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DK174087B1 - Fremgangsmåde til dampreforming af nitrogenholdige carbonhydrider med reduceret dannelse af ammoniak - Google Patents

Fremgangsmåde til dampreforming af nitrogenholdige carbonhydrider med reduceret dannelse af ammoniak Download PDF

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DK174087B1
DK174087B1 DK199300974A DK97493A DK174087B1 DK 174087 B1 DK174087 B1 DK 174087B1 DK 199300974 A DK199300974 A DK 199300974A DK 97493 A DK97493 A DK 97493A DK 174087 B1 DK174087 B1 DK 174087B1
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catalyst
nickel
steam reforming
copper
ammonia
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DK97493A (da
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Jens-Henrik Bak Hansen
Leif Storgaard
Poul Erik Jensen
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Topsoe Haldor As
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Priority to DK199300974A priority Critical patent/DK174087B1/da
Priority to ES94111699T priority patent/ES2111811T3/es
Priority to DE69407692T priority patent/DE69407692T2/de
Priority to EP94111699A priority patent/EP0640560B1/en
Priority to US08/295,285 priority patent/US5498404A/en
Priority to AU71473/94A priority patent/AU673451B2/en
Priority to NZ264308A priority patent/NZ264308A/en
Priority to NO19943145A priority patent/NO311207B1/no
Priority to CA002130953A priority patent/CA2130953C/en
Priority to JP6202443A priority patent/JP2958242B2/ja
Priority to KR1019940021186A priority patent/KR0124987B1/ko
Priority to RU94031156A priority patent/RU2132228C1/ru
Priority to ZA946517A priority patent/ZA946517B/xx
Publication of DK97493A publication Critical patent/DK97493A/da
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • C01B3/34Production 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
    • C01B3/38Production 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
    • C01B3/40Production 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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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005Arrangement or shape of catalyst
    • C01B2203/1011Packed bed of catalytic structures, e.g. particles, packing elements
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    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Description

- i - DK 174087 B1
Den foreliggende opfindelse angår fremstilling af hydrogen- og/eller carbonmonoxidrige gasser ved dampreform-ing af nitrogenholdige carbonhydrider med reduceret dannelse af ammoniak og nærmere bestemt anvendelse af nye 5 nikkelholdige reformingkatalysatorer ved en sådan proces.
Ved de kendte fremgangsmåder til fremstilling af hydrogen- og/eller carbonmonoxidrige gasser sendes en blanding af carbonhydridføde og damp og/eller carbondioxid ved høj temperatur og tryk gennem en reaktor, der er for-10 synet med et katalysatorleje med nikkel som dets aktive katalytiske materiale.
Carbonhydridfødemateriale, der egner sig til damp-reforming indbefatter naturgas, raffinaderiafgasser, propan, nafta, og flydendegjort petroleumgas. Ved eksempelvis is reforming af metan er reaktionerne, der finder sted repræsenteret ved følgende ligninger: (1) CH4 + HaO - CO + 3H2 (2) CH4 + C02 -* 2CO + 2H2 20 (3) CO + H20 C02 + H2
Produceret rågas fra dampreformingreaktoren behandles konventionelt ved kondensation og væske-gas faseseparation i et efterfølgende procestrin. Flydende proceskonden-25 sat består hovedsagelig af vand og sendes tilbage til dampreforming gennem en dampkedel.
Før kondensatet ledes til kedlen har det i mange fabrikker været behandlet til fjernelse af vandopløselige forbindelser og salte. Til dette formål sendes kondensatet 30 gennem en demineral i seringsenhed med ion-bytterharpikser.
Rensning af proceskondensatet, specielt kondensat fra dampreforming af et fødemateriale med et højt nitrogenindhold såsom naturgas fra bestemte områder, er problematisk ved konventionel dampreforming.
DK 174087 B1 - 2 -
Nitrogen i fødematerialet reagerer med hydrogen til ammoniak når det passerer gennem et nikkeldampreforming-katalysatorleje ved følgende reaktion: 5 - (4) Na + 3H2 6 2NH3
Ammoniak i den rå produktgas overgår næsten kvantitativt til proceskondensatet. Ammoniakmængder op til 300 dele pr. million er ikke usædvanligt i kondensatet fra 10 dampreforming af naturgas.
Sådanne høje ammoniakkoncentrationer kræver en hyppig regenerering eller fornyelse af dyrt ion-bytterma-teriale, der anvendes til demineralisering af kondensatet, hvilket i sig selv giver anledning til problemer ved drif-15 ten af dampreformingprocessen.
Det er således formålet med den foreliggende opfindelse, at forhindre ammoniakdannelse under dampreforming af carbonhydrider uden negativt at indvirke på den samlede proceseffektivitet.
20 Vi har observeret, at tilsætning af kobber til nikkeldampreformingkatalysatorer i høj grad formindsker dannelse af ammoniak. Selvom kobber nedsætter katalysatorernes aktivitet er disse stadig tilstrækkelig effektive ved dampreforming af carbonhydrider.
25 Baseret på denne observation angår opfindelsen en fremgangsmåde til katalytisk dampreforming af et nitrogen-holdigt carbonhydridfødemateriale med formindsket dannelse af ammoniak, hvilken fremgangsmåde er ejendommelig ved, at den omfatter et trin, hvor fødematerialet bringes i kontakt 30 med en båren nikkelkatalysator, som yderligere indeholder kobber i mængder på 0,01-10,0 vægt% beregnet på mængden af nikkel i katalysatoren.
Kobberholdige nikkelkatalysatorer til anvendelse ved fremgangsmåden kan fremstilles ved en hvilken som helst 35 af de konventionelle metoder. De kendte metoder omfatter i" - 3 - DK 174087 B1 imprægnering af et keramisk bæremateriale med en vandig opløsning af nikkel- og kobbersalte og kalcinering af det imprægnerede materiale i luft.
Andre metoder omfatter sammenfældning af opløselige 5 salte af bæremateriale, nikkel og kobber. Egnede salte er klorider, nitrater, carbonater, acetater og oxalater, som ved opvarmning i luft danner de ønskede metaloxider.
Egnet bæremateriale findes blandt oxiderne af aluminium, magnesium, titan, silicium, zirkonium, berylium, io torium, lantanium, kalcium og forbindelser og blandinger deraf. Foretrukne materialer er oxiderne af aluminium eller magnesium aluminium spinel.
De mængder kobber, der aktuelt inkorporeres i katalysatoren er afhængig af nitrogenindholdet i fødematerialet 15 og mængden af ammoniak, der kan tolereres i proceskondensatet. Kobberkoncentrationer på mellem 0,1 og 0,5 vægt% beregnet på katalysatorens samlede vægt er i de fleste tilfælde tilstrækkelige for at kunne undertrykke ammoniakdannelse og fører til ammoniakkoncentrationer under 50 ppm 20 i proceskondensatet.
Nikkel-kobberkatalysatorerne er almindeligvis anbragt som fast leje i en rørreformingreaktor. Afhængig af nitrogenindholdet i fødematerialet og den acceptable ammoniakkoncentration kan det være tilstrækkeligt, at an-25 bringe katalysatorerne som et lag i et fast leje af en konventionelt nikkeldampreforming katalysator. Dette lag kan udgøre mellem 25 og 75% af det samlede katalysatorleje.
Opfindelsen beskrives nærmere ved hjælp af de følgende Eksempler.
30
Eksempel 1
En serie nikkel-kobberkatalysatorer indeholdende 15 vægt% nikkel og forskellige mængder kobber blev fremstillet ved imprægnering af en spinelbærer (MgAl204) med en t - 4 - DK 174087 B1 vandig opløsning af nikkel- og kobbernitrat. Den imprægnerede bærer kalcineredes afslutningsvis i luft, hvorved nitraterne dekomponerede til oxiderne.
Katalysatorerne blev anbragt i en reaktor og akti-5 veret ved opvarmning til 800°C i en blanding af lige dele damp og hydrogen ved atmosfærisk tryk. Under aktiveringen reduceredes nikkeloxiderne og kobberoxiderne på bæreren til deres metalliske form. Temperaturen opretholdes ved 800°C i yderligere 150 timer for at tillade sintring af katalysa-10 torerne, hvilket er tilfældet ved industriel anvendelse.
Efter aktivering og sintring fjernedes katalysatorerne fra reaktoren og nedknustes til mindre partikler før en aktivitetsbestemmelse ved metandampreforming og en bestemmelse af ammoniakdannelse gennemførtes under følgende 15 betingelser: metan damp ammoniak reforming dannelse
Katalysator, mmpartikftelseøS-r^lieO. 5
Katalysator mængde, mg 30,0-50,0 1000,0
Temperatur, EC 400-650 650-750 Fødegas sammensætning, Nl/h CH4 4,0 0,0 H20 16,0 16,0 H2 1,6 30,0 N2 0,0 10,0
De ved 650EC opnåede aktiviteter er vist i Tabel 1.
/ 1 · DK 174087 B1 - 5 -
Tabel 1
Aktivitet ved 650EC.
Relativ Aktivitet 100*Cu/Ni Metan Damprefor- Ammoniakdannelse vægt/vægt ming
Kat. 1 0,00 100__100_
Kat. 2 0,20 77__59_
Kat. 3 0,67 72 44_
Kat. 4 1,33__70__28_
Kat. 5 3,33 50 11_
Selvom katalysatorpartikkelstørrelsen var lille, er dampreformingreaktionen begrænset af diffusionsrestriktio-5 ner ved 650°C. Aktiviteterne, der er opført i Tabel 1, er derfor beregnet ved ekstrapolation af aktiviteter, der er opnået ved lavere temperaturer ved hjælp af den velkendte Arrhenius graf.
ίο Eksempel 2
Katalysator 1 og katalysator 5 som beskrevet i Eksempel 1, blev yderligere prøvet ved metandampreforming i større målestok. Reaktoren kørtes med nedadgående gennemstrømning ved forhøjet tryk for at simulere industrielle is driftsbetingelser.
Katalysatorerne blev anbragt som bundlag i et lagdelt katalysatorleje. Bundlaget udgjorde 75% af lejet.
25% toplag var i begge undersøgelser ladet med konventionelt nikkeldampreformingkatalysator R-67R, som forhandles 20 af Haldor Topsøe A/S.
Undersøgelserne blev udført under følgende betingelser: - 6 - DK 174087 B1
Katalysator
Partikkelstørrelse mm 3,4-5,0
Katalysator mængde g 95,0
Temp, ind/ud EC 500/865
Tryk bar 18,6 Fødegas sammensætning, Nl/h CH4 109,0 ‘ H20 325,0 H2 2,5 N2 3,7 Mængden af ammoniak, der dannes ved undersøgelserne 5 er opstillet i Tabel 2 forneden. Ydeevnen af de to forskellige katalysatorer var den samme.
Tabel 2
Ammoniakdannelse ved metandampreforming i større målestok.
Ammoniak i proceskondensat vægt ppm Driftstimer Nikkelkatalysator Kobber/Nikkel
Katalysator 20 325 Ϊ40 Ϊ00 “ 3Ϊ0 ΪΟ0 200 230 85 300 255 75 ~ 400 235 70 450 230 65

Claims (4)

1. Fremgangsmåde til katalytisk dampreforming af et nitrogenholdig carbonhydridfødemateriale med reduceret 5 dannelse af ammoniak, kendetegnet ved, at den omfatter et trin til at bringe fødematerialet i kontakt med en båren nikkelkatalysator som yderligere indeholder kobber i en mængde på mellem 0,01-10,0 vægt% beregnet på nikkelmængden i katalysatoren. 10
2. Fremgangsmåde ifølge krav 1, kendetegnet ved, at nikkelmængden i katalysatoren ligger på 0,03-0,5 vægt% beregnet på katalysatorens samlede vægt. 15
3. Fremgangsmåde ifølge krav 1, kendetegnet ved, at den kobberholdige nikkelkatalysator er anbragt som et lag i et fast leje med en konventionel nikkeldampreforming katalysator. 20
4. Fremgangsmåde ifølge krav 3, kendetegnet ved, at laget udgør på mellem 25-75% af det samlede katalysator lejet.
DK199300974A 1993-08-27 1993-08-27 Fremgangsmåde til dampreforming af nitrogenholdige carbonhydrider med reduceret dannelse af ammoniak DK174087B1 (da)

Priority Applications (13)

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
ES94111699T ES2111811T3 (es) 1993-08-27 1994-07-27 Utilizacion de un catalizador soportado de niquel en la reformacion por vapor.
DE69407692T DE69407692T2 (de) 1993-08-27 1994-07-27 Benutzung eines Nickelträgerkatalysators zur Dampfreformierung
EP94111699A EP0640560B1 (en) 1993-08-27 1994-07-27 Use of supported nickel catalyst in steam reforming
US08/295,285 US5498404A (en) 1993-08-27 1994-08-24 Process for the steam reforming of hydrocarbons
NZ264308A NZ264308A (en) 1993-08-27 1994-08-25 Steam-reforming of hydrocarbons using a copper-containing nickel catalyst
AU71473/94A AU673451B2 (en) 1993-08-27 1994-08-25 Process for the steam reforming of hydrocarbons
NO19943145A NO311207B1 (no) 1993-08-27 1994-08-25 Fremgangsmåte for katalytisk dampreformering av nitrogeninneholdende hydrokarboner
CA002130953A CA2130953C (en) 1993-08-27 1994-08-26 Process for the steam reforming of hydrocarbons
JP6202443A JP2958242B2 (ja) 1993-08-27 1994-08-26 炭化水素の水蒸気改質方法
KR1019940021186A KR0124987B1 (ko) 1993-08-27 1994-08-26 탄화수소의 증기 개질방법
RU94031156A RU2132228C1 (ru) 1993-08-27 1994-08-26 Никелевый катализатор на носителе для получения богатого водородом и/или моноокисью углерода газа и способ получения указанного газа
ZA946517A ZA946517B (en) 1993-08-27 1994-08-26 Process for the steam reforming of hydrocarbons

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DK97493 1993-08-27
DK199300974A DK174087B1 (da) 1993-08-27 1993-08-27 Fremgangsmåde til dampreforming af nitrogenholdige carbonhydrider med reduceret dannelse af ammoniak

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DK97493A DK97493A (da) 1995-02-28
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AU (1) AU673451B2 (da)
CA (1) CA2130953C (da)
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EP1013603A1 (en) 1998-12-22 2000-06-28 Haldor Topsoe A/S Process for catalytical steam reforming of a hydrocarbon feedstock
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
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
CA2511039A1 (en) * 2002-12-20 2004-07-15 Honda Giken Kogyo Kabashiki Kaisha Platinum-alkali/alkaline-earth catalyst formulations for hydrogen generation
US7160533B2 (en) * 2002-12-20 2007-01-09 Honda Giken Kogyo Kabushiki Kaisha Platinum-ruthenium containing catalyst formulations for hydrogen generation
WO2004058396A2 (en) * 2002-12-20 2004-07-15 Honda Giken Kogyo Kabushiki Kaisha Methods for the preparation of catalysts for hydrogen generation
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DE69407692D1 (de) 1998-02-12
US5498404A (en) 1996-03-12
CA2130953C (en) 2002-07-30
RU94031156A (ru) 1996-08-20
ES2111811T3 (es) 1998-03-16
NZ264308A (en) 1996-03-26
KR950005962A (ko) 1995-03-20
JPH07144902A (ja) 1995-06-06
KR0124987B1 (ko) 1997-11-27
EP0640560A1 (en) 1995-03-01
EP0640560B1 (en) 1998-01-07
JP2958242B2 (ja) 1999-10-06
ZA946517B (en) 1995-03-28
AU673451B2 (en) 1996-11-07
NO311207B1 (no) 2001-10-29
DK97493D0 (da) 1993-08-27
AU7147394A (en) 1995-03-09
RU2132228C1 (ru) 1999-06-27

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