Ocena bilance vode v sistemu reformer/gorivne celice
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1 ELEKTRTEHNIŠKI ESTNIK 78(-): 6-66, 0 EXISTING SEPARATE ENGLISH EDITIN cea bilace vode v sisteu reforer/gorive celice Aljaž Čufar, ladiir Jova Uiverza v Ljubljai, Fakulteta za ateatiko i fiziko, Jadraska ulica 9, 000 Ljubljaa Istitut Jožef Stefa, Jaova 9, 000 Ljubljaa E-pošta: vladiir.jova@ijs.si Povzetek. PE gorive celice kot gorivo uporabljajo čisti vodik, ki pa ia zaradi svoje ajhe gostote tudi ajho gostoto v je shrajee eergije. Ea ized rešitev tega problea je, da vodik za delovaje gorivih celic sproti izdelujeo iz eergetsko gostejše sovi, pr. iz etaola. Pretvorbo iz etaola v vodik opravlja t. i. reforer, ki pa poleg etaola zaradi ačia delovaja (pari reforig) potrebuje tudi vodo. Pri reakciji v gorivih celicah pa voda astaja. Zaialo as je, kako je z vodo bilaco v sisteu reforer-gorive celice oz. ali je vodo v siste treba dodajati ali jo odvajati iz sistea. člaku je predstavlje odel, ki a z relativo alo podatki, ki jih dobio od proizvajalcev gorivih celic i reforerjev goriva ter ekaj preprostii eritvai/predpostavkai poaga oceiti bilaco vode. Iz te ocee je razvido, da v običajih okoliščiah i z avadii gorivii celicai i reforerji dobio presežek vode v sisteu. Na prieru reforerja s predpostavljeii karakteristikai i sisteo gorivih celic Nexa Power odule (karakteristike so dobili od proizvajalca) je tudi prikazao, kako oceio paraetre, potrebe za oceo vode bilace. Ključe besede: gorive celice, reforer goriva, etaol, voda bilaca Exteded abstract. I PE fuel cells pure hydroge is used as a fuel. Due to its low desity, the desity of its stored eergy is low, too. e of the possible solutios to this proble is productio of hydroge fro the eergy reach aterial, e.g. ethaol. Coversio of ethaol to hydroge is ade with reforer i a stea reforig process i which besides ethaol also water is eeded. the other had, water is oe of the products i the reactio betwee hydroge ad oxyge i fuel cells. The questio we wated to aswer was what is the total water balace i a syste cosistig of a ethaol reforer ad a fuel-cells-based geerator set ad should water be supplied or reoved fro the syste. The paper presets a odel capable of assessig the water balace usig soe siple assuptios ad coercial data fro suppliers of fuel-cell systes ad ethaol reforers. The odel evidetly shows that i oral states ad usig coercial reforer ad fuel cells syste, there is always a surplus of water preset. With a exaple of a syste cosistig of the Geesis 0 LE ethaol Reforer ad Nexa Fuel-cell Power odule it is show how the paraeters for the waterbalace odel ca be assessed. UD Gorive celice PE kot gorivo uporabljajo vodik. Ker je vodik zelo lahek eleet, je gostota v je shrajee eergije kljub jegovi visoki zgorevali toploti ajha, kar poei, da za shrajevaje porabio veliko prostora. Ea ized rešitev tega problea je, da vodik za gorive celice izdelujeo sproti iz eergetsko gostejših sovi, pr. iz etaola. Pretvorba iz etaola v vodik poteka v reforerju goriva (agl. fuel reforer) po pricipu parega Prejet. juij, 00 dobre 0. julij, 00 reforiga (agl. stea reforig) [,], ki poteka po reakciji: CH. () H H C H gorivih celicah PE pa poteka reakcija, () H torej v gorivih celicah voda astaja, v reforerju goriva pa se porablja. Zaialo as je kako je z vodo bilaco v sisteu reforer goriva gorive celice, ali z drugii besedai, se voda v te sisteu porablja ali jo je treba odvajati.. Preprosta ocea CENA ILANCE DE Da dobio občutek o probleu, lahko a siste reforer/gorive celice ajprej pogledao poeostavljeo. Iz zgorjih eačb je razvido, da za pretvorbo ee olekule etaola potrebujeo eo olekulo vode, iz ee olekule etaola pa astaejo tri olekule vodika, v gorivih celicah pa astae ravo toliko olekul vode, kot se porabi olekul vodika. pazio, da je v te poeostavljee odelu vodo treba odvajati, saj v gorivih celicah astae a vsako olekulo etaola več olekul vode, kot se je porabi v reforerju.
2 6 ČUFAR, JAN. Podrobejša ocea resici pa seveda i tako preprosto. Reforer goriva ia tudi v C u ekaj vode, vodo vsebuje tudi zrak, ki ga dovajao v gorive celice (dovajao areč okoliški zrak, e pa čistega kisika), voda ki astae v gorivih celicah, pa se izloči delo kot tekoča voda i delo kot para (iz katere lahko del vode še izločio). Poleg tega je treba upoštevati, da se ves vodik, ki je dovede v gorive celice, ta e porabi (eporablje se izloči skozi aodi ). tej ocei zaeario izgube vode skozi a aodi strai gorivih celic (ekaj vode areč z difuzijo preide skozi ebrao PE i lahko skupaj z eizkoriščei vodiko izhaja iz sistea). Če () vstavio v (4) dobio: ( odveč ) H ( porablje) ( ) Defiirao A z eačbo: ( zrak) ( reforer ) (5) H ( porablje) A ( celote) H, (6) kjer je ( celote) ožia, H dovajaega v gorive H celice, torej je A razerje ed H porabljei v gorivih celicah i H dovajai v gorive celice. zrak) ( T ), (7) H ( zrak ( T ), (8) kjer je relativa vlažost okoliškega zraka (zrak), pa a pove aksialo razerje ed aso vode v zraku i aso suhega zraka pri določei teperaturi (torej ko je ). Kot poavadi je asa i olska asa. Iz (7) i (8) sledi: Slika : Sheatiči prikaz sistea i sovih pretokov Če (a sliki ) pogledao vhode i izhode iz gorivih celic ter pot vode od izhoda iz gorivih celic do reforerja goriva, dobio eačbi: H ( porablje) ( odveč ) ( zrak) ( para) ( tekoče) ( para), () ( tekoče ) ( ), (4) ( reforer ) kjer je H ( porablje) ožia vodika, porabljeega za reakcije v gorivih celicah, kar je po () ožia astale H v gorivih celicah, H ( zrak) ožia v zraku, ki vstopa v gorive celice, H H ( para) je ožia H v zraku, ki izstopa iz gorivih celic, H ( tekoče) je ožia tekoče H, ki izstopa iz gorivih celic, H ( ) je ožia vode v u (izhodu iz razvlaževalika), ( odveč) H ožia a ovo astale odveče vode, H ( reforer) pa ožia vode, dovajae v reforer. ( ) zrak ( ) zrak T, (9) sietričo pa velja ( ) H ( ) Ta (0) Treba je določiti H ( reforer) i ( celote) glede a ( celote ) H CH (ožia etaola, ki jo dovajao v reforer). H ( celote) ( porablje) () ( porablje) C ( celote) () ( reforer) ( reakcijareforer) ( porablje) () C H ( reforer) ( celote) (4)
3 CENA ILANCE DE SISTEU REFRER/GRINE CELICE 6 Eačbi () i () defiirata kostati i C, kjer sta CH ( porablje) ožia etaola, H ( reakcijareforer) pa ožia vode, ki se porabita za reakcijo (). Iz tega sledi: ( odveč) C(A ) ( celote) zrak ( T ( T ) ) (5) Kostate A, i C lahko oceio iz podatkov proizvajalca [,4] ali z eritvai, prav tako zrak i H, vredosti prebereo iz tabel, izerio, pa v določeih prierih lahko določio že iz ačia razvlaževaja (katodega) a (pr., če razvlaževalec zraka zrak sao ohladi do teperature a, je ), drugače pa ga prav tako izerio. Če dobio ( odveč) ajše od 0, je vodo v ( celote) siste treba dodajati, če pa večje od 0 pa odvajati. Poavadi pa iao direktih podatkov/eritev o asih pretokih, apak o prostoriskih. Zrak ajvečkrat sestavlja bolj ali aj dober približek suhega zraka i voda para, zato lahko zapišeo zrak,, (6) kjer je zrak prostoria zraka, ki vstopa v gorive celice, H je parciala prostoria suhega zraka, pa parciala prostoria vode pare. Z uporabo eačbe (6) i eačb p, (7) H, (8) dobio: zrak p zrak i podobo za : p Za H ( ) T ( ) T (9).(0) lahko uporabio približek 9 kg/kol. Ker gorive celice porabljajo kisik, se povpreča olska asa suhega zraka spreei v. lahko oceio iz tega, da pozao sestavo suhega zraka, ki je približo: 75,5 % dušika (kiloolska asa približo 8 kg/kol),, % kisika ( kg/kol) i, % argoa (40 kg/kol). Iz tega vidio, da se olska asa e bo bistveo spreeila. Če se porabi ves kisik iz gorivih celic, bo padla a približo 8 kg/kol. Za atačejši raču uporabio eačbo: ii i i i eljata še eačbi: porablje porablje () zrak, () ( T ) porablje H ( porablje) ACCH ( celote) H () Sedaj potrebujeo sao še prostoriski pretok a. porablje, (4) kjer so vse prostorie erjee pri isti teperaturi (pri teperaturi a)!
4 64 ČUFAR, JAN p. porablje porablje Če upoštevao še eačbi () i () pa dobio: p p AC zrak ( celote). (5) (6) Zdaj lahko vse te eačbe vstavio v eačbo (5) i dobio eačbo, ki a pove, koliko olekul odveče vode (v povprečju) astae v sisteu a vložeo olekulo goriva. Eačbe e upoštevajo, da ob poajkaju kisika reakcije e potekajo optialo. cea iialega pretoka zraka, ki bi še zagotavljal zadosto količio kisika za reakcijo (): AC ( celote) (7) Za kisik v zraku pa velja: x x zrak, (8) ( Tokolica ) kjer je x asi delež kisika v zraku. Iz (7) i (8) sledi, da je iiali asi pretok: H zrak ( Tokolica ) ACCH H x.(9) Če to vstavio v eačbo zrak p zrak H, (0) dobio iiali zrak oz. ajajši prostoriski tok, ki (ob 00-odstoti izrabi kisika) še zagotavlja optialo delovaje gorivih celic. PRIER Zdaj lahko pogledao, kakše rezultate a da odel a reale prieru. Zaradi poajkaja izerjeih podatkov se v ocei zaašao a podatke proizvajalcev. Za prier reforerja goriva uporabljao reforer s 75-odstoti zkoristko, ki deluje a ešaico 65- odstotega etaola i 5 % vode [], za gorive celice pa agregat Nexa Power odule proizvajalca allard [4]. Natače specifikacije se verjeto razlikujejo od uporabljeih, poleg tega pa se spreijajo tudi z razerai v okolici i z obreeitvijo, vedar je tukaj bistve prikaz, kako preprosto oceio paraetre odela i iz tega oceio bilaco vode. delove poročilu i člakih [5,6,7] sta podatka, da ob poli obreeitvi v gorive celice dovajao 0,077g/s vodika, gorive celice pa porabljajo 0,065g/s. Iz tega oceio: 0,065 A 0,96 () 0,077 Privzeli so, da ia reforer 75-odstoti izkoristek, torej je razerje ed zgorevalo toploto pridobljeega vodika i zgorevalo toploto porabljeega etaola eako 0,75 (η ). S poočjo tega lahko oceio paraeter C, saj bi, če bi vse olekule etaola reagirale po eačbi (), dobili trikrat več vodika, kot bi bilo vložeega etaola. η HH HH,() H H H kjer HH poei specifiča zgorevala toplota, ki je za vodik 4,9J/kg, za etaol pa,7j/kg. H HHCH H η,9 () HH H H,9 C 0,64. (4) Iz podatka, da reforer uporablja ešaico 65 % etaola ( x ) i 5 % vode ( x ) (prostoriska deleža), pa lahko oceio še paraeter. CH ρ (5) ρ (6) Gostota vode je približo 000, etaola pa 79 kilograov a kubiči eter. Iz tega sledi:
5 CENA ILANCE DE SISTEU REFRER/GRINE CELICE 65 CH, ρ ρ, (7) etaola a ustrezo razerje, ki ga zahteva proizvajalec reforerja, vedo dovolj. torej dovajao,, brez izgub pa bi bilo, zato velja ocea:, (8) Potrebujeo še oceo asega toka etaola, če veo, kakše je asi tok vodika v gorive celice. C CH (9) H H CH 0, H H g/s. (40) C H Zaia as še, kolikokrat večji je tok zraka od ajajšega. Po eačbah (9) i (0), dobio, da je iiali zrači pretok 0,8 l/s. avodilih za uporabo gorivih celic pa piše, da je zrači tok v gorive celice ajveč,5 sl/s (kar je približo,6 l/s pri 5 C), torej je zrači tok do dvakrat večji, kot se biti ajajši tok pri poli obreeitvi, ki še dovaja zadosto količio kisika. Na podlagi a zaih podatkov so oceili, da ia aš siste pri (stacioari) poli obreeitvi vredosti paraetrov: A 0,96,, i C 0,64 ter asi tok etaola 0, g/s. Slika prikazuje relativo ožio odveče vode glede a relativo vlažost vhodega zraka, paraeter pa je asičea vlažost (torej teperatura) vhodega i izhodega zraka (teperaturo obeh privzaeo kot eako, kar i ajbolj realo. Po drugi strai pa iti i poebo, ali sta teperaturi eaki, saj lahko gledao ižje relative vlažosti i so a iste, kot če bi bila teperatura vhodega zraka ižja.). Pri teperaturi 0 C je asičea vlažost zraka približo 5 g vode pare/kg, pri 5 C približo 0 g/kg suhega zraka, pri 5 C približo 40 g/kg suhega zraka i pri 50 C približo 95 g/kg suhega zraka. Iz slike vidio, da lahko pride do aka proizvedee vode le pri višjih teperaturah (ad 50 C) i sočasi veliki suhosti okoljskega zraka. Če privzaeo še, da je zrači tlak bar, teperatura 5 C ( i a), za prostoriski tok zraka vzaeo,6 l/s, dobio reale razere pri delovaju agregata Nexa. idio, da je proizvedee vode iz agregata z gorivii celicai za razredčitev Slika : dveča voda za dai prier sistea reforer/gorive celice v odvisosti od relative vlažosti vhodega zraka 4 SKLEP praksi se kot alterativi vir električe eergije čedalje pogosteje pojavlja siste reforer etaola/pe gorive celice, kjer reforer zagotavlja čisti vodik, ki ga agregat a gorive celice z ustrezo elektrokeijsko reakcijo pretvarja v električo eergijo, kot straski produkt pa astajata še toplota i deioiziraa voda. člaku je predstavlje odel, ki a z relativo alo podatki, ki jih dobio iz tehičih podatkov proizvajalcev agregatov z gorivii celicai PE i reforerjev etaola ter ekaj preprostii predpostavkai poaga oceiti dejasko bilaco vode. Na prieru uporabe vzorčega sistea ethaol Reforer 0LE/Nexa T Power odule so ugotovili, da je tudi pri koercialih agregatih a gorive celice z realii izkoristki vode, ki je straski produkt delovaja agregata, dovolj, da jo lahko uporabio za postopek parega reforiga, ki poteka v reforerju etaola. Iz te ocee je razvido, da v oralih okoliščiah i z uporabo koercialih aprav, vedo dobio presežek vode v sisteu, ki ga lahko koristo uporabio. LITERATURA [] N. Saes: Fuel Cell Techology, Spriger erlag Lodo Ltd., 006 []. W. ech: Fuel Cell Egies, Joh Wiley & Sos, Ic., 008 [] odel 0LE Reforer peratig aual, Geesis Fueltech Ic., Jauary 00 [4] NexaT Power odule User's aual. allard Power Systes, Ic., Jue 00 [5]. Pere,. Jova: cea eergijskih tokov v sklopu s sklado gorivih celic NexaT Power odule, IJS DP-98, Ljubljaa, 008 [6]. Jova,. Pere, J. Petrovčič: Review of the eergetic flows i a coercial PE fuel-cell syste, ehydrgenia 009-the rd Europea & Iteratioal Coferece o Hydroge & Reewable Eergy Sources, Hydroge ased Eergy Storage Ad Theirs Ecooic/Eviroet Cosequeces, Septeber -, 009, ucharest, Rouija
6 66 ČUFAR, JAN [7]. Jova, J. Petrovčič, P. Pirat: A Trasportable Dwellig Cotaier with I-built Fuel Cells Cogeeratio Syste, 8th editerraea Coferece o Cotrol ad Autoatio - ED0, Jue -5, 00 arrakech, aroko Aljaž Čufar je študet Fakultete za ateatiko i fiziko Uiverze v Ljubljai. proste času dela a dseku za sistee i vodeje a Istitutu Jožef Stefa v Ljubljai, kjer se ukvarja predvse z aalizo asih i eergijskih tokov v sisteih z gorivii celicai. ladiir Jova je starejši raziskovalec a dseku za sistee i vodeje a Istitutu Jožef Stefa v Ljubljai. Področja jegovega strokovega dela obsegajo avtoatizacijo idustrijskih procesov, račuališko podprto vodeje proizvodih podjetij, v zadje času pa dela a vrsti projektov s področja uporabe agregatov z gorivii celicai kot alterativih virov električe i toplote eergije v idustriji i a drugih področjih ašega življeja.
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