DK3155074T3 - Fremgangsmåde til hydrogenbehandling af dieselfraktioner under anvendelse af en katalysator baseret på amorft, mesoporøst aluminiumoxid med høj konnektivitet - Google Patents

Fremgangsmåde til hydrogenbehandling af dieselfraktioner under anvendelse af en katalysator baseret på amorft, mesoporøst aluminiumoxid med høj konnektivitet Download PDF

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DK3155074T3
DK3155074T3 DK15730989.9T DK15730989T DK3155074T3 DK 3155074 T3 DK3155074 T3 DK 3155074T3 DK 15730989 T DK15730989 T DK 15730989T DK 3155074 T3 DK3155074 T3 DK 3155074T3
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catalyst
volume
alumina
acid
pores
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DK15730989.9T
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Malika Boualleg
Elodie Devers
Bertrand Guichard
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Ifp Energies Now
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    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
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Claims (14)

1. Fremgangsmåde til hydrogenbehandling af mindst en dieselfraktion fra mindst en dieselfraktion med en vægtet middeltemperatur på mellem 240 °C og 350 °C, foregående ved en temperatur på mellem 250 °C og 400 °C, ved et totalt tryk på mellem 2 MPa og 10 MPa, med et volumenforhold hydrogen pr. volumen carbonhydridføde på mellem 100 og 800 liter pr. liter og ved en rumhastighed, defineret som forholdet mellem volumenstrømmen af flydende carbonhydridføde og volumenet af katalysator påfyldt i reaktoren, på mellem 1 og 10 h_1, hvilken fremgangsmåde anvender mindst en katalysator, som omfatter mindst et metal fra gruppe VIB og/eller mindst et metal fra gruppe VIII i det periodiske system og en bærer, der omfatter et amorft, mesoporøst aluminiumoxid, hvilken fremgangsmåde omfatter mindst følgende trin til fremstilling af aluminiumoxidet: a) mindst et første trin a) til udfældning af aluminiumoxidet i et vandigt reaktionsmedie ud fra mindst en basisk precursor valgt blandt natriumaluminat, kaliumaluminat, ammoniak, natriumhydroxid og kaliumhydroxid, og mindst en sur precursor valgt blandt aluminiumsulfat, aluminiumchlorid, aluminiumnitrat, svovlsyre, saltsyre og salpetersyre, hvor mindst en af de basiske eller sure precursorer omfatter aluminium, idet den relative strømningshastighed af de sure og basiske precursorer er således valgt, at der opnås et pH af reaktionsmediet på mellem 8,5 og 10,5, og idet strømningshastigheden af den eller de sure og basiske precursorer indeholdende aluminium er således indstillet, at der opnås en reaktionsgrad i det første trin på mellem 40 og 100%, hvor reaktionsgraden er defineret som forholdet mellem dannet aluminiumoxid som Al2C>3-ækvivalenter i udfældningstrinnet a) og den totale mængde aluminiumoxid, der er dannet i udgangen af udfældningstrinnet eller udfældningstrinnene, hvor trinnet a) foregår ved en temperatur på mellem 10 og 50 °C og i et tidsrum på mellem 2 minutter og 30 minutter, b) et trin til varmebehandling af suspensionen, der er opnået i udgangen af trin a) , ved en temperatur på mellem 50 og 200 °C i et tidsrum på mellem 30 minutter og 5 timer, hvorved der opnås en aluminiumoxidgel, c) et trin til filtrering af suspensionen, der er opnået i udgangen af varmebehandlingstrinnet b) , efterfulgt af mindst et trin til vask af den opnåede gel, d) et trin til tørring af aluminiumoxidgelen, der er opnået i udgangen af trin c), for at opnå et pulver, e) et trin til formgivning af pulveret, der er opnået i udgangen af trin d), for at opnå et råmateriale, f) et trin til varmebehandling af råmaterialet, der er opnået i udgangen af trin e) , ved en temperatur på mellem 500 og 1000 °C i nærvær eller ej af en luftstrøm indeholdende op til 60 volumen-% vand.
2. Fremgangsmåde ifølge krav 1, hvor den anvendte dieselfraktion er valgt blandt dieselfraktionerne, der stammer fra direkte destillation alene eller i blanding med mindst en fraktion, der stammer fra en forkoksningsenhed, eller mindst en fraktion, der stammer fra katalytisk krakning, eller mindst en dieselfraktion, der hidrører fra andre omdannelsesfremgangsmåder, såsom mild hydrokrakning eller hydrogenbehandling af restprodukter.
3. Fremgangsmåde ifølge et af kravene 1 eller 2, hvor grundstofferne fra gruppe VIII er valgt blandt cobalt og nikkel taget alene eller i blanding.
4. Fremgangsmåde ifølge et af kravene 1 til 3, hvor grundstofferne fra gruppe VIB er valgt blandt wolfram og molybden taget alene eller i blanding.
5. Fremgangsmåde ifølge et af kravene 1 til 4, hvor koncentrationen af metal fra gruppe VIB ligger på mellem 10 og 35 vægt-% oxid i forhold til den totale masse af katalysatoren, og koncentrationen af ikke-ædelmetal fra gruppe VIII ligger på mellem 1 og 10 vægt-% oxid i forhold til den totale masse af katalysatoren, i det tilfælde hvor katalysatoren omfatter mindst et metal fra gruppe VIB i kombination med mindst et ikke-ædelmetal fra gruppe VIII.
6. Fremgangsmåde ifølge et af kravene 1 til 5, hvor katalysatoren indeholder mindst et doteringsgrundstof valgt blandt phosphor, bor, fluor og silicium, alene eller i blanding.
7. Fremgangsmåde ifølge krav 6, hvor koncentrationen af phosphor i katalysatoren ligger på mellem 0,5 og 15 vægt-% P2O5 ·
8. Fremgangsmåde ifølge et af kravene 1 til 7, hvor katalysatorens bærer omfatter et amorft, mesoporøst aluminiumoxid, som har en konnektivitet (Z) på mellem 3 og 7.
9. Fremgangsmåde ifølge et af kravene 1 til 8, hvor katalysatoren udviser en konnektivitet (Z) på mellem 3 og 7.
10. Fremgangsmåde ifølge et af kravene 1 til 9, hvor katalysatorens bærer udviser følgende porefordeling, målt ved kviksølvporosimetri: - procentdelen af volumenet, der er indeholdt i porer med en størrelse på mellem 2 og 6 nm, i forhold til det samlede porevolumen, ligger på mellem 1 og 25 %, - procentdelen af volumenet, der er indeholdt i porer med en størrelse på over 6 nm og under 15 nm, svarer til mellem 60 og 95 % af det samlede porevolumen, - procentdelen af volumenet, der er indeholdt i porer med en størrelse på mellem 15 og 50 nm, repræsenterer 0 til 8 % af det samlede porevolumen, og - procentdelen af volumenet, der er indeholdt i porer med en størrelse på mellem 50 og 7000 nm, svarende til det makroporøse volumen, repræsenterer 0 til 5 %.
11. Fremgangsmåde ifølge et af kravene 1 til 10, hvor bæreren udviser en middeldiameter af mesoporerne, målt ved kviksølvporosimetri og bestemt på volumenbasis, på mellem 7 og 12,5 nm.
12. Fremgangsmåde ifølge et af kravene 1 til 11, hvor bæreren udviser et volumen af mesoporerne, målt ved kviksølvporosimetri, på mellem 0,5 og 0,8 ml/g.
13. Fremgangsmåde ifølge et af kravene 1 til 12, hvor katalysatorens udviser følgende porefordeling, bestemt ved kviksølvporosimetri: - procentdelen af volumenet, der er indeholdt i porer med en størrelse på mellem 2 og 6 nm, i forhold til det samlede porevolumen, ligger på mellem 1 og 25 %, - procentdelen af volumenet, der er indeholdt i porer med en størrelse på over 6 nm og under 15 nm, svarer til mellem 60 og 95 % af det samlede porevolumen, - procentdelen af volumenet, der er indeholdt i porer med en størrelse på mellem 15 og 50 nm, repræsenterer 0 til 15 % af det samlede porevolumen, og - procentdelen af volumenet, der er indeholdt i porer med en størrelse på mellem 50 og 7000 nm, svarende til det makroporøse volumen, repræsenterer 0 til 5 % af det samlede porevolumen.
14. Fremgangsmåde ifølge et af kravene 1 til 13, hvor katalysatoren udviser et samlet porevolumen, målt ved kviksølvporosimetri, der er større end eller lig med 0,35 ml/g.
DK15730989.9T 2014-06-13 2015-06-09 Fremgangsmåde til hydrogenbehandling af dieselfraktioner under anvendelse af en katalysator baseret på amorft, mesoporøst aluminiumoxid med høj konnektivitet DK3155074T3 (da)

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