DK171701B1 - Fremgangsmåde til genvinding af brugt syrekatalysator fra alkylering af carbonhydrider - Google Patents

Fremgangsmåde til genvinding af brugt syrekatalysator fra alkylering af carbonhydrider Download PDF

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DK171701B1
DK171701B1 DK081393A DK81393A DK171701B1 DK 171701 B1 DK171701 B1 DK 171701B1 DK 081393 A DK081393 A DK 081393A DK 81393 A DK81393 A DK 81393A DK 171701 B1 DK171701 B1 DK 171701B1
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acid
tar
alkylation
catalyst
acid catalyst
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Sven Ivar Hommeltoft
Claus J H Jacobsen
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Topsoe Haldor As
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Priority to ES94109869T priority patent/ES2108338T3/es
Priority to EP94109869A priority patent/EP0633063B1/en
Priority to DE69405654T priority patent/DE69405654T2/de
Priority to RU94023252A priority patent/RU2122991C1/ru
Priority to US08/271,117 priority patent/US5457258A/en
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
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    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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Description

DK 171701 B1 - i -
Den foreliggende opfindelse angår en fremgangsmåde til genvinding af en syrekatalysator bestående af en fluor-ineret sulfonsyre fra tjære, der dannes ved alkylering af carbonhydrider og som indeholder værdifulde mængder af 5 brugt syrekatalysator.
Syrekatalyseret alkylering af alifatiske carbonhydrider med olefiniske carbonhydrider er en velkendt proces til fremstilling af benzinprodukter med højt oktan tal. Alkylering af alifatiske carbonhydrider gennemføres 10 almindeligvis i væskefase ved behandling af paraffiner med olefiner i nærvær af en stærk sur katalysator.
Konventionelt anvendte syrekatalysatorer i industrielle alkyleringsprocesser er hydrogenfluorid og svovlsyre .
15 Anvendelse af fluorinerede sulfonsyrer, som alky- leringskatalysatorer ved alkylering af alifatiske carbonhydrider med olefiner, er endvidere omtalt i europæisk patentansøgning nr. 433.954. Ved den i dette patentskrift omtalte proces omsættes en processtrøm indeholdende et 20 carbonhydridfødemateriale og et olefinisk alkyleringsmiddel i nærvær af en fluorineret sulfonsyrekatalysator i et fast leje af et polært kontaktmateriale. På kontaktmaterialet dannes en reaktionszone med den fluorinerede sulfonsyrekatalysator adsorberet indenfor et afgrænset område af kon-25 taktmaterialet. I reaktionszonen omsættes processtrømmen under alkyleringsbetingelser til en produktstrøm af alky-lerede carbonhydrider katalyseret af den adsorberede sulfonsyre .
Under alkyleringsrektionen flyttes syrekatalysa-30 toren og dermed reaktionszonen som et velafgrænset bånd mellem reaktorens ud- og indløb, efter indvirkningen af processtrømmen, der strømmer igennem og omsættes i reaktionszonen.
- 2 - DK 171701 B1
Under vandring på kontaktmaterialet bibeholder sulfonsyren sin katalytiske aktivitet i alt væsentligt uforandret, og syren er stadig lige katalytisk aktiv når reaktionszonen nærmer sig reaktorudgangen.
5 Det er muligt at genanvende syrekatalysatoren uden oparbejdning når syren nærmer sig reaktorudgangen ved at vende processtrømmens retning i alkyleringsreaktoren. Små mængder af syren fanges imidlertid løbende i et tjærebiprodukt, der dannes under sidereaktioner ved processen. Tjæren 10 absorberes ligesom syrekatalysatoren som et bevægeligt bånd på kontaktmaterialet i en zone ved siden af reaktionszonen. Det er således muligt at udlede tjæren fra reaktoren, så snart tjærebåndet når reaktorens udgang.
Selvom tjæren kun indeholder små mængder brugt 15 syrekatalysator er det ønskeligt at genvinde katalysatoren fra tjæren for at forbedre alkyleringsprocessens økonomi.
Konventionelle metoder, såsom destillation eller ekstraktion af syren direkte fra tjæren, er uvirksomme på grund af syrens kraftige binding til basiske bestanddele i 20 tjæren.
Det er således formålet med denne opfindelse at tilvejebringe en fremgangsmåde til mere effektiv genvinding af brugt syrekatalysator. Opfindelsen angår således en fremgangsmåde til genvinding af syrekatalysator bestående 25 af en fluorineret sulfonsyre fra tjære, der dannes ved alkylering af carbonhydrider og som indeholder værdifulde mængder af brugt syrekatalysator kendetegnet ved, at man behandler tjæren med hydrogen i nærvær af en katalysator omfattende en eller flere metaller fra gruppe VIII 30 i det periodiske system afsat på en syrebestandig bærer; og recirkulerer syrefasen i den således behandlede tjære til alkyleringsprocessen.
Nyttige hydrogeneringskatalysatorer til anvendelse ved genvinding af syrekatalysatorerne er især platin, 35 palladium eller blandinger deraf afsat på siliciumoxid, zeolitiske materialer eller aktiveret carbon.
- 3 - DK 171701 B1
Hydrogenering af tjæren vil i industrielle alkyler ingsenheder fortrinsvis blive udført i en omrørt beholder ved et hydrogen partialtryk på mellem 0,1 og 1,5 MPa og en temperatur på 20-300°C.
5 Alternativt kan hydrogenering gennemføres i konti nuert drevne fastleje reaktorer.
I de følgende eksempler hydrogeneres syretjære fra alkylering af isobutan med buten for at genvinde trifluor-metansulfonsyre (CF3S03H) , der anvendes som alkylerings-10 katalysator.
Eksempel 1
Sammensætningen af hydrogeneringskatalysatoren og reaktionsbetingelserne anvendt i dette Eksempel er opsum-15 meret i Tabel 1-3 forneden. En vejet mængde syretjære blev overført til en autoklave. Tjæren hydrogeneres og køles efter hydrogeneringen i en acetone i tørisblanding før autoklaven åbnes. Autoklaven skyldes grundigt med vand (5 gange med ca. 100 ml) for at ekstrahere syren. Mængden af 20 syre bestemmes herefter som anion ved hjælp af ion kromo-grafi.
En i alt væsentligt fuldstændig hydrogenering opnåedes ved 150°C og 3,2 MPa autogent tryk i løbet af 48 timer.
25 Som det fremgår af Tabel 2, er blandede palladium- og platinkatalysatorer mere aktive end katalysatorer, der indeholder disse to metaller separat. Høje hydrogenerings-hastigheder opnås ved at de blandede katalysatorer anvendes ved 200°C og 2,9 MPa tryk eller ved 150°C og 3,5 MPa, hvor 30 ca. 84% henholdsvis 82% af syren var genvundet i løbet af 24, henholdsvis 72 timer.
Indflydelse af hydrogenpartialtrykket undersøgtes ved at sammenligne resultater fra Tabel 2 og Tabel 3. Af disse resultater fremgår det, at reaktionshastigheden ikke 35 er begrænset af hydrogendiffusion i reaktionsblandingen ved de undersøgte temperaturer og tryk.
- 4 - DK 171701 B1
Ved en temperatur på 200°C og et hydrogentryk på 4,8 MPa i 24 timer var det således muligt at genvinde mere end 93% af den oprindelige syremængde i syretjæren.
- 5 - TABEL 1 DK 171701 B1 « Forsøg nr. 1 2 3 4 5 6 7 g katalysator 0.50g O.SOg 0.50g O.SOg 0.30 0.50 2%Pt/SiOj 2%Pt/SiOj 2%Pt/SiO, 2%Pt/SiO, 2%Pt/SiO, 2%Pt/SiO,
Syretjære 15ml 15ml 15ml 15ml 15ml 15ml T/"C 50 75 100 125 90 90 P/MPa 1,9 2,2 2,4 2,5 2,3 2,3 t/h IS 18 18 20 48 72
Omrøring + + + + + +
Br.No. § 34.9 37.8 24.5 24.5 11.4 27.4 27.1
Syre + 63% 64.3% 70.7% 69.2% 71.0% 66.4% 68.0% % H20 2.43 2.67 2.06 4.67 3.29 3.67 3.68
Syretjære start brom tal 46,3, CF3SO3H 61,3% vægt%, H20 2.20% vægt%.
§ : Bromtal + : Mængde CF3SO3H i hydratiseret tjære.
- 6 - TABEL 2 DK 171701 B1
Forsøg nr. 8 9 10 11 12 13 14 g kata- 0.50g,0.8% 0.50g,0.8% 0.50g,0.8% 0.50g,0.8% 0.50g,0.8% 0.50,0.8% 0.50,0.8% lysator Pd,0.2%Pt Pd.0.2%Pl Pd,0.2%Pt Pd,0.2%Pt Pd,0.2%Pt Pd,0.2%Pt Pd,0.2%Pt /SiO, /SiO, /SiOj /SiO, /SiO, /SiO, /SiO,
Syretjære 15ml 15ml 15ml 15ml 15ml 15ml 20ml/26.65g
Tre 80 125 150 75 200 150 200 P/MPa 2,1 2,5 2,8 2,0 2,9 3,9 4,8 t/h 18 18 18 18 24 72 18
Omrøring + + + + + + +
Br.No.§ 36.3 13.8 10.9 44.1 1.18 3.50
Syre + 65.3% 65.7% 68.2% 63.2% 84.1% 81.6% % H,0 3.05 3.65 3.77 2.76 3.21 6.02
Syretjære start brom tal 46,3, CF3S03H 61,3% vægt%, H20 2.20% vægt%.
§ : Bromtal + : Mængde CF3S03H i hydratiseret tjære.
- 7 - TABEL 3 DK 171701 B1
Forsøg nr. 15 16 g katalysator 0.50g,0.8% 0.50g,0.8%
Pd,0.2%Pt Pd,0.2%Pl /Si02 /Si02
Syretjære 15ml 15ml
TrC 125 100 P/MPa 7,8 7,3 t/h 20 18
Omrøring + +
Br.No. § 11.7 26.1
Syre + 63.8% 68.2% % HjO 4.30 3.18
Syretjære start brom tal 46,3, CF3S03H 61,3% vægt%, H20 2.20% vægt%.
§ : Bromtal + : Mængde CF3S03H i hydratiseret tjære.
- 8 - DK 171701 B1
Eksempel 2 50 ml syretjære hydrogeneredes i en 2 liter autoklave ved et starthydrogentryk på 1,8 MPa ved 25°C. Efter 18 timer ved 200°C køledes autoklaven. Da temperaturen nåede 45°C, bestemtes sammensætningen af carbonhydriderne i gasfasen ved gaskromatografi: propan 10 %(w/w) isobutan 54 %(w/w/) n-butan 5 %(w/w) isopentan 21 %(w/w) n-pentan l %(w/w) C6+ 9 %(w/w)
Efter yderligere køling var autoklaven ved normaltryk, og en væske dekanteredes fra autoklaven. En gasprøve, der blev taget over det dekanterede produkt, viste følgende indhold af organiske bestanddele: propan 5 %(w/w) isobutan 36 %(w/w) n-butan 4 %(w/w) isopentan 24 %(w/w) n-pentan 1 %(w/w) C6+ 30 %(w/w)
En lille mængde af en lettere og noget mere flygtig organisk fase kunne separeres fra en tungere syrefase. GC-MS analysen af denne lett.e organiske fase viste et indhold på ca. 50% monocykliske alkaner (substituerede cyklopenta-ner, cyklohexaner) og ca. 25% mono-aromater (substituerede benzener). 80% af prøven havde et kogepunkt under ca. 150°C og kun ca. 5% havde kogepunkt på over 200°C.
Syrefasen indeholdt ca. 15% organisk materiale.
- 9 - DK 171701 B1
For at undersøge den genvundne syres katalytiske aktivitet, anbragtes en 10 ml prøve af syrefasen i en 100 ml reaktor pakket med silika gel (Merck 100, 0,2-0,5 mm partikler) og en carbonhydrid fødestrøm indeholdende 5% (w/w) 2-buten i isobutan (samlet strøm: 150 g/hr) ledtes gennem reaktoren. 2-buteri omdannedes kvantitativt til alkylat. Alkylatets sammensætning analyseredes ved hjælp af gaskromografi. Baseret på sammensætning af forskellige prøver, der opnåedes ved en temperatur på mellem 0°C og 30°C beregnedes oktantallene i disse prøver som er opstillet i Tabel 4 forneden.
TABEL 4
TEMPERATUR RON MON
°C ___ _30__93__91 _25__94__92 _20__95__92 _15_;__96__93 _10__97__94 _5__97__94 _0__98__95

Claims (1)

1. Fremgangsmåde til genvinding af en syrekatalysator bestående af en fluorineret sulfonsyre fra tjære, der 5 dannes ved alkylering af carbonhydrider og som indeholder værdifulde mængder af brugt syrekatalysator kendetegnet ved, at man behandler tjæren med hydrogen i nærvær af en katalysator omfattende en eller flere metaller fra gruppe VIII 10 i det periodiske system afsat på en syrebestandig bærer; og recirkulerer syrefasen i den således behandlede tjære til alkyleringsprocessen.
DK081393A 1993-07-06 1993-07-06 Fremgangsmåde til genvinding af brugt syrekatalysator fra alkylering af carbonhydrider DK171701B1 (da)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DK081393A DK171701B1 (da) 1993-07-06 1993-07-06 Fremgangsmåde til genvinding af brugt syrekatalysator fra alkylering af carbonhydrider
ES94109869T ES2108338T3 (es) 1993-07-06 1994-06-27 Recuperacion de catalizador acido agotado procedente de la alquilacion de hidrocarburos.
EP94109869A EP0633063B1 (en) 1993-07-06 1994-06-27 Recovery of spent acid catalyst from alkylation of hydrocarbons
DE69405654T DE69405654T2 (de) 1993-07-06 1994-06-27 Verfahren zur Wiedergewinnung von verbrauchten, sauren Katalysatoren in Alkylierungsverfahren
RU94023252A RU2122991C1 (ru) 1993-07-06 1994-07-06 Способ регенерации отработанного кислотного катализатора
US08/271,117 US5457258A (en) 1993-07-06 1994-07-06 Recovery of spent acid catalyst from alkylation of hydrocarbons

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DK081393A DK171701B1 (da) 1993-07-06 1993-07-06 Fremgangsmåde til genvinding af brugt syrekatalysator fra alkylering af carbonhydrider
DK81393 1993-07-06

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DK81393D0 DK81393D0 (da) 1993-07-06
DK81393A DK81393A (da) 1995-01-07
DK171701B1 true DK171701B1 (da) 1997-04-01

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RU (1) RU2122991C1 (da)

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DE69405654T2 (de) 1998-01-22
DK81393D0 (da) 1993-07-06
DK81393A (da) 1995-01-07
EP0633063B1 (en) 1997-09-17
RU2122991C1 (ru) 1998-12-10
RU94023252A (ru) 1996-05-27
US5457258A (en) 1995-10-10
ES2108338T3 (es) 1997-12-16
EP0633063A1 (en) 1995-01-11
DE69405654D1 (de) 1997-10-23

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