NO318107B1 - Fremgangsmate for fremstilling av syntesegass ved dampreformering ved anvendelse av katalysert materiale - Google Patents

Fremgangsmate for fremstilling av syntesegass ved dampreformering ved anvendelse av katalysert materiale Download PDF

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NO318107B1
NO318107B1 NO19980274A NO980274A NO318107B1 NO 318107 B1 NO318107 B1 NO 318107B1 NO 19980274 A NO19980274 A NO 19980274A NO 980274 A NO980274 A NO 980274A NO 318107 B1 NO318107 B1 NO 318107B1
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steam reforming
gas
reforming catalyst
reactor
tubular reactor
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Jens Richard Rostrup-Nielsen
Peter Seier Christensen
Viggo Lucassen Hansen
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Haldor Topsoe As
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00504—Controlling the temperature by means of a burner
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
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Description

Foreliggende oppfinnelse er rettet mot fremstillingen av syntesegass ved dampreformering av et hydrokarbonråstoff i kontakt med katalysert hardt materiale (hardware).
Betegnelsen katalysert hardt materiale (hardware) anvendes for et katalysatorsystem hvor et lag av katalysator er fiksert på en overflate av annet materiale, f.eks. metalliske overflater. Det andre materialet tjener som bærerstrukturen som gir styrke til systemet. Dette tillater utforming av katalysatorformer som ellers ikke ville hatt tilstrekkelig mekanisk styrke i seg selv. Foreliggende system består av rør hvorpå et tynt lag av reformeringskatalysator er plassert på innerveggen.
Syntesegass fremstilles fra hydrokarboner ved dampreformering ved reaksjonene (1) -
(3):
Teknikkens stand vedrørende dampreformeringsteknologi gjør bruk av reformeringskatalysator i form av pellets av forskjellige størrelser og former. Katalysatorpelletene plasseres i reaktorer med fiksert sjikt (reformerrør). Reformeringsreaksjonen er endoterm. I konvensjonelle reformerings innretninger tilføres den nødvendige varmen for reaksjonen fra miljøet utenfor rørene, vanligvis ved en kombinasjon av stråling og konveksjon til den ytre siden av reformeringsrøret. Varmen overføres til innersiden av røret ved varmeledning gjennom rørveggen, og overføres til gassfasen ved konveksjon. Endelig overføres varmen fra gassfasen til katalysatorpelleten ved konveksjon. Katalysatortemperaturen kan være mer enn 100°C lavere enn temperaturen på rør-innerveggen ved den samme aksiale posisjonen av reformeringsrøret.
EP 124 226 beskriver en fremgangsmåte som anvender en dobbelt rørformet damp-reformeruingsreaktor med et belegg av katalysator på yttersiden av det indre røret som oppvarmes indirekte med forbrenningsgass. Denne fremgangsmåten adskiller seg på vesentlige punkter fra fremgangsmåten ifølge foreliggende oppfinnelse.
Det er funnet at varmetransport er mer effektiv når katalysert hardt materiale (hardware) anvendes i dampreformeringsprosessen. Varmetransporten til katalysatoren finner sted ved ledning fra den indre rørveggen. Dette er en langt mer effektiv transportmekanisme enn transporten ved konveksjon via gassfasen. Resultatet er at temperaturene av den indre rørveggen og katalysatoren er tilnærmet identiske (forskjellen under 5°C). Videre kan rørtykkelsen reduseres, se nedenfor, hvilket gjør temperaturdifferansen mellom inner- og yttersiden av reformeirngsrøret mindre. Det er følgelig mulig å ha både en høyere katalysatortemperatur og en lavere rørtemperatur, idet alle andre betingelser er de samme når de konvensjonelle reformeringsrørene erstattes med katalyserte hard-materiale-rør. En lav temperatur på ytre rørvegg er ønskelig, siden dette forlenger levetiden av røret. En høy katalysatortemperatur er fordelaktig, siden reaksjons-hastigheten øker med temperatur og siden likevekten av reaksjon (3) forskyves mot høyre, hvilket resulterer i en bedre utnyttelse av råstoffet.
Følgelig tilveiebringer foreliggende oppfinnelse en fremgangsmåte for fremstilling av hydrogen og karbonmonoksydrik syntesegass ved dampreformering av et hydrokarbonråstoff i nærvær av en dampreformeringskatalysator båret som tynn film på en rørformet reaktor, kjennetegnet ved at den innbefatter trinnene: (a) føring av en prosessgass av prereformert hydrokarbon gjennom en rørformet reaktor som er utstyrt med en tynn film av dampreformeringskatalysatoren og som oppvarmes ved brenning av brennstoff, slik at det derved oppnås en partielt dampreformert gasseffluent og en varm avgass; (b) føring av effluenten fra den rørformede reaktoren til en dampreformeringskatalysator med fiksert sjikt; og (c) fjerning fra det fikserte sjiktet av en produktgass av hydrogen og karbonmonoksydrik syntesegass.
Trykkfall i det katalyserte reformeringsrøret er langt lavere enn i konvensjonelle tilfeller for den samme rørdiameteren. Dette muliggjør anvendelse av reaktorrør med en mindre diameter, mens det samtidig opprettholdes et akseptabelt trykkfall. Mindre rørdiameter resulterer i en forøket levetid for røret, tåler høyere temperaturer og reduserer forbruket av rørmaterialet.
Endelig reduseres katalysatormengden når det anvendes reformeringsrør av katalysert hardt materiale (hardware), sammenlignet med den konvensjonelle reformeringsinnretningen med et fiksert sjikt av reformeringskatalysator.
Fig. 1 viser forenden av et anlegg som produserer syngass. Råstoff 2 foroppvarmes, avsvovles i enhet 4, blandes med prosessdamp 6 og oppvarmes ytterligere før det trer inn i en adiabatisk pre-reformeringsinnretning 8. Effluentstrømmen fra pre-reformeringsinnretningen 8 oppvarmes ytterligere i en krets anordnet i avgasskanal 12 og sendes til rørformet reformeringsinnretning 14, hvor omdanningen av metan til hydrogen, karbonmonoksyd og karbondioksyd finner sted. Bearbeidelsen av effluentgass nedstrøm for den rørformede reformeringsinnretningen avhenger av anvendelsen av produktet.
Katalysert hardt materiale (hardware) kan anvendes i to av enhetene vist i fig. 1:
1. I foroppvarmerspolen 10 for oppvarming av pre-reformeringsinnretning-effluent gass før den trer inn i den rørformede reformeringsinnretningen 14.
2. I rørformet reformeringsinnretning 14.
Nedenfor er resultatene oppnådd for anlegget i fig. 1 presentert når katalysert hardt materiale anvendes i de to ovenfor nevnte enhetene. Katalysatoren anvendt for det katalyserte harde materialet er R-67R nikkeldamp-reformeringskatalysator tilgjengelig fra Haldor Topsøe A/S. Resultatene er sammenlignet med det konvensjonelle tilfellet. Formålet med foroppvarmerspolen er å anvende varmeinnholdet i avgassen for foroppvarming av prosessgassen før den trer inn i den rørformede reformeringsinnretningen. Avgassen anvendes for foroppvarming av prosessgass og for foroppvarming av for-brenningsluften for den rørformede reformeringsinnretningen (ikke vist i fig. 1). Imidlertid er varmeinnholdet av avgassen større enn det som kan anvendes for disse formålene og den gjenværende varmen anvendes for dampproduksjon. Det vil være en fordel dersom en større mengde av varmeinnholdet i avgassen kan overføres til prosessgassen. Dette vil redusere den nødvendige mengden brennstoff i den rørformede reformeringsinnretningen, og det vil redusere størrelsen av reformeringsinnretningen, idet en mindre mengde varme må overføres i enheten.
Den konvensjonelle foroppvarmingsinnretningen er begrenset ved faren for karbon-dannelse ved dekomponering av metan. Dette setter en øvre grense for rørvegg-temperaturen, som kan aksepteres. Fiksering av et lag av katalysert hardt materiale på den indre rørveggen 6 av foroppvarmerspolen 10 (som vist i fig. 2) resulterer i en reduksjon av både rørveggtemperaturen og prosessgasstemperaturen. Dette muliggjør overføringen av en høyere belastning i spolen uten at man får en høyere rørtemperatur.
Foroppvarmerspolen anvendt i beregningene består av 8 rør hvori prosessgassen strømmer inne i rørene. Avgassen flyter på den ytre siden. Strømningsmønsteret er tverrstrøm/samstrøm. Fig. 2 viser utformingen for ett rør. De to tilfellene med og uten katalysert hardt materiale er sammenfattet i tabell 1. Det er åpenbart at den overførte effekten (varmeenergi) er 49 % høyere i tilfelle med katalysert hardt materiale, sammenlignet med det konvensjonelle tilfellet. Tykkelsen av katalysatorlaget i tilfelle med det harde katalysatormaterialet er 1,0 mm.
Den effektive rørlengden er lengden av røret inne i avgasskanalen.
Den konvensjonelle rørformede reformeringsinnretningen består av et antall rør som er fylt med katalysatorpellets. Prosessgassen strømmer inne i rørene. Rørene er plassert i en ovn som er oppvarmet ved forbrenning av et brennstoff.
I tilfelle med det katalyserte harde materialet erstattes rørene fylt med katalysatorpellets med et antall rør med et lag av katalysert hardt materiale på innerveggen. Katalysator-lagtykkelsen er 0,25 mm. En ytterligere adiabatisk reformeringsreaktor med fiksert sjikt er plassert nedstrøm for den rørformede reaktoren, siden omdanningen av metan i den rørformede reformeringsinnretningen med katalysert hardt materiale er underlegen det konvensjonelle tilfellet. Denne reaktoren betegnes post-reformeringsinnretning. Katalysatoren anvendt i post-reformeringsinnretningen er RKS-2 nikkel-dampreformeringskatalysatoren tilgjengelig fra Haldor Topsøe A/S.
De to tilfellene er sammenfattet i tabell 2. Det fremgår at katalysatorforbruket reduseres med en faktor 11,5, og at materialforbruket for rørene i den rørformede reformeringsinnretningen er redusert 24 % i tilfelle med katalysert hardt materiale, sammenlignet med det konvensjonelle tilfellet.
Et flytskjema for en prosess ifølge oppfinnelsen er vist i fig. 3. Tallene i trekantene refererer til tabellen nedenfor, hvori samlede tall for prosessen er sammenlignet. Brennstoff-forbruket reduseres med 7,4 % i tilfelle med katalysert hardt materiale, sammenlignet med det konvensjonelle tilfellet.

Claims (3)

1. Fremgangsmåte for fremstillingen av hydrogen og karbonmonoksydrik syntesegass ved dampreformering av et hydrokarbonråstoff i nærvær av en dampreformeringskatalysator båret som en tynn film på en rørformet reaktor, karakterisert ved at den innbefatter trinnene (a) føring av en prosessgass av prereformert hydrokarbon gjennom en rørformet reaktor som er utstyrt med en tynn film av dampreformeringskatalysatoren og som oppvarmes ved brenning av brennstoff, slik at det derved oppnås en partielt dampreformert gasseffluent og en varm avgass; (b) føring av effluenten fra den rørformede reaktoren til en dampreformeringskatalysator med fiksert sjikt; og (c) fjerning fra det fikserte sjiktet av en produktgass av hydrogen og karbonmonoksydrik syntesegass.
2. Fremgangsmåte ifølge krav 1, karakterisert ved at den før trinn (a) omfatter det ytterligere trinnet med at prosessgass av prereformert hydrokarbon føres gjennom en rørformet reaktor med en tynn film av dampreformeringskatalysator båret på en vegg av reaktoren i varmeledende relasjon med den varme avgassen fra det etterfølgende prosesstrinn (a).
3. Fremgangsmåte ifølge krav 1, karakterisert ved at fiksert sjikt-dampreformeirngskatalysatoren opereres ved adiabatisk tilstand. FiOTgangsmåte ifølge kravl, karakterisert ved at dampreformeringskatalysator, innbefatter nikkel og/eller ruthenium.
NO19980274A 1997-01-22 1998-01-21 Fremgangsmate for fremstilling av syntesegass ved dampreformering ved anvendelse av katalysert materiale NO318107B1 (no)

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CA2227598A1 (en) 1998-07-22
CA2227598C (en) 2007-09-11
UA61888C2 (uk) 2003-12-15
KR100547540B1 (ko) 2006-03-23
EP0855366A1 (en) 1998-07-29
DE69800734D1 (de) 2001-06-07
TW482741B (en) 2002-04-11
ATE200884T1 (de) 2001-05-15
ES2158621T3 (es) 2001-09-01
CN1196330A (zh) 1998-10-21
DK0855366T3 (da) 2001-08-13
JP4521735B2 (ja) 2010-08-11
RU2218301C2 (ru) 2003-12-10
NZ329613A (en) 1998-11-25
AU5215898A (en) 1998-07-30
JPH10297904A (ja) 1998-11-10
AU728728C (en) 2001-08-30
KR19980070692A (ko) 1998-10-26
AU728728B2 (en) 2001-01-18
DE69800734T2 (de) 2001-08-09
NO980274L (no) 1998-07-23
EP0855366B1 (en) 2001-05-02
US5932141A (en) 1999-08-03
NO980274D0 (no) 1998-01-21
CN1269724C (zh) 2006-08-16

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