NO311207B1 - Fremgangsmåte for katalytisk dampreformering av nitrogeninneholdende hydrokarboner - Google Patents
Fremgangsmåte for katalytisk dampreformering av nitrogeninneholdende hydrokarboner Download PDFInfo
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- NO311207B1 NO311207B1 NO19943145A NO943145A NO311207B1 NO 311207 B1 NO311207 B1 NO 311207B1 NO 19943145 A NO19943145 A NO 19943145A NO 943145 A NO943145 A NO 943145A NO 311207 B1 NO311207 B1 NO 311207B1
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- Prior art keywords
- catalyst
- nickel
- copper
- steam reforming
- nitrogen
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- 238000000034 method Methods 0.000 title claims description 18
- 229930195733 hydrocarbon Natural products 0.000 title claims description 8
- -1 nitrogen-containing hydrocarbons Chemical class 0.000 title claims description 3
- 238000002407 reforming Methods 0.000 title description 5
- 230000003197 catalytic effect Effects 0.000 title description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- 238000000629 steam reforming Methods 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 238000001193 catalytic steam reforming Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000011021 bench scale process Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005115 demineralization Methods 0.000 description 2
- 230000002328 demineralizing effect Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—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
- C01B3/34—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
- C01B3/38—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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—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
- C01B3/34—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
- C01B3/38—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
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
- C01B2203/1017—Packed bed of catalytic structures, e.g. particles, packing elements characterised by the form of the structure
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- C—CHEMISTRY; METALLURGY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- C—CHEMISTRY; METALLURGY
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- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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- C01B2203/1241—Natural gas or methane
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- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1247—Higher hydrocarbons
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- General Health & Medical Sciences (AREA)
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Description
Foreliggende oppfinnelse angår produksjon av hydrogen og/elle-r karbonmonooksidrike gasser ved dampref ormer ing av hydrokarboner. Særlig angår foreliggende oppfinnelse en kobberinneholdende nikkelreformerende katalysator for anvendelse i dampreformering av et hydrokarbonråstoff.
I kjente fremgangsmåter for produksjon av hydrogen og/eller karbonmonoksidrike gasser, blir en blanding av hydrokarboner og damp og/eller karbondioksid ført ved forhøyet temperatur og trykk gjennom en reaktor pakket med en katalysator, hovedsakelig bestående av nikkel som den aktive katalytiske komponenten.
Dampreformeringskatalysatorer basert på nikkel og som omfatter kobber for forbedret dampreformeringsaktivitet er videre kjent fra BE-Å-676590 og GB-A-1032754.
Hydrdkarbonråstoffet som er velegnet for dampreformering er f.eks. naturgass, raffineringsavgasser, propan, nafta og vaeskedannede petroleumgasser. Ved å benytte metan som eksempel kan reaksjoner som foregår, være representert ved følgende ligninger:
Råproduktgassen som forlater dampreformeringsreaktoren blir konvensjonelt prosessert ved kondensasjon og væske-gass-faseseparasjonsbehandling etter dampreformering. Væske-prosesskondensatet, hovedsakelig bestående av vann, blir deretter resirkulert tilbake til dampreformeringsseksjonen via en koker for dampgenerering.
Før innføring i kokeren, blir kondensatet i mange anlegg gjenstand for fjerning av vannoppløselige forbindelser og salter. For dette formål blir kondensatet ført gjennom en demineraliseringsenhet som opererer typisk på ione-bytter-harpik&er.
Et hovedproblem ved konvensjonell dampreformeringsprosesser fremkommer under rensing av prosesskondensatet, særlig kondensåt fra dampref ormer ing av et råstoff med et høyt innhold av nitrogen, som naturgass fra visse felter.
Nitrogen som er inneholdt i råstoffer reagerer med hydrogen til ammoniakk i reaksjon:
når det passerer gjennom et sjikt av nikkeldampreformerende katalysator. Ammoniakk i råproduktgassen blir nesten kvantitativt fjernet i prosesskondensatet under prosessering av gassen. Mengder av ammoniakk opptil 300 ppm i prosesskondensatet er ikke uvanlig, når man prosesserer råproduktgassen fra dampreformering av naturgass.
Slike høye konsentrasjoner av ammoniakkbehov frekventerer regenerering eller fornyelse av kostbare ione-byttermate-rialer anvendt for demineralisering av prosesskondensat, som er uhensiktsmessig for operasjon av dampreformeringspro-sessen.
Det er således et hovedmål med oppfinnelsen å forhindre ammoniakkdannelse i dampreformering av hydrokarboner uten negativ påvirkning av samlet prosesseffekt.
Det er nå observert at inkludering av kobber i nikkeldampreformeringskatalysator reduserer i stor grad dannelse av uønsket ammoniakk i dampreformering av nltrogeninneholdende karbonråstoff. Selv om kobber minsker den katalytiske aktiviteten av nikkelkatalysatoren svakt, vil katalysatorene fremdeles skaffe tilveie tilstrekkelig effektiv aktivitet for dampreformering.
Basert-på observasjonen over, er en vid utførelsesform av oppfinnelsen, rettet mot en fremgangsmåte for katalytisk dampreformering av et nitrogeninneholdende hydrokarbonholdig råstoff med redusert dannelse av ammoniakk, der råstoffet er brakt i kontakt med en båret nikkelkatalysator som videre innbefatter kobber i en mengde på 0,1-10 vekt-# beregnet på mengde av nikkel i katalysatoren.
Kobberinneholdende nikkelkatalysatorer kan bli fremstilt ved en hvilken som helst av metodene som konvensjonelt blir anvendt innenfor fagområdet, inkludert impregnering av et brytende bæremateriale med en nikkel- og kobberinneholdende vandig oppløsning og kalsinering av det impregnerte mate-rialet i luft.
Ytterligere fremgangsmåter omfatter ko-utfelling av oppløse-lige salter av bærematerialet, nikkel og kobber. Egnede salter er klorider, nitrater, karbonater, acetater og oksalater, som ved oppvarming i luft danner oksider av metallene.
Bærematerialer blir hensiktsmessig valgt fra gruppen av aluminiumoksid, magnesiumoksid, titaniumoksid, silisiumoksid, zirkoniumoksid, berylliumoksid, thoriumoksid, lantaniumoksid,
kalsiumoksid og forbindelser eller blandinger av disse. Foretrukkede materialer omfatter aluminiumoksid eller magnesiumaluminiumspinell.
Den virkelige mengden kobber som er inkorporert i katalysatoren vil avhengig av innhold av nitrogen i råstoffet og av mengden ammoniakk som er tolerert i prosesskondensatet. Konsentrasjoner av kobber mellom 0,1-0,5 vekt-# beregnet på total katalysatorvekt skaffer vanligvis tilveie tilstrekkelig undertrykking av ammoniakkdannelse, og resulterer i ammo-niakkonsentrasjoner under 50 ppm i prosesskondensatet. Nikkel-kobberkatalysatorer blir typisk ordnet som fiksert sjikt i-, en rørformet ref ormeringsreaktor.
Avhengig av nitrogeninnhold i råstoffet og ammoniakkonsentra-sjon som kan tolereres i prosesskondensatet, kan være tilstrekkelig og ordne nikkel-kobberkatalysatorene som et underlåg i et fiksert sjikt av konvensjonell nikkeldamp-reformeringskatalysatoren. Nikkel-kobberkatalysatorlaget utgjør fortrinnsvis 25-7556 av katalysatorbed.
Oppfinnelsen vil bli ytterligere beskrevet i følgende eksempler.
Eksempel 1
Intrus. lonsaktivitet
En serie av nikkel/kobberkatalysatorprøver inneholder 15 vekt-# nikkel og inneholdende varierende innhold av kobber ble fremstilt ved impregnering av en spinellbærer (MgA1204) med vandige oppløsninger av blandede nikkel/kobbernitrat. Den impregnerte bæreren ble til slutt kalsinert i luft, hvorved nitratene dekomponeres til oksider.
Katalysatorene ble tilsatt til en reaktor og aktivert under oppvarming til 800°C i en strømmende blanding av like mengder
damp og hydrogen ved atmosfærisk trykk. Under aktivering ble nikkel/kobberoksidet på bæreren redusert til metallisk tilstand. Temperaturen ble holdt ved 800°C i ytterligere 150 timer for å tillate sintring av katalysatorene som under industriell operasjon.
Etter aktivering/sintring, ble katalysatorene fjernet fra reaktoren og knust til mindre partikkelstørrelse forut for bestemmelse av intrusjonsaktivitet for metandampreformering og for ammoniakksyntese under følgende betingelser:
Aktivitetene oppnådd ved 650°C er vist i tabell 1.
Til tross for liten katalysatorstørrelse, ble metandamprefor-mer ingsreaksj onen utsatt for diffusjonsrestriksjoner ved 650°C, og derfor ble aktiviteten gitt i tabell 1 oppnådd gjennom ekstrapolering av aktiviteter oppnådd ved lavere temperaturer ved hjelp av den velkjente Arrhenius-grafen.
Eksempel 2
Benk- skalatester
Katalysator 1 og katalysator 5 fremstilt som beskrevet i eksemplet over ble videre undersøkt i en metandampreformer-ende bénk-skalareaktor operert med nedstrøm ved forhøyet trykk som simulerer industriell operasjon.
Katalysatorene ble plassert i nedre 75$ av katalysator-sjiktet. Det 25$ øvre av katalysatorsj iktet ble i begge testene ladd med konvensjonell nikkeldampreformerende katalysator R-67R tilgjengelig fra Haldor Topsøe A/S, Danmark. Testene ble gjennomført ved betingelsene under:
Resultatene relatert til den observerte ammoniakkdannelsen er gitt i tabell 2. Yteevnen til de to ulike katalysatorene kunne ellers ikke skilles.
Claims (4)
1.
Fremgangsmåte for katalytisk dampreformering av et nitrogeninneholdende hydrokarbonholdig råstoff med redusert dannelse av ammoniakk, karakterisert ved at råstoffet blir brakt i kontakt med en båret nikkelkatalysator som videre innbefatter kobber i en mengde på 0,01-10 vekt-# beregnet på mengden av nikkel i katalysatoren.
2.
Fremgangsmåte ifølge krav 1, karakterisert ved at mengden av kobber i katalysatoren er mellom 0,03-0,50 vekt-# beregnet på total katalysatorvekt.
3.
Fremgangsmåte ifølge krav 1, karakterisert ved at den kobberinneholdende nikkelkatalysatoren er arrangert i et underlag i et fiksert sjikt av en konvensjonell nikkeldampreformeringskatalysator.
4.
Fremgangsmåte ifølge krav 3, karakterisert ved at underlaget utgjør mellom 25$ og 75$ av totalt katalysatorsj ikt.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK199300974A DK174087B1 (da) | 1993-08-27 | 1993-08-27 | Fremgangsmåde til dampreforming af nitrogenholdige carbonhydrider med reduceret dannelse af ammoniak |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO943145D0 NO943145D0 (no) | 1994-08-25 |
| NO943145L NO943145L (no) | 1995-02-28 |
| NO311207B1 true NO311207B1 (no) | 2001-10-29 |
Family
ID=8099599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO19943145A NO311207B1 (no) | 1993-08-27 | 1994-08-25 | Fremgangsmåte for katalytisk dampreformering av nitrogeninneholdende hydrokarboner |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5498404A (no) |
| EP (1) | EP0640560B1 (no) |
| JP (1) | JP2958242B2 (no) |
| KR (1) | KR0124987B1 (no) |
| AU (1) | AU673451B2 (no) |
| CA (1) | CA2130953C (no) |
| DE (1) | DE69407692T2 (no) |
| DK (1) | DK174087B1 (no) |
| ES (1) | ES2111811T3 (no) |
| NO (1) | NO311207B1 (no) |
| NZ (1) | NZ264308A (no) |
| RU (1) | RU2132228C1 (no) |
| ZA (1) | ZA946517B (no) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1013603A1 (en) * | 1998-12-22 | 2000-06-28 | Haldor Topsoe A/S | Process for catalytical steam reforming of a hydrocarbon feedstock |
| RU2161064C1 (ru) * | 1999-04-06 | 2000-12-27 | Институт катализа им. Г.К. Борескова Сибирского отделения РАН | Способ осуществления трехфазных каталитических процессов |
| FR2795339B1 (fr) * | 1999-06-24 | 2001-09-21 | Peugeot Citroen Automobiles Sa | Catalyseur et procede de reformage de l'ethanol ainsi que systeme de pile a combustible les utilisant |
| US6376114B1 (en) | 2000-05-30 | 2002-04-23 | Utc Fuel Cells, Llc | Reformate fuel treatment system for a fuel cell power plant |
| JP4568448B2 (ja) * | 2001-03-30 | 2010-10-27 | 出光興産株式会社 | 水素製造プラントおよび水素製造方法 |
| RU2241657C2 (ru) * | 2001-04-16 | 2004-12-10 | Открытое акционерное общество "Концерн Стирол" | Способ конверсии метана |
| CN1729050A (zh) * | 2002-12-20 | 2006-02-01 | 本田技研工业株式会社 | 用于氢产生的含铂－钌催化剂配方 |
| AU2003301060A1 (en) * | 2002-12-20 | 2004-07-22 | Honda Giken Kogyo Kabushiki Kaisha | Noble metal-free nickel catalyst formulations for hydrogen generation |
| CA2511016A1 (en) * | 2002-12-20 | 2004-07-15 | Honda Giken Kogyo Kabushiki Kaisha | Methods for the preparation of catalysts for hydrogen generation |
| CN1729141B (zh) * | 2002-12-20 | 2010-04-28 | 本田技研工业株式会社 | 用于氢产生的铂-碱金属/碱土金属催化剂配方 |
| CA2511019A1 (en) * | 2002-12-20 | 2004-07-15 | Honda Giken Kogyo Kabushiki Kaisha | Alkali-containing catalyst formulations for low and medium temperature hydrogen generation |
| AU2003297313A1 (en) * | 2002-12-20 | 2004-07-22 | Honda Giken Kogyo Kabushiki Kaisha | Platinum-free ruthenium-cobalt catalyst formulations for hydrogen generation |
| JP2006511427A (ja) * | 2002-12-20 | 2006-04-06 | 本田技研工業株式会社 | 白金およびロジウムおよび／または鉄を含有する水素生成用触媒配合物 |
| CA2511018A1 (en) * | 2002-12-20 | 2004-07-15 | Honda Giken Kogyo Kabushiki Kaisha | Catalyst formulations for hydrogen generation |
| EP1454671A1 (en) * | 2003-03-07 | 2004-09-08 | Karsten Pedersen | A catalyst for use in production of hydrogen by conversion of organic matter in water |
| JP4607715B2 (ja) * | 2005-09-06 | 2011-01-05 | 株式会社東芝 | 触媒及び触媒の製造方法 |
| JP4706857B2 (ja) * | 2006-05-30 | 2011-06-22 | 戸田工業株式会社 | 金属カルボニルを除去する触媒、水素を含む混合改質ガスを製造する方法、金属カルボニルを除去する方法、燃料電池システム |
| RU2418632C1 (ru) * | 2007-01-09 | 2011-05-20 | Мурата Мэньюфэкчуринг Ко., Лтд. | Катализатор углекислотного риформинга и способ его получения |
| US7695708B2 (en) * | 2007-03-26 | 2010-04-13 | Air Products And Chemicals, Inc. | Catalytic steam reforming with recycle |
| JP4665044B2 (ja) * | 2009-09-14 | 2011-04-06 | 株式会社東芝 | 燃料改質用触媒、改質器及び燃料電池システム |
| JP5812253B2 (ja) * | 2011-04-27 | 2015-11-11 | 戸田工業株式会社 | 炭化水素を分解する触媒及び燃料電池システム |
| WO2013042314A1 (ja) * | 2011-09-22 | 2013-03-28 | パナソニック株式会社 | 水素含有ガスの生成方法および燃料電池システムの運転方法 |
| EP3095760A1 (en) * | 2015-05-21 | 2016-11-23 | Casale SA | A method for increasing the capacity of an ammonia plant |
| RU2650495C1 (ru) * | 2017-05-22 | 2018-04-16 | Акционерное общество "Ангарский завод катализаторов и органического синтеза" (АО "АЗКиОС") | Катализатор для паровой конверсии углеводородов |
| WO2021175785A1 (en) * | 2020-03-03 | 2021-09-10 | Haldor Topsøe A/S | Process for the production of synthesis gas |
| GB202012614D0 (en) * | 2020-08-13 | 2020-09-30 | Johnson Matthey Plc | Steam reforming |
| GB202012613D0 (en) | 2020-08-13 | 2020-09-30 | Johnson Matthey Plc | Steam reforming |
| JP7695142B2 (ja) * | 2021-07-30 | 2025-06-18 | 三菱化工機株式会社 | 水素製造装置及び水素製造装置の運転方法 |
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| GB1032754A (en) * | 1962-12-17 | 1966-06-15 | Ici Ltd | Improvements in or relating to the steam reforming of hydrocarbons and catalysts therefor |
| GB1045616A (en) * | 1964-07-20 | 1966-10-12 | Gas Council | Improvements in or relating to the production of combustible gases |
| FR1433595A (fr) * | 1965-02-17 | 1966-04-01 | Azote Office Nat Ind | Perfectionnements aux catalyseurs de reformage des hydrocarbures pétroliers par la vapeur |
| US4000987A (en) * | 1973-02-03 | 1977-01-04 | Japan Gasoline Co., Ltd. | Low-temperature steam reforming process for hydrocarbons |
| US4000988A (en) * | 1973-06-20 | 1977-01-04 | Japan Gasoline Co., Ltd. | Low-temperature steam reforming process for hydrocarbons |
| US4073750A (en) * | 1976-05-20 | 1978-02-14 | Exxon Research & Engineering Co. | Method for preparing a highly dispersed supported nickel catalyst |
| GB8308343D0 (en) * | 1983-03-25 | 1983-05-05 | Ici Plc | Steam reforming |
| DK165946C (da) * | 1985-03-21 | 1993-07-05 | Haldor Topsoe As | Reformingproces under varmeudveksling og reaktor dertil |
| GB8728882D0 (en) * | 1987-12-10 | 1988-01-27 | Ici Plc | Hydrogen |
| US5026536A (en) * | 1988-12-20 | 1991-06-25 | Nippon Oil Co., Ltd. | Hydrogen production from hydrocarbon |
| JPH0312301A (ja) * | 1989-06-07 | 1991-01-21 | Mitsubishi Heavy Ind Ltd | メタノールの改質方法 |
| JP2659836B2 (ja) * | 1989-12-28 | 1997-09-30 | 三菱重工業株式会社 | メタノールの改質方法 |
| JP2738975B2 (ja) * | 1990-10-02 | 1998-04-08 | 三菱重工業株式会社 | メタノールの改質方法 |
| JP2851406B2 (ja) * | 1990-10-02 | 1999-01-27 | 三菱重工業株式会社 | メタノール改質用触媒 |
| JPH0567336A (ja) * | 1992-02-04 | 1993-03-19 | Brother Ind Ltd | 光記録媒体および光記録装置 |
-
1993
- 1993-08-27 DK DK199300974A patent/DK174087B1/da not_active IP Right Cessation
-
1994
- 1994-07-27 DE DE69407692T patent/DE69407692T2/de not_active Expired - Lifetime
- 1994-07-27 EP EP94111699A patent/EP0640560B1/en not_active Expired - Lifetime
- 1994-07-27 ES ES94111699T patent/ES2111811T3/es not_active Expired - Lifetime
- 1994-08-24 US US08/295,285 patent/US5498404A/en not_active Expired - Lifetime
- 1994-08-25 NO NO19943145A patent/NO311207B1/no not_active IP Right Cessation
- 1994-08-25 AU AU71473/94A patent/AU673451B2/en not_active Expired
- 1994-08-25 NZ NZ264308A patent/NZ264308A/en not_active IP Right Cessation
- 1994-08-26 CA CA002130953A patent/CA2130953C/en not_active Expired - Lifetime
- 1994-08-26 KR KR1019940021186A patent/KR0124987B1/ko not_active Expired - Lifetime
- 1994-08-26 JP JP6202443A patent/JP2958242B2/ja not_active Expired - Lifetime
- 1994-08-26 ZA ZA946517A patent/ZA946517B/xx unknown
- 1994-08-26 RU RU94031156A patent/RU2132228C1/ru active
Also Published As
| Publication number | Publication date |
|---|---|
| US5498404A (en) | 1996-03-12 |
| DE69407692T2 (de) | 1998-04-16 |
| EP0640560A1 (en) | 1995-03-01 |
| KR950005962A (ko) | 1995-03-20 |
| DE69407692D1 (de) | 1998-02-12 |
| JPH07144902A (ja) | 1995-06-06 |
| RU2132228C1 (ru) | 1999-06-27 |
| AU7147394A (en) | 1995-03-09 |
| DK174087B1 (da) | 2002-06-03 |
| EP0640560B1 (en) | 1998-01-07 |
| RU94031156A (ru) | 1996-08-20 |
| ES2111811T3 (es) | 1998-03-16 |
| KR0124987B1 (ko) | 1997-11-27 |
| CA2130953A1 (en) | 1995-02-28 |
| DK97493A (da) | 1995-02-28 |
| AU673451B2 (en) | 1996-11-07 |
| ZA946517B (en) | 1995-03-28 |
| JP2958242B2 (ja) | 1999-10-06 |
| NZ264308A (en) | 1996-03-26 |
| NO943145L (no) | 1995-02-28 |
| NO943145D0 (no) | 1994-08-25 |
| CA2130953C (en) | 2002-07-30 |
| DK97493D0 (da) | 1993-08-27 |
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| MK1K | Patent expired |