US3766286A - Process for the isomerization of hydrocarbons - Google Patents

Process for the isomerization of hydrocarbons Download PDF

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US3766286A
US3766286A US00156822A US3766286DA US3766286A US 3766286 A US3766286 A US 3766286A US 00156822 A US00156822 A US 00156822A US 3766286D A US3766286D A US 3766286DA US 3766286 A US3766286 A US 3766286A
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acid
catalyst
isomerization
pentafluoride
group
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G Olah
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
    • C07C5/271—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with inorganic acids; with salts or anhydrides of acids
    • C07C5/2718—Acids of halogen; Salts thereof; complexes thereof with organic compounds
    • C07C5/2721—Metal halides; Complexes thereof with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
    • C07C5/2727—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with hydrides or organic compounds
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions
    • 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
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/20—Non-coordinating groups comprising halogens
    • B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate

Definitions

  • Paraffinic and/or alkyl substituted aromatic hydrocarbons are isomerized with a catalyst comprising (a) a Lewis acid of the formula MX where M is selected from Group IV-B, V or VI-B of the Periodic Table, X is a halogen and n varies from 3 to 6, and (b) a strong Bronsted acid comprising fiuorosulfuric acid, trifluoromethanesulfonic acid, trifluoroacetic acid or mixtures thereof.
  • a catalyst comprising (a) a Lewis acid of the formula MX where M is selected from Group IV-B, V or VI-B of the Periodic Table, X is a halogen and n varies from 3 to 6, and (b) a strong Bronsted acid comprising fiuorosulfuric acid, trifluoromethanesulfonic acid, trifluoroacetic acid or mixtures thereof.
  • the present invention relates to a process for isomerizing paraffins and/or alkyl substituted aromatic hydrocarbons. More particularly, the invention relates to the isomerization of branched and straight chain aliphatic and cycloaliphatic hydrocarbons and/or alkyl substituted aromatic hydrocarbons at isomerization conditions in the presence of a strong acid catalyst. Still more particularly, the invention relates to the isomerization of C to C paraflins and alkyl substituted aromatic hydrocarbons in the presence of a catalyst comprising a Lewis acid and a strong Bronsted acid.
  • isomerizable hydrocarbons selected from the group consisting of paraffin-s,
  • alkyl substituted aromatic hydrocarbons and mixtures thereof, containing, preferably, 4 to 20 carbon atoms per molecule are isomerized at low temperatures in the presence of a catalyst comprising (a) one or more Lewis acids of the formula MX where M is selected from Group IV-B, Group V or Group V'IB elements of the Periodic Table, X is a halogen, preferably fluorine, and n varies from 3 to 6, and (b) a strong Bronsted acid, preferably comprising a strong halogen-substituted acid such as fiuorosulfuric acid, trifluoromethanesulfonic acid, trifluoroacetic acid or mixtures thereof.
  • a catalyst comprising (a) one or more Lewis acids of the formula MX where M is selected from Group IV-B, Group V or Group V'IB elements of the Periodic Table, X is a halogen, preferably fluorine, and n varies from 3 to 6, and (b) a strong Bronsted acid,
  • the Periodic Table referred to is that described in The Encyclopedia of Chemistry, Reinhold Publishing Corporation, 2nd ed. (1966) at p. 790.
  • the term elements as used herein refers to the metals and metalloids of the aforementioned groups of the Periodic Table.
  • Lewis acids include antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, niobium pentafluoride, vanadium pentafluoride, titanium tetrafluoride, bismuth pentafluoride, phosphorus pentafluoride, molybdenum hexafluoride, zirconium tetrafiuoride, mixtures thereof and the like.
  • chlorine, bromine or iodine may be substituted for fluorine without affecting the efficiency of the catalyst system.
  • the catalyst composition will comprise only one Lewis acid and one Bronsted acid.
  • Exemplary of such catalyst compositions that are encompassed by this invention are the following.
  • Antimony pentafluoride-fluorosulfuric acid 2 Arsenic pentafluoride-fiuorosulfuric acid. 3 Tantalum pentafluoride-fluorosulfuric acid. 4 Niobium pentafluoride-fluorosulfuric acid. 5 Vanadium pentafiuoride-fluorosulfuric acid. 6 Titanium tetrafiuoride-fluorosulfuric acid. 7 Molybdenum hexafiuoride-fluorosulfuric acid. 8 Antimony pentafluoride-chlorosulfuric acid. 9 L Antimony pentafluoride-trifluoromethanesulfonic acid.
  • Tantalum pentafluoride-trifluoroacetic acid 18 Tantalum pentafluoride-trifluoroacetic acid. 19 Arsenic pentafluoride-trifluoroacetic acid. 20 Titanium tetrafluoride-trifluoroacetic acid. 21 Zirconium tetrafluoride-trifluoroacetic acid. 22 Vanadium pentafluoride-trifluoroacetic acid. 23 Molybdenum hexafluoride-trifluoroacetic acid. 24 Niobium pentafluoride-trifluoroacetic acid.
  • Preferablwthe' amount of catalyst present in I zone can rangejfrom '1 tolO'pa'rts; by weightoiithe ata; lysti compositioniper pareby weight'of; the'hy rocar n r volume ratio can'range. from about 550:1 to l": I' and erablyjfromflOcgltoZrl! f "in V j
  • the icatalystjsystem? mayJbef 'employed incorporated with a suitable SQlid carrierorfsupport; AIlY fSQlldQCBl lyst support maybe used that iss'ubstantially inert.
  • catalyst underthe reactionfconditions;Thefsupportfshould p able solid supports include fluoride-treatedor coated res-ins I a 7 such assu-lfo'natejd cation exchange resins, fluoride rented r acidic chalcides such as alurnina; and aluminosilicate' and i rjasite
  • the supp V able.manner such asfby coriventional methodsincludiug dry mixing cpprecipitation: or impregnationtiln on hating a suitablev deactivatedsupport with a meta fiuOn such asantimony pentafluoride and then with a Bronsted l acidsuch asifluorosulfuricacid.
  • p V "The weight' ratio' ofxthe Lew s acid to the supper,
  • the molar .raftio of Bronste i Lewis aci range from, about 2011' to 5 1 :Pr'eferably a 5: 1: t molar ratio islemployed.
  • Theamountof, the cataly' r V U present'thereiri can from: about 0.01 to 100 parts; or ieven higherby The catalystmaybe used as the neat liquid; as a The catalyst, may be: used? as theizneat liquid,
  • the apparatus employedv may be of a conventional,nature and f may com prise a' single reactor sucl'rv asa fluid ized-bed be pretreated, suchlias ibyheating, chemical treatment or coating, towremoye substantially'all water and/or hy-Q I droxylic sites thatmight b'e.present.
  • Active support may be renderedinert by coatingnthem' withfanwinertjmaterial such a's antimony trifluoride or aluminum trifiuoridefSu acid resisjtant olecular' sieves such as a zeolite'e ortejd catalysts can be'prepared in bodi-ment," the supported catalyst is prepared nvactifinrpressure can range from'about 1 atmosphere to 1:35.
  • Thetweightratio ofthe'Bronsted-acid to thesiupport may'range fr to 1:35. .7 7 r i 7 Feedstocks that may be used in the instant process and mixtures thereof;
  • n-butane n-pentane
  • methylpentane methylpentane
  • methylhexane methylhexane
  • the ,cycloaliphatic hydrocarbons can contain 6 to carbon atoms per molecule, preferably 6-12 carbon atoms, and may be exemplified by methylcyclopentane, the dimethylcyclopentanes, ethylcyclohexane, n-pentylcyclohexane and the like. Depending.
  • isomerization of the ring i.e. ring expansion or contraction
  • side chainmatic hydrocarbons such as the xylenes, n-butyl benzene and the like. Both positional isomerizationof the alkyl groups substituted on the ring and side chain isomerization may occur depending on reactionconditions.
  • Other aliphatic or alic'yclic hydrocarbons commonly found in conventional petroleum, hydrocarbon light naphtha '1 streams may also bepresent.
  • the feed may; contaiu'various cracking .inh'hitors or I moderators suchas hydrogen and the like s'fhe inhibitors during the isomerization, When hydroge is used,-; it" is employed, in; amounts ranging, preferab Y mole" percent based" on, hydrocarbon teed ,fimpurities such aswater; there rerthe.
  • alikylatioushonld I be conductedsubstantially; 1n the ,abjsenceot large amounts of moisturaiie.
  • n-hexane is p introduced into isomerizationzone 2, in the liquid phase, from a source, not shown, by way of line 1.
  • An equimolar mixture of antimony pentafluoride and trifluoromethane sulfonic acid is introduced intoezone 2 via 1ine3, The amount of catalyst chargedlis. 20 g. per g. of n-hexane.
  • the temperature within the isomerization zone is maintained between the range of 20 to 25 C. while the pressure is maintained at 1 atmosphere.
  • the isomerization zone is provided with an agitator to ensure thorough contacting of the reactants.
  • the contacting time I is. about 2-6 hours. 7
  • the .isomerized product is discharged from zone 2 via line 4 and sent to settling zone 5. Upon standing for a period of time, the product separates into a hydrocarbon phase and an inorganic phase containing the acid catalyst that is essentially insoluble. in the hydrocarbon phase. The separated acid catalyst is then withdrawn from zone 5 and recycled to the isomerization zone 2 via line 6 for reuse.
  • the separated hydrocarbon phase is discharged from settling zone 5 via line 7 and contacted therein with caustic (e.g. about 20% by weight sodium hydroxide) introduced via line 8. The amount of caustic added thereto is gms. per 100 gms. of n-hexane.
  • n-hexane/caustic mixture is introduced into mixing zone 9 and intimate- 1y mixed therein.
  • the mixture is then withdrawn from the mixing zone by means of line 10 and introduced into settling zone 11, wherein the caustic phase separates from the hydrocarbon phase.
  • the caustic phase is removed via line 12 and the hydrocarbon phase is removed via line 13 and introduced into a separation zone 14 illustrated as a distillation zone that is provided with a heating means such as steam coil 15 and with lines 16, 17, 18, 19 and 20. Conditions of temperature and pressure are adjusted in zone 14 to recover the product either in one fraction (line 16) or in several fractions by lines 17 and 18 While unreacted nhexane feed may be discharged by line 19 and preferably recycled to isomerization zone 2 via lines 19 and 1. The heavy side products are discharged from the separation Zone 14 by line 20.
  • Product analysis Table I summarizes isomerization product compositions as determined by gas-liquid chromatography using a 150 foot, 0.01 inch I.D. squalene column and a hydrogen ionization flame detector.
  • a process for the isomerization of isomerizable hydrocarbons selected from the group consisting of paraffins, alkyl substituted aromatic hydrocarbons and mixtures thereof comprising contacting said isomerizable hydrocarbon at isomerization conditions with a catalyst comprising (a) a Lewis acid of the formula MX where M is selected from the Group V elements of the Periodic Table, X is a halogen and It varies from 3 to 6, and (b) a Bronsted acid comprising fluorosulfuric acid, said contacting occurring substantially in the liquid phase.
  • paraffins contain 4 to 20 carbon atoms per molecule and are selected from the group consisting of aliphatic and cycloaliphatic hydrocarbons and where said alkyl substituted aromatic hydrocarbons contain 7 to 20 carbon atoms per molecule.
  • Lewis acid is selected from the group consisting of antimony pentafluoride, tantalum pentafluoride, niobium pentafluoride, vanadium pentafluoride, bismuth pentafiuoride, arsenic pentafluoride, and phosphorus pentafluoride.
  • said diluent is selected from the group consisting of sulfuryl chloride fluoride, sulfuryl fluoride and fiuorinated hydrocarbons.
  • a catalytic isomerization process comprising contacting isomerizable hydrocarbons selected from the group consisting of C to C paraffins, C to C alkyl substituted aromatic hydrocarbons and mixtures thereof, at isomerization conditions with a catalyst comprising (a) a metal fluoride wherein the metal is selected from the group consisting of titanium and Group V and Group TABLE I.-n-HEXANE ISOMERIZATION Run 1 Reaction conditions:
  • X is a halogenrand n varies, from ⁇ to 6, and '(b) a Bronsted acid selected fromthe group consistingfljof trifluoromethanesulfonic"acid and trifluoroacetic acid;
  • a process for the isomerization of an isomerizable a hydrocarbonselected from the group consisting of paraf- M is slected from the group consistingrof titaniur'nfand L Group V and Group 'YLB elements of v the Periodic Table, X is a halogen and 'n varies, from 3 to '6, andtb) fiuorosulfuric acid, where said fluorosulfuric acid and fins, alkyl :isubstituted: aromatic hydrocarbons and zmixa ⁇ tures thereof comprising contacting said" isomerizablefhyi drocarbons at isomerization conditions with'a catalyst comprising (a) a Lewis acid of the'formula MX' where?
  • r Lewis acid are supported 'stautiaily inert. to said supported-"acids, siaid solidcarrier selected from the group consistingof fluoride-treated I, resins, fluoride-treated acidic chali d'es andacid-resistant gen and n' varies from 3 to 6, an'd: (blaBronsted on a solid carrier that 'is subrno'lecular sieves.
  • a process for the isomerizationof isomerizablc v hydrocarbons selected from the group consi sting'of paraffins,;alky1 substituted aromatichydrocarbons andmixtures thereof comprising contacting said isomezrizable by a idrocarbons at isomerization conditions "witha catalyst comprising (a) a Lewis acid of the formula MXg where o t M is selected from the group consisting of titanium and Group YI-B elements of the Periodic Table; X is a halocom-prising fluorosulfuric acid V 17.
  • an isomeriz- V able hydrocarbon selected from thegroup copsistiug' of 'paraffins, alkyl substituted aromatic hydrocarbons and i mixtures thereof

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US00156822A 1971-06-25 1971-06-25 Process for the isomerization of hydrocarbons Expired - Lifetime US3766286A (en)

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3855346A (en) * 1972-01-28 1974-12-17 Phillips Petroleum Co Isomerization of paraffinic hydrocarbons with trifluoromethanesulfonic acid
US3867476A (en) * 1971-10-15 1975-02-18 Bernard Torck Isomerization of saturated hydrocarbons with hexafluoroantimonic acid and a metal cation
US3878261A (en) * 1973-08-24 1975-04-15 Phillips Petroleum Co Hydroisomerization of paraffin hydrocarbon with a supported catalyst of SbF{HD 5 {B and CF{HD 3{B SO{HD 3{B H
US4022847A (en) * 1976-03-04 1977-05-10 Shell Oil Company Hydrocarbon conversion process using an unsupported perfluorinated polymer catalyst
US4035286A (en) * 1972-12-20 1977-07-12 Standard Oil Company (Indiana) Octane upgrading of light naphtha streams using a fluoroalkanesulfonic acid-antimony pentafluoride mixture
US4123468A (en) * 1975-12-29 1978-10-31 Uop Inc. Titanium tetrachloride as heterogeneous catalyst for isomerization of alkylaromatic hydrocarbon
US4144282A (en) * 1973-08-03 1979-03-13 Standard Oil Company (Indiana) Octane upgrading of light naphtha streams using a fluorosulfonic acid, hydrofluoric acid and antimony pentafluoride catalyst
US4300008A (en) * 1980-09-25 1981-11-10 Standard Oil Company (Indiana) Preparation of 2,6-dimethyldecalin and its isomers
US4547606A (en) * 1980-03-14 1985-10-15 Pcuk Produits Chimiques Ugine Kuhlmann Selective isomerization of di-isopropyl benzene to meta-di-isopropyl benzene
FR2566794A1 (fr) * 1984-06-28 1986-01-03 El Paso Products Co Procede pour ameliorer une essence naturelle de faible indice d'octane derivee du gaz naturel
US4830998A (en) * 1986-07-16 1989-05-16 Compagnie De Raffinage Et De Distribution Total France Hydrocarbon isomerization catalyst, process for its preparation, and use thereof
USRE33080E (en) * 1981-08-31 1989-10-03 Exxon Research And Engineering Company Adamantane catalyzed paraffin isomerization
US5245103A (en) * 1992-10-19 1993-09-14 Phillips Petroleum Company Isomerization processes and catalysts therefor
US5256277A (en) * 1991-07-24 1993-10-26 Mobil Oil Corporation Paraffin isomerization process utilizing a catalyst comprising a mesoporous crystalline material
US5489564A (en) * 1994-09-07 1996-02-06 Phillips Petroleum Company Alkane disproportionation
US5516964A (en) * 1994-01-21 1996-05-14 Sun Company, Inc. (R&M) Hydrocarbon isomerization using solid superacid catalysts comprising platinum metal
US5629257A (en) * 1994-01-21 1997-05-13 Sun Company, Inc. (R&M) Solid superacid catalysts comprising platinum metal
WO2003020668A1 (en) * 2001-08-31 2003-03-13 Bp Oil International Limited A process for the production of triptane
US20030187316A1 (en) * 2000-10-11 2003-10-02 Boesveld Willem Marco Isomerisation process
US20040019235A1 (en) * 2000-12-18 2004-01-29 Friedrich-Georg Martin Method for producing higher (meth)acrylic acid esters
US20040204607A1 (en) * 2003-04-09 2004-10-14 Basf Aktiengesellschaft Heterogeneously catalyzed partial direct oxidation of propane and/or isobutane
US20060122439A1 (en) * 2002-11-01 2006-06-08 Takeshi Kawai Process for producing alkylaromatic compound
US20150141730A1 (en) * 2012-06-29 2015-05-21 Mitsubishi Gas Chemical Company, Inc. Method and apparatus for separating alkyl aromatic hydrocarbon

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1129809B (it) * 1979-03-26 1986-06-11 Ugine Kuhlmann Composizione catalitica per la conversione di idrocarburi e procedimento per la disidratazione di acidi perfluoroalcansolfonici destinati a fare parte bella composizione
US4814544A (en) * 1983-12-14 1989-03-21 El Paso Products Company Isomerization of butane

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867476A (en) * 1971-10-15 1975-02-18 Bernard Torck Isomerization of saturated hydrocarbons with hexafluoroantimonic acid and a metal cation
US3855346A (en) * 1972-01-28 1974-12-17 Phillips Petroleum Co Isomerization of paraffinic hydrocarbons with trifluoromethanesulfonic acid
US4035286A (en) * 1972-12-20 1977-07-12 Standard Oil Company (Indiana) Octane upgrading of light naphtha streams using a fluoroalkanesulfonic acid-antimony pentafluoride mixture
US4144282A (en) * 1973-08-03 1979-03-13 Standard Oil Company (Indiana) Octane upgrading of light naphtha streams using a fluorosulfonic acid, hydrofluoric acid and antimony pentafluoride catalyst
US3878261A (en) * 1973-08-24 1975-04-15 Phillips Petroleum Co Hydroisomerization of paraffin hydrocarbon with a supported catalyst of SbF{HD 5 {B and CF{HD 3{B SO{HD 3{B H
US4123468A (en) * 1975-12-29 1978-10-31 Uop Inc. Titanium tetrachloride as heterogeneous catalyst for isomerization of alkylaromatic hydrocarbon
US4022847A (en) * 1976-03-04 1977-05-10 Shell Oil Company Hydrocarbon conversion process using an unsupported perfluorinated polymer catalyst
US4547606A (en) * 1980-03-14 1985-10-15 Pcuk Produits Chimiques Ugine Kuhlmann Selective isomerization of di-isopropyl benzene to meta-di-isopropyl benzene
US4300008A (en) * 1980-09-25 1981-11-10 Standard Oil Company (Indiana) Preparation of 2,6-dimethyldecalin and its isomers
USRE33080E (en) * 1981-08-31 1989-10-03 Exxon Research And Engineering Company Adamantane catalyzed paraffin isomerization
FR2566794A1 (fr) * 1984-06-28 1986-01-03 El Paso Products Co Procede pour ameliorer une essence naturelle de faible indice d'octane derivee du gaz naturel
US4830998A (en) * 1986-07-16 1989-05-16 Compagnie De Raffinage Et De Distribution Total France Hydrocarbon isomerization catalyst, process for its preparation, and use thereof
US5256277A (en) * 1991-07-24 1993-10-26 Mobil Oil Corporation Paraffin isomerization process utilizing a catalyst comprising a mesoporous crystalline material
US5245103A (en) * 1992-10-19 1993-09-14 Phillips Petroleum Company Isomerization processes and catalysts therefor
US5629257A (en) * 1994-01-21 1997-05-13 Sun Company, Inc. (R&M) Solid superacid catalysts comprising platinum metal
US5516964A (en) * 1994-01-21 1996-05-14 Sun Company, Inc. (R&M) Hydrocarbon isomerization using solid superacid catalysts comprising platinum metal
US5489564A (en) * 1994-09-07 1996-02-06 Phillips Petroleum Company Alkane disproportionation
US20030187316A1 (en) * 2000-10-11 2003-10-02 Boesveld Willem Marco Isomerisation process
US6855857B2 (en) 2000-10-11 2005-02-15 Bp Oil International Limited Isomerisation process
US20040019235A1 (en) * 2000-12-18 2004-01-29 Friedrich-Georg Martin Method for producing higher (meth)acrylic acid esters
WO2003020668A1 (en) * 2001-08-31 2003-03-13 Bp Oil International Limited A process for the production of triptane
US20040249228A1 (en) * 2001-08-31 2004-12-09 Boesveld Willem Marco Process for the production of triptane
US7332638B2 (en) 2001-08-31 2008-02-19 Bp Oil International Limited Process for the production of triptane
US7518025B2 (en) * 2002-11-01 2009-04-14 Mitsubishi Gas Chemical Company, Inc. Process for producing alkyl aromatic compound
US20060122439A1 (en) * 2002-11-01 2006-06-08 Takeshi Kawai Process for producing alkylaromatic compound
US20040204607A1 (en) * 2003-04-09 2004-10-14 Basf Aktiengesellschaft Heterogeneously catalyzed partial direct oxidation of propane and/or isobutane
US8338640B2 (en) * 2003-04-09 2012-12-25 Basf Aktiengesellschaft Heterogeneously catalyzed partial direct oxidation of propane and/or isobutane
US20150141730A1 (en) * 2012-06-29 2015-05-21 Mitsubishi Gas Chemical Company, Inc. Method and apparatus for separating alkyl aromatic hydrocarbon
US9896397B2 (en) * 2012-06-29 2018-02-20 Mitsubishi Gas Chemical Company, Inc. Method and apparatus for separating alkyl aromatic hydrocarbon
US10207967B2 (en) 2012-06-29 2019-02-19 Mitsubishi Gas Chemical Company, Inc. Method and apparatus for separating alkyl aromatic hydrocarbon

Also Published As

Publication number Publication date
CA980798A (en) 1975-12-30
FR2143432A1 (it) 1973-02-02
DE2227336A1 (it) 1972-12-28
BE785322A (fr) 1972-12-27
NL7208562A (it) 1972-12-28
FR2143432B1 (it) 1977-12-23
GB1387748A (en) 1975-03-19
IT959972B (it) 1973-11-10

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