuchiscaivuttixtwilxiurestiltobt<iudbyweittlossmethod.3.3 ElectrochemicalimpedancespectroscopymeasurerrentsCaxrosimbelu7

32、iarafcvboaxsteeLmthesohmanmtht<b-seiuearprescutofthegemnunufactmts«t血optmxmtancennttxniaf35ngLwereiiwertig<tedbyEEm“juremenls.Thecan*ecpoidiiNyqiustdiagzifandBodeplotsareshownmFg2TheNyquistplotscwberegirded<soneputafasemxrclt.Theshttlydepressedcipacxtvt$emKir-cltvdwseceitreibelowthex-&

33、lt;xkisthechanctairtxfarsolidelectrodestiidhisbeenatninitedtoroumtrandotherii-hcanogeiutiesafbeelectrode.InspectionaftheF<2revedthxtttudiameterofthesemicirclenxcreases$i©iificaiUVmtlxpresaueof血dffenntgemhi$wf<ctaitb.RXcleetluLtucoarosioixofcarbon$t«elmbrmesolniaii(om>&uHS<n

34、dCOisobvuni$lyinhibited.IE(彳)isestmiatedframthedwgetnnrferresutancevaluesaccordingtothefollowupeqivrtinx:(4)whereR<ndRtxe血durgetransferresiUxuevaluswifli-4W035003000250020001500100050000500100015fl020002500300035004000maorri100908070:60?50B40!M20100F2Kyquiit(i)«ndImftrcritn(twlrbrin*selutbns

35、«uintedbyHSsdCO.«t(0#Cwith«rwithoutdifferent嚴viiturhatnu«f35mr-LoutcidwitligemiuairfacKixB.respecmety.R(oibeJtenfranitheBodeplots(Fig2b)tlutthereisonetimecavtctLsothempednued«Uctaxbeaiulyaduigthe$xuipbequ>«hiitcircuitslwwiiinFig3wlitreRmdRarethesolttioairesirtinceund

36、thechargetransferresKtcut.re-jpectpely.ThecaistuUpluseelonaxLCPEismtroAuedithecircuitinsteadofapuredoublelayercaptciartopreamarernnttfitThempedanceoftheCPE(Zn)isdefnxed<$:Z/M(j»)(5)witen?<ndnaretheCPEccnxstuttmdexponent,respetveV3“theaixcuhrfrequency/)innd$(w=2VXj=<nnoagnwynumberThedou

37、blelayercq)aciUn£es(C)<recakxihtedfromthefollowingeqiunon:Zg點(6)"thefreqtwncy«tvdxkhthtimagnuiycaanpoxuiTtofthempeduueismAdmal.Thempednueqivattii«tiveremitsarehrttdmTable4.Hc<nleseenthxtJtvahiembliaksohttianis104.4Q*anandiiureuesto21850anhipresenceof12-3OH12.increasesto3766

38、Qcminpresenceaf14-3OH-14.<id4endecreasesslidyto1295«nd521.3Q*aninpresenceaf16-3OH-16.1S-30H-1S.respectively.Cvthiesdecrm”bthtpaesaueofgemnusurfactants,duchcanremifraa<deattseinlocaldielenccoavtttUndtaranmareasemthetluclaussaftheeMetricaldcniblehyer.nyeEngthm血snfactetti&ohailesctbyadso

39、rptionatthemetalAohitionmterface.Thisbelx«viarrevekth«tthenRndC.vahiesareccasedbythedualrepheementafwatermoleculesbyadsorptionofthtgemmimrfqcUntmoleculesonthemetalsurfate.Thegemimsurfactwtmokculesin«yfoxm<protectiveltyeroaidiecubaiisteelAnface.reducing;theextentafcono-swedisohttian

40、fartlxecarbonrtee1Btlsoc<nbeittexnttedtluttlieadsaiptiaidegreematas-eswiththe<kyldulllengthfrom12to14uiddecreetsslivelywilthe<Ikyldunlengthfrom16toIS.Themhi)it»IHFg3Euivlentciraicm«4elftrthenuie4fewhisurha«ntsingrffkiauyfoltowstheorder:14-30H-14>12.30H42>3OH-16>1S-3O

41、H-1S.RemisobtainedfromEEmeasurements<rehgoodAgreementwithtlutobtainedfrombothweittlossttLidpatentiodyiuazikpolAnziomaevireineiiB.3.4 AdsorptionisothermIthubeencansideredtlutorpaucn>hi)normorcule$ertab-lislitheircaxrooaLiniliibitiaiipeifomiuesiwdsarptioaxofthenhibitaroato他metal$uxf«ce.andt

42、hemhibitumefficiencyisdirectprapoatimultowrfactAHtcoverage()Adsaip-tioaiisothamsintrynnpartuUmunderstandingthtmxlunimofcaxrosiaiimhibition.Inprevxnismdie久itwasfoundthattheinortfrequentlyvised<dsa*ptiaisdlumjofthegemiu<reLmgmuir皿oiptianmodel.Assummtluttheadsooptxmcftheprep<redgeinnuAufactant

43、sonccbonrttelsurfaceobeyLuigmuirAdsorptionbo-thenngnmbythefollowuxgeqiutxni:0/U-0FKC，(7)whereCisthe(oxueixlr41iaiafgemhunnfactiitb.0istheAir-f<cecarencewhxhcaiibecalcuLttedframweittlossexpeimentalresuhstixdKisthe$t<xd«rd<d$aiptwneqiiilibmuiicoauttttLrehtedtothe$t<ndardfreeenergyaf&l

44、t;dsazption(AG.)bythefollowingqqumai:'X=(l/555)exp(-LGJKT(8)wherethevdmaf55.5istheihoIaxcancentntianofw«terinsolutionmmolLRbthegwcoiirt«Ltt.TisAbsolutetemperatureandLG.isH(Uithrdfreeenergyaf«dscaptionprocess.TheplouafC/6Cyield<line<sshowninFic.4.ImpectiaxafdieFig.4revealthat

45、duobt«ivedplotsofthegeiniuAuf&ctAixKaxehe«rwihbotlicant1atiancoeffiieiuaixddiestopeiie«r1except1S-3OH-1S.Sottieadsoiptiaixofthegeiniuaufacunts»-3OH-jii(»=12.14.16)anthecarbonrteelsxufaceobeystlieLmxiirtdsaiptionisotlima$.TiltofX<ndAC?,wmrec<lc訕mduangEq$.(7)<nd(S

46、Kstope(a)andthenttffcept(JhweredeniedfromtheplotsofC/0C.ThertAibweresumiuccedntTable5.Thenegitivevahxeaf4G亠hdi£<tesaspantmeoustdsaip-tianafthepreparedgeinnuHufactcttsanccbansteel$urftce.uGtixerdly.LG.valuesmarenegativetlvai40kJmoliwolvedurgedurnxgartransferfromthenivibitariaolecultstothemeta

47、lsurfacetofarmavoardhutetypeafband(chemisoaptimnduleLG.valuesaround-20kJmolarlowerme<11physisoiptiaitThecalaihttedv<lw$xnd>catetluttheAcboxptxnniechttu$nioftlupreparedgmhiAir-fictmtbJH-30H-»(»=12.14.16)ancaibaiisteelinbrmesolvb4Impd«nce«rtmecenf»rc«ri«nste

48、elinbrhostlutbnonttinh;HSC0；t60°Cwith«rwrthtutdiff©rentinisurfictnu«ttheoncentm“tf35mpLs«ritawmX4O(a»*lARman)yjtpof*)C-XF-cm1benkIJ42016771044SU>2804$-I2JOH-I221760.1H4H2I8S4IQ0M19S07I4OH-I4IMS0196637MS140W4O>724I6-3OH-I617«90.16501295l»l17989204IS3OH42J

49、59OSSKMS2IJIflOHI375«Fir4uir«4s«q>tbnfbu*fcriensteeliibrin«sicenttinvifHS«n4COwiththepernnisurhcttntsTtbIoSAJ$qtn.r*meters<thomntsurHctnts«nthoc*nfteelsurhceSurfMlMItjraAtL«mol|“Wtn3jI2-JDH421(DOO0*9|JT10的21I4.X)H4409WO096SSi.»oio7I<4-2t3SI5-3OH46O

50、9;/MMO«l7.47O-IO*133.9-246104171OJSII1M4U>'S93S-2244ticngmuiungHSandCOkamccedplxysical«nddwnicaldsarptian.35InhibitionmechanismAhhouQitheadsoxptxxnofgtmimnofctmsan血$teelnifaceiscoxnpHeatedbeewisethegemiuHufactcttsccattailtwolxydropluhcgrovesandtwohydrophobicgroq>$theaboveresultse

51、iublethe<uflwntopropose<rehtcveV$mpleinhibiianmedvausm.bHS$ohtia.HSioi訂maybeprefeitniiilfy<dscubedanccbcaisteel$urf4cethereby.mAkmcthe$utf4cenegativechffged*Then,thetwoqiiAtenuryamammahedgro®(N)afgeanunufArtUTtmohGilescouldbeabserbedanthelayeraftdsoibeduiiaivby<nelectro$t«ticrt

52、enctxm.Sxxbse-queittly.chemisoaptianm«yt«keplice.Astresultthetixtad-soebedlayerofgsnimsxirf<cUittsonthectibaixsteelAirftcec<uoUn血caxrosiremtdM<iviretardthtcarrosianreAC-ticn.Thtpmininnfactnittmokailtsmaybelyhganmetalnrf4ce<tbwerconcentntioiv.<ndatluurconcertrationsapetpeiulicuUrdsarptxniUlcespucetsaresulatmltter-lvy-drophobicduniYteiMtiai.ThtgeiaxiiAnftcUittmoleculestnaboadsaxbeddxtodiemetalAuftceQxrouithetwo<m*mGnmmhedgrouiK(N).3 Conclusions(1) Theinhibitingefficiencyafthesynilusiadgemiujut-fftcuntsfarca