NO328552B1 - Fremgangsmate for fremstilling av hydrogen- og karbonmonoksidrik gass ved dampreformering av hydrokarbonrastoff i naervaeret av en dampreformeringskatalysator - Google Patents

Fremgangsmate for fremstilling av hydrogen- og karbonmonoksidrik gass ved dampreformering av hydrokarbonrastoff i naervaeret av en dampreformeringskatalysator Download PDF

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NO328552B1
NO328552B1 NO20006711A NO20006711A NO328552B1 NO 328552 B1 NO328552 B1 NO 328552B1 NO 20006711 A NO20006711 A NO 20006711A NO 20006711 A NO20006711 A NO 20006711A NO 328552 B1 NO328552 B1 NO 328552B1
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steam reforming
reactor
gas
reforming catalyst
hydrogen
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NO20006711L (no
NO20006711D0 (no
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Jens Richard Rostrup-Nielsen
Ib Dybkjaer
Peter Seier Christensen
Viggo Lucassen Hansen
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Haldor Topsoe As
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Publication of NO328552B1 publication Critical patent/NO328552B1/no

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Abstract

Fremgangsmåte for fremstilling av hydrogen- og karbonmonoksid-rik gass ved dampreformering av hydrokarbonråstoff i nærvær av en dampreformerings- katalysator avsatt som tynn film på veggen av en reaktor, som omfatter trinnene (a) valgfritt føring av en prosessgass av hydrokarbonråstoff gjennom en første reaktor med en tynn film av dampreformerings- katalysator avsatt på vegger av reaktoren i varme- ledende forhold med en varm gasstrøm; (b) føring av den utstrømmende gassen fra den første reaktoren til en påfølgende rørformet reaktor som er utstyrt med en tynn film av dampreformeringskatalysator og/eller dampreformeringskatalysatorpellets og som oppvarmes ved brenning av brensel, for derved å oppnå en delvis dampreformert utstrømmende gass og en varm gasstrøm av avgass; (c) føring av den utstrømmende gassen fra den andre reaktoren til en autotermisk reformer; og (d) uttrekking fra den autotermiske reformeren av en varm gasstrøm av produktgass rik på hydrogen og karbon-monoksid.

Description

Oppfinnelsen angår fremstillingen av syntesegass ved dampreformering av et hydrokarbonråstoff i kontakt med katalysert hardware.
Uttrykket katalysert hardware er anvendt for et katalysatorsystem hvor et lag av katalysator er festet på en overflate av et annet materiale, f.eks. metalloverflater. Det andre materialet fungerer som støttestrukturer som gir fasthet til systemet. Dette gjør det mulig å utforme katalysatorformer som ikke ville ha tilstrekkelig mekanisk fasthet i seg selv. Systemet her består av rør hvorpå det er plassert et tynt lag av reformeringskatalysator på innerveggen.
Alternative løsninger kan omfatte rør med et katalysatorlag på utsiden, plater med katalysatorbelegg, eller andre egnede former.
Syntesegass produseres fra hydrokarboner ved dampreformering ved reaksjonene (l)-(3):
En annen metode for fremstilling av syntesegass er autotermisk reformering (ATR). I autotermisk reformering utføres forbrenning av hydrokarbonføde med substøkiometriske mengder av oksygen ved flammereaksjoner i en forbrenningssone og deretter dampreformering av det delvis forbrente råstoffet i et stasjonært sjikt av dampreformeringskatalysator. Oksidanten kan være luft, anriket luft, eller ren oksygen.
En tredje metode for fremstilling av syntesegass er kombinasjonen av først å føre hydrokarbonføden gjennom et stasjonært sjikt av reformeringskatalysator og deretter føre den delvis reformerte føden gjennom en autotermisk reformer. Det stasjonære sjiktet kan innbefatte et stort antall rør plassert i et brennkammer. Denne kombinasjonen kalles totrinns reformering eller primært etterfulgt av sekundær reformering og er spesielt egnet for produksjon av syntesegass for metanol og ammoniakkproduksjon. Ved å kontrollere mengden av reformering som skjer i den stasjonære sjiktdampsreformeren før ATR, kan det produseres en syntesegass med den korrekte støkiometrien for metanolsyntese eller en syntesegass med det korrekte forholdet mellom hydrogen og nitrogen for ammoniakksyntese.
Teknikkens stand innen reformeringsteknologi gjør bruk av reformeringskatalysator i formen av pellets av forskjellige størrelser og former. Katalysator-pelletsene er plassert i stasjonære sjiktreaktorer (reformerrør). Reformeringsreaksjonen er endotermisk. I konvensjonelle reformere er den nødvendige varmen for reaksjonen tilført fra omgivelsen på utsiden av rørene vanligvis ved en kombinasjon av stråling og konveksjon til yttersiden av reformerrøret. Varmen overføres til innsiden av røret ved varmekonveksjon gjennom rørveggen og overføres til gassfasen ved konveksjon. Til slutt overføres varmen fra gassfasen til katalysatorpelletsen ved konveksjon. Katalysatortemperaturen kan være mer enn 100 °C lavere enn innerrørveggtemperaturen ved den samme aksialposisjonen til reformerrøret.
Det har blitt funnet at varmetransport er mer effektivt når katalysert hardware er anvendt i dampreformeringsprosessen. Varmetransporten til katalysatoren skjer ved konduksjon fra innerrørveggen. Dette er en mye mer effektiv transportmekanisme enn transporten ved konveksjon via gassfasen. Resultatet er at temperaturene på innerrørveggen og katalysatoren er nesten identisk (forskjellen er under 5 °C). Videre kan rørtykkelsen reduseres, se det etterfølgende, som gjør temperatur-forskjellen mellom inner- og yttersiden av reformerrøret mindre. Det er således mulig å ha både en høyere katalysatortemperatur og en lavere rørtemperatur, idet andre betingelser er de samme når man erstatter de konvensjonelle reformerrørene med katalyserte hardware-rør. En lav ytterrørveggtemperatur er ønskelig siden det forlenger levetiden på røret. En høy katalysatortemperatur er fordelaktig siden reduksjonshastigheten øker med temperatur og siden likevekten til reaksjonen (3) går mot høyre, noe som resulterer i bedre utnyttelse av føden.
Trykkfall i det katalyserte reformeringsrøret er mye lavere enn i det konvensjonelle tilfellet for den samme rørdiameteren. Dette muliggjør anvendelsen av reaktorer av ikke-tradisjonelle former, f.eks. rør med liten diameter og fortsatt opprettholdelse av akseptable trykkfall. Mindre rørdiameter resulterer i en øket rørlevetid, tolererer høyere temperaturer og reduserer rørmaterialforbruk.
Til slutt reduseres katalysatormengden ved anvendelse av katalyserte hardware-reformeringsrør sammenlignet med den konvensjonelle reformeren med et stasjonært sjikt av reformeringskatalysator.
Den mindre mengde av katalysator krever anvendelsen av et råstoff fritt for katalysatorgifter. Dette kan f.eks. oppnås ved å sende råstoffet gjennom en prereformer.
Fig. 1 viser et eksempel på et anlegg som produserer syngass. Føde 2 forvarmes, avsvovles i enhet 4, blandes med prosessdamp 6, og ytterligere oppvarmes før den går inn i en adiabatisk prereformer 8. Avløpsstrømmen fra prereformer 8 oppvarmes ytterligere i en varmevekslerspole arrangert i avgasskanal 12 og sender til den rørformede reformeren 14, hvor omdannelse av metan til hydrogen, karbonmonoksid, og karbondioksid skjer. Avgassen passeres til autotermiske reformer 16, hvor forbrenning utføres med oksidantstrøm 18. Prosesseringen av avgass 20 nedstrøms for den autotermiske reformeren avhenger av den tilsiktede anvendelsen av produktet.
Katalysert hardware kan anvendes i to av enhetene vist i fig. 1:
1.1 forvarmerspolen 10 for oppvarming av prereformeravgassen før den går inn i den rørformede reformeren 14.
2.1 den rørformede reformeren 14.
Denne oppfinnelsen tilveiebringer en fremgangsmåte for fremstillingen av hydrogen- og karbonmonoksidrik gass ved dampreformering av hydrokarbonråstoff i nærvær av en dampreformeringskatalysator avsatt som tynn film på veggen av en reaktor, som er kjennetegnet ved trinnene
(a) føring av en prosessgass av hydrokarbonråstoff gjennom en første reaktor med en tynn film av dampreformeringskatalysator avsatt på vegger av reaktoren i et varmeledende forhold med en varm gasstrøm av avgass; (b) føring av den utstrømmende gassen fra den første reaktoren til en påfølgende rørformet reaktor som har en tynn film av dampreformeringskatalysator og/eller dampreformeringskatalysatorpellets og som oppvarmes ved brenning av brensel, for derved å oppnå en partiell dampreformert utstrømmende gass og den varme gasstrømmen av avgass; (c) føring av den utstrømmende gassen fra den andre reaktoren til en autotermisk reformer; og (d) uttrekking fra den autotermiske reformeren av en varm gasstrøm av produktgass rik på hydrogen og karbonmonoksid.
Eksempel 1
En katalysert hardware-reformeringsreaktor er blitt testet. Testenheten består av et system for mating av fødene til reaktoren, selve reaktoren, og utstyr for etterbehandling og analyse av den utstrømmende gassen fra reaktoren. Reaktoren består av en 1/4" rør med lengde 1050 mm som er, i midten 500 mm, belagt på innerveggen med RKNR-nikkeldampreformeringskatalysator. Katalysatoren har den samme sammensetningen som den RKNR-pelletsformede dampreformeringskatalysatoren tilgjengelig fra Haldor Topsøe A/S. Tykkelsen av katalysatorlaget er 0,31 mm. Det katalyserte reaktorrøret plasseres i et hus laget av fast metall, som har et hull som tetter godt rundt det katalyserte røret. En rekke valsede fordyp-ninger, hvori varmeelementer er plassert er utført langs hullet. Ett av varme-elementene er bevegelig slik at en veggtemperaturprofil av det katalyserte røret kan oppnås. I tillegg er varmeelementer plassert i gasskanalen i det katalyserte røret som måler gasstemperaturen ved innløpet til og utløpet fra den katalyserte sonen. Reaktoren med hus plasseres i en elektrisk oppvarmet ovn, hvor temperaturen kan kontrolleres separat i seks forskjellige soner.
Fødestrømmene består av hydrogen, metan, karbondioksid og damp. Føde-strømmene blandes og forvarmes før de går inn i reaktoren. Etter reaktoren kjøles den utstrømmende gassen, det kondenserte vannet separeres fra gassen, og gassammensetningen måles ved bruk av en gasskromatograf.
To innstillinger av betingelser ble testet. En innstilling ved lavere temperatur for å simulere anvendelse av katalysert hardware i en forvarmerspole (test nr. 1), og en innstilling av høyere temperatur for å simulere en rørformet reformer (test nr. 2). Betingelsene er vist i tabell 1. Trykket var i begge tilfeller 28 bar g. Temperatur-profilen på reaktorveggen målt av det bevegelige varmeelementet er vist i fig. 2.
Den målte utstrømmende gassammensetningen er vist i tabell 2. Gassammensetningen er på tørr basis.
Den utstrømmende gassen er i begge tilfeller i likevekt med hensyn på reformeringsreaksjonen ved utløpsgasstemperaturen innenfor eksperimentell usikkerhet. Dette viser at en omdannelse lignende en stasjonær sjiktreaktor kan oppnås i en katalysert hardware-reaktor.

Claims (2)

1. Fremgangsmåte for fremstilling av hydrogen- og karbonmonoksidrik gass ved dampreformering av hydrokarbonråstoff i nærværet av en dampreformeringskatalysator avsatt som tynn film på veggen av en reaktor, karakterisert ved at den omfatter trinnene (a) føring av en prosessgass av hydrokarbonråstoff gjennom en første reaktor (10) med en tynn film av dampreformeringskatalysator avsatt på vegger av reaktoren (10) i et varmeledende forhold med en varm gasstrøm av avgass; (b) føring av den utstrømmende gassen fra den første reaktoren (10) til en påfølgende rørformet reaktor (14) som er utstyrt med en tynn film av dampreformeringskatalysator og/eller dampreformeringskatalysatorpellets og som oppvarmes ved brenning av brensel, for derved å oppnå en partielt dampreformert utstrømmende gass og den varme gasstrømmen av avgass; (c) føring av den utstrømmende gassen fra den andre reaktoren (14) til en autotermisk reformer (16); og (d) uttrekking fra den autotermiske reformeren (16) av en varm gasstrøm av produktgass (20) rik på hydrogen og karbonmonoksid.
2. Fremgangsmåte som angitt i krav 1, karakterisert ved at dampreformeringskatalysatoren omfatter nikkel og/eller edelmetaller.
NO20006711A 1998-07-21 2000-12-29 Fremgangsmate for fremstilling av hydrogen- og karbonmonoksidrik gass ved dampreformering av hydrokarbonrastoff i naervaeret av en dampreformeringskatalysator NO328552B1 (no)

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