NO332183B1 - Apparatur og fremgangsmate for oppvarming av katalysator ved oppstarting av en kompakt brennstoffprosessor - Google Patents

Apparatur og fremgangsmate for oppvarming av katalysator ved oppstarting av en kompakt brennstoffprosessor Download PDF

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Publication number
NO332183B1
NO332183B1 NO20032522A NO20032522A NO332183B1 NO 332183 B1 NO332183 B1 NO 332183B1 NO 20032522 A NO20032522 A NO 20032522A NO 20032522 A NO20032522 A NO 20032522A NO 332183 B1 NO332183 B1 NO 332183B1
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Norway
Prior art keywords
catalyst
heating element
catalyst layer
electric heating
heating
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NO20032522A
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English (en)
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NO20032522D0 (no
NO20032522L (no
Inventor
Paul Martin
T Glenn Scott
Jennifer L Phan
James F Stevens
Curtis L Krause
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Texaco Development Corp
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Publication of NO20032522D0 publication Critical patent/NO20032522D0/no
Publication of NO20032522L publication Critical patent/NO20032522L/no
Publication of NO332183B1 publication Critical patent/NO332183B1/no

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    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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    • B01J8/0476—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more otherwise shaped beds
    • B01J8/0488—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more otherwise shaped beds the beds being placed in separate reactors
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Abstract

Fremgangsmåte og apparatur for å oppvarme et katalysatorsjikt (410) for oppstarting og for å tilføre varme til dette under transient drift for å opprettholde ønsket reaksjonstemperatur. Katalysatoren kan oppvarmes direkte eller indirekte med et elektrisk vameelement (400). Direkte oppvarming oppnås gjennom direkte kontakt mellom varmeelementet (400) og katalysatoren. Indirekte oppvarming oppnås gjennom direkte oppvarming av et fluid, som en prosesstrøm, som i sin tur strømmer gjennom katalysatoren og dermed overfører varme til katalysatoren. I tillegg kan indirekte oppvarming bli oppnådd ved å anbringe varmeelementet (400) innenfor en kappe i direkte kontakt med enten katalysatoren eller fluidet som strømmer gjennom katalysatoren. Katalysatorvarmeren (400) kan benyttes for katalysatorer med mange utforminger, som granulater, ekstrudater, kuler og monolitter. Katalysatorvarmeren (400) kan være fremstilt med enhver type motstandstråd, patron eller stav som kan kobles til en kraftkilde som gir energi til å produsere varmen.

Description

BAKGRUNN FOR OPPFINNELSEN
Brenselceller gir elektrisitet fra kjemiske oksidasjons-reduksjons-reaksjoner og har vesentlige fordeler fremfor andre former for kraftgenerering når det gjelder renhet og effektivitet. Typisk benytter brenselcellene hydrogen som brennstoff og oksygen som oksidasjonsmiddel. Kraftgenereringen er proporsjonal med forbrukshastigheten av reaktantene.
En vesentlig ulempe som hindrer omfattende bruk av brenselceller, er mangelen på en utbredt hydrogen-infrastruktur. Hydrogen har forholdsvis lav volumetrisk energi-densitet og er vanskeligere å lagre og transportere enn hydrokarbonbrennstoffene som i dag anvendes i de fleste kraftgenereringssystemer. Én måte å overvinne denne vanskelig-het på, er anvendelse av reformere som omdanner hydrokarbonene til en hydrogenrik gass som så kan anvendes som råstoff for brenselceller.
Hydrogenbaserte brennstoffer, så som naturgass, LPG, bensin og diesel, krever konverteringsprosesser for å kunne bli anvendt som brennstoff for de fleste brenselceller. I dagens teknikk anvendes flertrinnsprosesser som kombinerer en første konverterings-prosess med flere renseprosesser. Den første prosess er oftest dampreformering (SR), autotermisk reformering (ATR), katalytisk partiell oksidasjon (CPOX) eller ikke-katalytisk partiell oksidasjon (POX). Renseprosessene består vanligvis av en kombinasjon av avsvovling, vanngassforskyvning ved høy temperatur, vanngassforskyvning ved lav temperatur, selektiv CO-oksidasjon eller selektiv CO-metanisering. Alternative prosesser innbefatter hydrogenselektive membranreaktorer og filtere.
I dokumentene EP 0913357 Al og EP 0967174 Al avdekkes reformerings-katalysatorer innbefattende elektrisk oppvarming for oppvarming av katalysatoren. Også i US 5063029 A beskrives oppvarming av en katalytisk reformer. Oppvarmingsenheten er en del av reformeren som har "honeycomb"-struktur og innbefatter elektroder for oppvarming av gass som strømmer gjennom.I US 4033133 A beskrives en hydrogen-generator der katalysatormaterialet forvarmes til en bestemt temperature for å oppnå et optimalt reaksjonsutbytte.
På tross av det ovennevnte, så er det fortsatt behov for en enkel enhet for konvertering av et hydrokarbonråstoff til en hydrogenrik gass som kan anvendes i brenselceller. En praktisk hindring man støter på ved enhver løsning av dette problem, er behovet for å starte opp katalysatorsjiktet og opprettholde den ønskede reaksjonstemperatur under transient drift. Den foreliggende oppfinnelse angår dette behov.
SAMMENFATNING AV OPPFINNELSEN
Den foreliggende oppfinnelse angår spesifikt fremgangsmåte, som angitt i krav 1 og apparatur som angitt i krav 13, for oppvarming av et katalysatorsjikt for oppstarting og for å tilveiebringe varme til et katalysatorsjikt under transient drift slik at det opprettholdes den ønskede reaksjonstemperatur. Slike fremgangsmåter og apparaturer kan anvendes i en brennstoffprosessor for å gjøre oppstarten av brennstoffprosessoren hurtigere og enklere. Det er mange katalysatorer som i henhold til den foreliggende oppfinnelse kan anvendes i brennstoffprosessorer, innbefattende, men ikke begrenset til, katalysatorer for autotermisk reformering, for partiell oksidasjon, for dampreformering, for vanngassforskyvning og for selektiv oksidasjon, og svovelabsorbenter, samt katalysatorer for oksidasjon av restgass ved anoden i forbindelse med en tilknyttet brenselcelle.
Som vist med utførelsesformer av den foreliggende oppfinnelse kan et elektrisk varmeelement oppvarme katalysatoren direkte eller indirekte. På denne måten kan det hurtig oppnås den ønskede reaksjonstemperatur inne i katalysator sjiktet. Direkte oppvarming av katalysatoren oppnås med direkte kontakt mellom varmeelementet og katalysatoren. Indirekte oppvarming oppnås med direkte oppvarming av et fluid, så som en prosesstrøm, som i sin tur strømmer gjennom katalysatoren og derved overfører varmen til katalysatoren. I tillegg kan indirekte oppvarming oppnås ved å omgi varmeelementet med en kappe som så er i direkte kontakt med enten katalysatoren eller fluidet som strømmer gjennom katalysatoren. Innen rammen for den foreliggende oppfinnelse er det tatt i betraktning at en katalysatorvarmer kan anvendes for en lang rekke katalysator-utforming, innbefattende granulater, ekstrudater, kuler og monolitter. I én utførelsesform som illustrerer den foreliggende oppfinnelse, kan en katalysatorvarmer i henhold til denne oppfinnelse omfatte enhver type motstandstråd, patroner eller staver som kan bli formet som beskrevet nedenfor. En kraftkilde, så som elektrisk kraft, kan gi energi til å danne varmen som anvendes til å forvarme katalysatorsjiktet.
Én illustrerende utførelsesform av den foreliggende oppfinnelse er en brennstoffprosessor med en reaktor som innbefatter et katalysatorsjikt, en kjølekveil posisjonert inne i katalysatorsjiktet for å fjerne overskuddsvarmen under normal drift, og et elektrisk varmeelement posisjonert inne i kjølekveilen for å oppvarme katalysatoren til en ønsket reaksjonstemperatur under oppstartingen og under transient drift. Et slikt foretrukket og
illustrerende eksempel er i den foreliggende beskrivelse generelt henvist til som skjermet oppvarming. Viktige, illustrerende fordeler med denne belyste utførelsesform innbefatter: varmetilførsel til katalysatoren for hurtig og effektiv oppstarting, forvarming av hydrokarbonbrennstoffet som tilføres til brennstoffprosessoren, og assistanse til å opprettholde reaksjonstemperaturen i reaktoren under transient drift.
KORT BESKRIVELSE AV TEGNINGENE
Beskrivelsen er presentert med henvisning til de vedføyede tegninger, hvor: Figur 1 viser et enkelt flytdiagram for en prosess med en brennstoffprosessor.
Figur 2 illustrerer en kompakt brennstoffprosessor, og
Figur 3 illustrerer en belysende utførelsesform av en plan varmer for et katalysatorsjikt. Figur 4 illustrerer en belysende utførelsesform hvor et elektrisk varmeelement er flettet inn i et monolittisk katalysatorsjikt. Figur 5 illustrerer en belysende utførelsesform hvor et monolittisk katalysatorsjikt er innhyllet i et elektrisk varmeelement.
BESKRIVELSE AV BELYSENDE UTFØRELSESFORMER
Den foreliggende oppfinnelse er generelt rettet på en apparatur og fremgangsmåte for oppvarming av et katalysatorsjikt ved oppstarting og for å tilveiebringe varme til et katalysatorsjikt under transient drift for å opprettholde ønskede reaksjonstemperaturer. I et foretrukket aspekt angår apparaturen og fremgangsmåten beskrevet her å tilveiebringe varme til et katalysatorsjikt i en kompakt brennstoffprosessor ved produksjon av en hydrogenrik gasstrøm fra et hydrokarbonråstoff. Hydrogenrik gass produsert i slike kompakte brennstoffprosessorer vil ha økende viktighet med utviklingen av brenselceller, innbefattende brenselceller som gir kraft til drift av kjøretøyer. Andre mulige anvendelser er imidlertid tatt i betraktning med hensyn til apparaturene og fremgangsmåtene beskrevet her, innbefattende oppstarting og opprettholdelse av reaksjonstemperatur for eksoterme katalysatorsjikt som ikke brukes i brennstoffprosessorer. Selv om oppfinnelsen er beskrevet her i sammenheng med kompakte brennstoffprosessorer og brenselceller, er følgelig rammen for oppfinnelsen ikke begrenset til slik bruk.
Hver av de belysende utførelsesformer ifølge den foreliggende oppfinnelse angår eksoterme katalysatorsjikt i forbindelse med brennstoffprosessorer hvor hydrokarbonråstoff blir ledet gjennom brennstoffprosessoren. Så lenge hydrokarbonbrennstoffet kan bli fordampet, kan det være flytende eller gassformig ved de omgivende betingelser. Slik det anvendes her, vil begrepet "hydrokarbon" innbefatte organiske forbindelser som har C-H-bindinger og som ved slike reaksjoner som partiell oksidasjon eller dampreformering er i stand til å danne hydrogen. Det er ikke utelukket at andre atomer enn karbon og hydrogen kan være til stede i forbindelsens molekylstruktur. Egnede brennstoffer for anvendelse ved fremgangsmåten og apparaturen beskrevet her innbefatter således, men er ikke begrenset til, hydrokarbonbrennstoffer som naturgass, metan, etan, propan, butan, nafta, bensin og diesel, og alkoholer som metanol, etanol, propanol og lignende.
Råstoffene til brennstoffprosessoren innbefatter hydrokarbonbrennstoff, oksygen og vann. Oksygenet kan være i form av luft, anriket luft eller hovedsakelig rent oksygen. Vannet kan bli tilført som væske eller damp. Sammensetning av råstoffkomponenter i blandingen bestemmes av de ønskede driftsbetingelser, som diskutert nedenfor.
Utløpsstrømmen fra brennstoffprosessoren innbefatter hydrogen og karbondioksid, men kan også innbefatte noe vann, uomsatte hydrokarboner, karbonmonoksid, forurensninger (for eksempel hydrogensulfid og ammoniakk) og inerte komponenter (for eksempel nitrogen og argon, spesielt dersom luft er en komponent i råstoffstrømmen).
På figur 1 vises et generelt flytdiagram for prosessen med en brennstoffprosessor. Fagfolk på området vil forstå at en viss mengde progresjon er nødvendig i reaktantstrøm-men gjennom reaktorene beskrevet her.
Prosesstrinn A er en autotermisk reformeringsprosess hvor to reaksjoner, partiell oksidasjon (reaksjonsligning I nedenfor) og eventuelt også dampreformering (reaksjonsligning II nedenfor), er kombinert for å omdanne råstoffstrømmen F til en syntesegass som inneholder hydrogen og karbonmonoksid. Reaksjonsligningene I og II er eksempler på reaksjonsligninger hvor hydrokarbonet er metan:
Den partielle oksidasjonsreaksjon går svært hurtig med fullstendig omsetning av tilsatt oksygen, samtidig som det produseres varme. Dampreformeringsreaksjonen går saktere og forbruker varme. En høyere konsentrasjon av oksygen i råstoffstrømmen vil favorisere partiell oksidasjon, mens en høyere konsentrasjon av vanndamp vil favorisere dampreformering. Forholdet mellom oksygen og karbon, og forholdet mellom vann og hydrokarbon, blir karakteriserende parametre. Disse forhold vil påvirke driftstemperaturen og hydrogenutbyttet.
Driftstemperaturen ved det autotermiske reformeringstrinn kan være i området fra ca. 550 °C til ca. 900 °C, avhengig av råstoffbetingelsene og katalysatoren. Ifølge oppfinnelsen anvendes et katalysatorsjikt med katalysator for partiell oksidasjon, med eller uten en dampreformeringskatalysator. Katalysatoren kan være i enhver form, innbefattende granulater, kuler, ekstrudater, monolitter og lignende. Katalysatorer for partiell oksidasjon bør være vel kjent av fagfolk på området og består ofte av edelmetaller som platina, palladium, rhodium og/eller ruthenium på et aluminasubstrat i form av monolitt, ekstrudat, granulat eller annen bærer. Ikke-edelmetaller som nikkel og kobolt er også blitt anvendt. Andre substrater som titania, zirkonia, silika og magnesia er blitt nevnt i litteraturen. Mange ytterligere materialer som lantan, cerium og kalium er blitt nevnt i litteraturen som "akseleratorer" som forbedrer virkningen hos katalysatoren ved partiell oksidasjon.
Dampreformeringskatalysatorer bør være kjent av fagfolk på området og kan innbefatte nikkel med andeler av kobolt eller et edelmetall som platina, palladium, rhodium, ruthenium og/eller iridium. Katalysatoren kan være båret for eksempel på magnesia, alumina, silika, zirkonia eller magnesiumaluminat, alene eller i kombinasjon. Alternativt kan dampreformeringskatalysatoren innbefatte nikkel, fortrinnsvis båret på magnesia, alumina, silika, zirkonia eller magnesiumaluminat, alene eller i kombinasjon, og som akselerator et alkalimetall som kalium.
Prosesstrinn B er et kjøletrinn for å avkjøle syntesegasstrømmen fra prosesstrinn A til en temperatur på ca. 200 °C til ca. 600 °C, fortrinnsvis fra ca. 300 °C til ca. 500 °C, og mer foretrukket fra ca. 375 °C til ca. 425 °C, i den hensikt å optimalisere temperaturen i utløpsstrømmen med syntesegass med sikte på neste trinn. Denne avkjøling kan oppnås med varmekapper, varmerør eller varmevekslere avhengig av konstruksjonsspesifika-sjonene og behovet for å gjenvinne/resirkulere varmeinnholdet i gasstrømmen. Én utfør-elsesform som belyser trinn B er anvendelse av en varmeveksler hvor råstoffstrømmen F utnyttes som kjølemiddel som sirkulerer gjennom varmeveksleren. Varmeveksleren kan være av enhver hensiktsmessig konstruksjon som er kjent av fagfolk på området, innbefattende skall og rør, plate, spiral, etc. Alternativt, eller i tillegg til dette, kan kjøletrinn B utføres ved å sprøyte inn ytterligere råstoffkomponenter som brennstoff, luft eller vann. Vann foretrekkes på grunn av dets evne til å absorbere en stor mengde varme når det fordamper til damp. Mengden tilsatte komponenter avhenger av ønsket grad av kjøling og kan lett bestemmes av fagfolk på området.
Prosesstrinn C er et rensetrinn. Én av de største forurensningene i hydrokarbon-strømmen er svovel, som ved autotermisk reformering i trinn A omdannes til hydrogensulfid. Behandlingskjernen anvendt i prosesstrinn C innbefatter fortrinnsvis sinkoksid og/eller et annet materiale med evne til å absorbere og konvertere hydrogensulfid, og den kan innbefatte en bærer (for eksempel monolitt, ekstrudat, granulat, etc). Avsvovlingen utføres ved å konvertere hydrogensulfidet til vann i henhold til følgende reaksjonsligning ffl:
Andre forurensninger, så som klorider, kan også bli fjernet. Reaksjonen utføres fortrinnsvis ved en temperatur fra ca. 300 °C til ca. 500 °C, og mer foretrukket fra ca. 375 °C til ca. 425 °C. Sinkoksid er en effektiv absorbent for hydrogensulfid innen et bredt temperaturområde fra ca. 25 °C til ca. 700 °C og gir stor fleksibilitet med hensyn til å optimalisere rekkefølgen av prosesstrinnene gjennom et hensiktsmessig valg av drifts-temperatur.
Avløpsstrømmen kan så bli sendt til blandetrinn D hvor vann eventuelt tilsettes til gasstrømmen. Tilsetningen av vann senker temperaturen i reaktantstrømmen når vannet fordamper og det tilfører mer vann til vanngassforskyvningsreaksjonen i prosesstrinn E (diskutert nedenfor). Vanndampen og de andre komponentene i utløpsstrømmen blandes ved at de blir ført gjennom en behandlingskjerne av inerte materialer som keramiske perler eller tilsvarende materialer som effektivt blander og/eller hjelper til med å for-dampe vannet. Alternativt kan en del av vannet, eller alt tilsatt vann, bli ført inn sammen med råstoffet, og blandetrinnet kan bli reposisjonert for å oppnå bedre blanding av oksidantgassen i CO-oksidasjonstrinnet G beskrevet nedenfor.
Prosesstrinn E er en vanngassforskyvningsreaksjon som omdanner karbonmonoksid til karbondioksid i henhold til reaksjonsligning IV:
Dette er et viktig trinn fordi karbonmonoksid i tillegg til å være svært toksisk for mennesker, er en gift for brenselceller. Konsentrasjonen av karbonmonoksid bør bli senket, fortrinnsvis til et nivå som kan tolereres av brenselcellene, typisk til under 50 ppm. Generelt kan vanngassforskyvningsreaksjonen finne sted ved en temperatur fra 150 °C til 600 °C, avhengig av den anvendte katalysator. Under slike betingelser vil det meste av karbonmonoksidet i gasstrømmen bli omdannet i dette trinn.
Katalysatorer for forskyvning ved lav temperatur virker i et område fra ca. 150 °C til ca. 300 °C og innbefatter for eksempel kobberoksid, kobber båret på andre overgangsmetalloksider som zirkonia, sink båret på overgangsmetalloksider eller ildfaste bærere som silika, alumina, zirkonia, etc, eller et edelmetall som platina, rhenium, palladium, rhodium eller gull på en egnet bærer som silika, alumina, zirkonia, og lignende.
Katalysatorer for forskyvning ved høy temperatur virker fortrinnsvis ved temperaturer i området fra ca. 300 °C til ca. 600 °C og kan innbefatte overgangsmetalloksider som ferrioksid eller kromioksid, og eventuelt innbefattende en akselerator som kobber eller jernsilicid. Også innbefattet som katalysatorer for forskyvning ved høy temperatur, er bårede edelmetaller, så som båret platina, palladium og/eller andre medlemmer av platinagruppen.
Behandlingskjernen anvendt ved utførelsen av dette trinn kan innbefatte et pakket sjikt med katalysatorer for forskyvning ved høy temperatur eller lav temperatur, som beskrevet over, eller en kombinasjon av katalysatorer for forskyvning ved både høy temperatur og lav temperatur. Prosessen bør utføres ved enhver temperatur som er egnet for vanngassforskyvningsreaksjonen, fortrinnsvis ved en temperatur fra 150 °C til ca. 400 °C, avhengig av anvendt type katalysator. Eventuelt kan et kjøleelement så som en kjøleolje bli anbrakt i behandlingskjernen i forskyvningsreaktoren for å senke reaksjonstemperaturen inne i sjiktet med pakket katalysator. Lavere temperaturer favoriserer omdannelse av karbonmonoksid til karbondioksid. I trinn C kan det også utføres en renseprosess mellom konverteringene ved høy og lav temperatur ved å tilveiebringe separate trinn for forskyvninger ved høy temperatur og lav temperatur med en avsvov-lingsmodul mellom trinnene for forskyvning ved høy temperatur og lav temperatur.
Prosesstrinn F er et kjøletrinn utført ifølge én illustrerende utførelsesform, med en varmeveksler. Varmeveksleren kan være av en hver hensiktsmessig konstruksjon innbefattende skall og rør, plate, spiral, etc. Alternativt kan det benyttes et varmerør eller en annen form for varmekappe. Hensikten med varmeveksleren er å redusere tempera turen i gasstrømmen slik at det produseres en utløpsgass med en temperatur fortrinnsvis i området fra ca. 90 °C til ca. 150 °C.
Oksygen tilsettes til prosessen i trinn F. Oksygenet forbrukes ved reaksjonene i prosesstrinn G beskrevet nedenfor. Oksygenet kan være i form av luft, anriket luft eller hovedsakelig rent oksygen. Varmeveksleren kan ha enhver utforming som gir blanding av luften med den hydrogenrike gass. Alternativt kan den illustrerende utførelsesform av prosesstrinn D bli anvendt til å utføre blandingen.
Prosesstrinn G er et oksidasjonstrinn hvor nesten alt gjenværende karbonmonoksid i avløpsstrømmen blir konvertert til karbondioksid. Prosesseringen utføres i nærvær av en katalysator for oksidasjon av karbonmonoksid. Katalysatoren kan ha enhver hensiktsmessig form, så som granulater, kuler, monolitter, etc. Oksidasjonskatalysatorer for karbonmonoksid er kjent og innbefatter typisk edelmetaller (for eksempel platina, palladium) og/eller overgangsmetaller (for eksempel jern, krom, mangan) og/eller edelmetall-eller overgangsmetallforbindelser, særlig oksider. En foretrukket oksidasjonskatalysator er platina på et alumina-substrat. Substratet kan påføres på en monolitt, et ekstrudat, en granulat eller en annen bærer. Ytterligere materialer som cerium eller lantan kan bli tilsatt for å forbedre virkningen. Mange andre formuleringer er blitt angitt i litteraturen, og noen praktikere hevder å ha oppnådd bedre virkning med rhodium- eller aluminakatalysatorer. I litteraturen er det angitt at ruthenium, palladium, gull og andre materialer er aktive for denne anvendelse.
To reaksjoner forekommer i prosesstrinn G: den ønskede oksidasjon av karbonmonoksid (ligning V) og den uønskede oksidasjon av hydrogen (ligning VI) som vist:
Den foretrukne oksidasjon av karbonmonoksid favoriseres av lave temperaturer. Siden begge reaksjoner produserer varme, så kan det være fordelaktig eventuelt å innlemme et kjøleelement, så som en kjølespiral anbragt inne i prosessen. Driftstemperaturen for prosessen holdes fortrinnsvis i området fra ca. 90 °C til ca. 150 °C. I prosesstrinn G reduseres fortrinnsvis karbonmonoksidnivået til mindre enn 50 ppm, som er et egnet nivå for anvendelse i brenselceller, men fagfolk på området vil forstå at den foreliggende oppfinnelse kan bli tilpasset fremstilling av et hydrogenrikt produkt med både høyere og lavere nivåer med karbonmonoksid.
Avløpsstrømmen som forlater brennstoffprosessoren er en hydrogenrik gass som inneholder karbondioksid og andre bestanddeler som kan være til stede, så som vann, inerte komponenter (for eksempel nitrogen, argon), gjenværende hydrokarbon, etc. Produktgassen kan bli anvendt som et råstoff i en brenselcelle eller for andre anvendelser hvor det er ønskelig med en hydrogenrik tilførselsstrøm. Eventuelt kan produktgassen bli sendt til viderebehandling, for eksempel for å fjerne karbondioksid, vann eller andre komponenter.
Én utførelsesform som illustrerer en brennstoffprosessor, er en kompakt brennstoffprosessor med moduloppbygging omfattende individuelle modulenheter som kan adskilles, omordnes og individuelt byttes ut. Med henvisning til figur 2 så innbefatter en kompakt brennstoffprosessor 100 en serie med individuelle moduler (110, 120, 130, 140, 150, 160 og 170). Modulenhetene kan bli anvendt i enhver orientering, for eksempel vertikal eller horisontal orientering, og de er tilpasset bruk i forbindelse med en brenselcelle slik at den hydrogenrike produktgass fra reaktoren beskrevet her, tilføres direkte til en brenselcelle som en tilførselsstrøm. Selv om modulene kan ha enhver tverrsnittskonfi-gurasjon, så som sirkulær, rektangulær, triangulær etc, så foretrekkes et sirkulært tverr-snitt slik at brennstoffprosessoren 100 i allmennhet vil vær rørformet.
Med brennstoffprosessoren 100 vist på figur 2 utføres prosessen illustrert med flytdiagrammet på figur 1. Tilførselsstrøm F føres inn gjennom innløpsrør 102 og produktgass P trekkes ut via utløpsrør 103. Apparaturen 100 innbefatter flere moduler som kan være stablet på hverandre til en moduloppbygging som kan bli modifisert ved å bytte ut individuelle moduler. Hver modul utfører en separat driftsfunksjon og er generelt sammenstilt som vist på figur 2. Modul 110 er den autotermiske reformeringsmodul tilsvarende prosesstrinn A på figur 1. Modul 120 er et kjøletrinn tilsvarende prosesstrinn B på figur 1.1 denne illustrerte utførelsesform er varmeveksleren 121 vist som en generell varmekappe for modul 120. Modul 130 er en rensemodul tilsvarende prosesstrinn C på figur 1. Modul 140 er et valgfritt blandetrinn tilsvarende prosesstrinn D på figur 1. Gjennom matedyse 131 tilføres en eventuell vannstrøm til modul 140 for å hjelpe til med å drive vanngassforskyvningsreaksjonen (ligning IV) i modul 150. Modul 150 er en vann-gassforskyvningsmodul tilsvarende prosesstrinn E på figur L Gjennom matedyse 151 tilføres en oksygenholdig gass til prosessgassen for oksidasjonsreaksjonen (ligning V) i modul 170. Modul 150 inneholder også en varmeveksler (ikke vist) posisjonert inne i eller rundt katalysatorsjiktet slik at det kan opprettholdes en ønsket temperatur for vanngassforskyvningsreaksjonen. Modul 160 er et kjøletrinn tilsvarende prosesstrinn F på figur 1.1 denne illustrerte utførelsesform er varmeveksleren 161 vist som en generell varmekappe i modul 160. Modul 170 er et oksidasjonstrinn tilsvarende prosesstrinn G på figur 1. Modul 170 inneholder også en varmeveksler (ikke vist) posisjonert inne i eller omkring katalysatorsjiktet slik at det opprettholdes en ønsket temperatur for oksidasjonsreaksjonen. Fagfolk på området vil forstå at prosessutformingen beskrevet i denne illustrerende utførel-sesform kan variere avhengig av mange faktorer, innbefattende men ikke begrenset til, råstoffkvalitet og ønsket produktkvalitet.
Den foreliggende oppfinnelse angår spesifikt fremgangsmåter og apparaturer for oppvarming av et katalysatorsjikt for oppstarting og for å tilveiebringe varme til et kataly satorsjikt under transient drift for å opprettholde ønskede reaksjonstemperaturer. Transient drift innbefatter, men er ikke begrenset til, endringer i hydrokarbonråstoffet tilført til brennstoffprosessoren, prosessforstyrrelser, endringer i katalysatoraktivitet og øket eller minsket volumetrisk råstofftilførsel til brennstoffprosessoren. I slike brennstoffprosessorer som beskrevet over, kan mange katalysatorer bli anvendt i henhold til den foreliggende oppfinnelse, innbefattende katalysatorer for autotermisk reformering, partiell oksidasjon, dampreformering, vanngassforskyvning og selektiv oksidasjon, og svovelabsorbenter. I disse eksoterme katalysatorsjikt er oppvarming av katalysatoren til reaksjonstemperaturen viktig for å oppnå effektiv oppstarting av en brennstoffprosessor fra kaldstart. Fordi ett bruksområde for kompakte brennstoffprosessorer vil være i kjøretøyer, er det ønskelig med en løsning hvor det benyttes elektriske varmeelementer. Transient drift er dessuten viktig når det gjelder å sikre tilførsel av hydrogenrik gass til en brenselcelle som får tilførselen direkte fra en brennstoffprosessor.
Generelt kan katalysatoren oppvarmes direkte eller indirekte med et elektrisk varmeelement. Direkte oppvarming av katalysatoren oppnås gjennom direkte kontakt mellom varmeelementet og katalysatoren. Indirekte oppvarming oppnås med direkte oppvarming av et fluid, så som en prosesstrøm, som i sin tur strømmer gjennom katalysatoren og derved overfører varme til katalysatoren. I tillegg kan indirekte oppvarming oppnås ved å anbringe varmeelementet innenfor en kappe som så er i direkte kontakt enten med katalysatoren eller fluidet som strømmer igjennom katalysatoren. Ved hjelp av disse innretninger kan katalysatoroppvarmingen bli benyttet for katalysatorer med mange utforminger, innbefattende granulater, ekstrudater, kuler og monolitter. Katalysatorvarmeren i henhold til denne oppfinnelse kan være fremstilt med enhver type motstandstråd, patroner eller stenger som kan være utformet som forklart nedenfor. En kraftkilde, så som en elektrisk kraftkilde, gir energi til å produsere varmen.
Nå med henvisning til figur 3, så kan en flatevarmer 300 bli benyttet til å tilføre varme til en katalysatorsjiktflate 310.1 en utførelsesform kan eksempelvis katalysator-sjiktflaten være én ende av et sylindrisk formet katalysatorsjikt. Det vil forstås av fagfolk på området at i den foreliggende oppfinnelse kan katalysatorsjiktets orientering være enten vertikal eller horisontal. I denne viste utførelsesform er flatevarmeren 300 et elektrisk varmeelement i spiralform anbragt mot endeflaten på katalysatorsjiktet, selv om en annen utførelsesform kan benyttes til å gi tilstrekkelig varmeoverføring til katalysatorsjiktets endeflate. Ved å føre en liten strøm med reaktanter gjennom det elektriske varmeelementet og katalysatorsjiktet, blir den eksoterme reaksjon initiert i endeflaten av katalysatorsjiktet. Varmen tilført med flatevarmeren diffunderer gjennom hele katalysatorsjiktet og i tillegg vil reaksjons varmen dannet i katalysatorsjiktets endeflate propagere gjennom katalysatorsjiktet og derved oppvarme katalysatorsjiktet for oppstarting. Et foretrukket aspekt ved denne viste utførelsesform er anvendelse av flatevarmeren 300 på katalysatorsjiktets oppstrømsflate (dvs. enden på katalysatorsjiktet som ligger mot reaktortilførselen) slik at reaksjons varmen føres inn i den "kalde" katalysatoren for derved å forbedre effektiviteten ved oppstartingen med katalysatoren.
Nå med henvisning til figur 4, så er det elektriske varmeelement 400 flettet gjennom katalysatorsjiktet 410.1 den viste utførelsesform er det elektriske varmeelement flettet gjennom enten et katalysatorsjikt med granulater, ekstrudater, kuler, etc., eller gjennom en monolittisk katalysatorstruktur. Flettemønsteret (så som en spole) kan være utformet for å oppnå optimal oppvarming av katalysatorsjiktet. Med denne viste utførelsesform tilføres oppvarming fra innsiden av katalysatorsjiktet og utover. Det er valgfritt å la et fluid strømme gjennom katalysatoren under oppvarmingen.
Nå med henvisning til figur 5, så er det elektriske varmeelement 500 viklet rundt en monolittisk katalysatorstruktur 510. Dette medfører oppvarming av katalysatoren fra utsiden og innover mot sentrum. Det er valgfritt å la et fluid strømme gjennom katalysatoren under oppvarmingen.
En annen belysende utførelsesform innbefatter en reaktor i en brennstoffprosessor, hvor det er innbefattet et katalysatorsjikt, en kjølespiral posisjonert inne i katalysatorsjiktet for å fjerne overskuddsvarme under normal drift, og et elektrisk varmeelement posisjonert i kjølespiralen for å oppvarme katalysatoren til en ønsket reaksjonstemperatur under oppstarting og under transient drift. Dette er et eksempel på den indirekte oppvarming beskrevet over. Fagfolk på området vil forstå at denne viste utførelsesform har mange fordeler ved at det tilføres varme til katalysatoren for å oppnå hurtig og effektiv oppstarting, hydrokarbonråstoffet til brennstoffprosessoren forvarmes ved at det kan passere gjennom kjølespiralen i en brennstoffprosessor som har kompakt oppbygning, og ved at det hjelper til med å opprettholde reaksjonstemperaturen under transient drift.
Selv om apparatur, blandinger og fremgangsmåter ifølge denne oppfinnelse er blitt beskrevet ved hjelp av foretrukne eller illustrerende utførelsesformer, så vil det være åpenbart for fagfolk på området at det kan foretas variasjoner i prosessen beskrevet her uten å avvike fra konseptet og rammen for oppfinnelsen. Alle slike erstatninger og modifikasjoner som er åpenbare for fagfolk på området, er ment å ligge innen rammen og konseptet for oppfinnelsen slik den er angitt i de følgende krav.

Claims (16)

1. Fremgangsmåte for oppvarming av et katalysatorsjikt for oppstarting,karakterisert vedat den omfatter: et elektrisk varmeelement posisjonert i et katalysatorsjikt som har en kjølespiral posisjonert inne i katalysatorsjiktet for å fjerne overskuddsvarme hvori det elektriske varmeelementet er i direkte kontakt med katalysatorsjiktet og er posisjonert i kjøle-spiralen; en liten strøm med reaktanter føres gjennom det elektriske varmeelementet og katalysatorsjiktet, og det elektriske varmeelementet oppvarmes og initierer en eksoterm reaksjon i katalysatorsjiktet, hvorved reaksjonsvarmen sprer seg gjennom katalysatorsjiktet og derved oppvarmer katalysatorsjiktet slik at det er klart for oppstarting.
2. Fremgangsmåte ifølge krav 1, hvor det elektriske varmeelementet posisjoneres langs oppstrøms-endeflaten på katalysatorsjiktet.
3. Fremgangsmåte ifølge krav 1, hvor det elektriske varmeelementet er utformet som en spiral og anbringes mot én endeflate av katalysatorsjiktet.
4. Fremgangsmåte ifølge krav 1, hvor katalysatorsjiktet velges blant granulater, ekstrudater, kuler, monolitter og enhver kombinasjon av disse.
5. Fremgangsmåte ifølge krav 1, hvor katalysatorsjiktet inneholder katalysatorer valgt blant katalysatorer for autotermisk reformering, partiell oksidasjon, dampreformering, vanngassforskyvning, selektiv oksidasjon og oksidasjon av restgass ved anoden, samt svovelabsorbenter.
6. Fremgangsmåte ifølge krav 1, hvor det elektriske varmeelementet oppvarmes slik at det opprettholder en ønsket temperatur på katalysatorsjiktet.
7. Fremgangsmåte ifølge krav 6, hvor det elektriske varmeelementet er flettet inn i kataly satorsj iktet.
8. Fremgangsmåte ifølge krav 6, hvor katalysatorsjiktet er en monolitt.
9. Fremgangsmåte ifølge krav 8, hvor det elektriske varmeelementet er viklet rundt monolitten.
10. Fremgangsmåte ifølge krav 1, hvor: det elektriske varmeelementet posisjoneres på oppstrømssiden av katalysatorsjiktet, og et fluid føres gjennom det elektriske varmeelementet og gjennom katalysatorsjiktet, hvorved katalysatorsjiktet oppvarmes til den ønskede temperatur.
11. Fremgangsmåte ifølge krav 7-10, hvor den ønskede temperatur er oppstarts-temperaturen.
12. Fremgangsmåte ifølge krav 7-10, hvor den ønskede temperatur er den ønskede reaksjonstemperatur under transient drift.
13. Reaktormodul for anvendelse i en kompakt brennstoffprosessor,karakterisert vedat den omfatter: et katalysatorsjikt, en kjølespiral posisjonert inne i katalysatorsjiktet for å fjerne overskuddsvarme under normal drift, og et elektrisk varmeelement posisjonert i kjølespiralen på katalysatorsjiktet, hvor varmeelementet er i stand til å initiere en eksoterm reaksjon i oppstrømsendeflaten på katalysatorsjiktet i nærvær av en liten strøm med reaktanter.
14. Reaktormodul ifølge krav 13, hvor det elektriske varmeelementet er utformet som en spiral.
15. Reaktormodul ifølge krav 13, hvor katalysatorsjiktet er valgt blant granulater, ekstrudater, kuler, monolitter og enhver kombinasjon av disse.
16. Reaktormodul ifølge krav 13, hvor katalysatorsjiktet inneholder en katalysator valgt blant katalysatorer for autotermisk reformering, partiell oksidasjon, dampreformering, vanngassforskyvning, selektiv oksidasjon og oksidasjon av anoderestgass, samt svovelabsorbenter.
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