US3855346A - Isomerization of paraffinic hydrocarbons with trifluoromethanesulfonic acid - Google Patents
Isomerization of paraffinic hydrocarbons with trifluoromethanesulfonic acid Download PDFInfo
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- US3855346A US3855346A US00221777*A US22177772A US3855346A US 3855346 A US3855346 A US 3855346A US 22177772 A US22177772 A US 22177772A US 3855346 A US3855346 A US 3855346A
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- trifluoromethanesulfonic acid
- isomerization
- catalyst
- paraffinic hydrocarbons
- hydrocarbons
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 32
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 32
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000006317 isomerization reaction Methods 0.000 title claims description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 229910001512 metal fluoride Inorganic materials 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000792 Monel Inorganic materials 0.000 description 4
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 4
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 2
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 101150101537 Olah gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 101150115425 Slc27a2 gene Proteins 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- 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
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2794—Catalytic processes with hydrides or organic compounds
Definitions
- Paraffinic hydrocarbons are converted to other hydrocarbons by contacting with a catalyst comprising trifluoromethanesulfonic acid.- In another embodi- Vb metal fluoride.
- isoparaffinic and branched chain'paraffin hydrocarbons are of greater commercial value to the petroleum industry than the corresponding straight chain hydrocarbons.
- 2.2-.dimethylbutane has a higher octane rat: ing than the isomeric normal hexane.
- Isobutane is more valuable than normal butane since the former can be used as a basis for the preparation of 8-carbon-atom, branched chainhydrocarbons by alkylation with butylene.
- an object of this invention is to provide an improved hydrocarbon conversion process.
- Another object of this invention is to provide an isomerization process whereby high selectivity to skeletal isomers is achieved.
- Another object of this invention is to provide an improved isomerization process for the conversion of paraffmic hydrocarbons.
- a further object of this invention is to provide an improved catalyst for hydrocarbon conversion and isomerization.
- a process for the conversion of paraffinic hydrocarbons to other hydrocarbons comprises contacting the hydrocarbons with a catalyst comprising trifluoromethanesulfonic acid. It has been found that trifluoromethanesulfonic acid alone effects the isomerization and cracking of paraffinic hydrocarbons such as normal hexane.
- normalparaffins can be isom'erized with high selectivity to branched isomers containing the 7 same number of carbon atoms by contacting the hydrocarbons with a catalyst comprising trifluoromethanesulfonic acid and a Group Vb metal fluoride.
- nhexane isomerizes to predominantly neohexane in the presence of a catalyst comprising trifluoromethanesulfonic acid and at least one of phosphorus pentafluoride, antimonypentafluoride.and arsenic pentafluoride.
- a catalyst comprising trifluoromethanesulfonic acid and at least one of phosphorus pentafluoride, antimonypentafluoride.and arsenic pentafluoride.
- Trifluoromethanesulfonic acid has various advantages not possessed by known superacid catalyst systems including (1) it has a much higher boiling point, hence less is loston recycle in continuous operation; (2) it does not attack glass so sight gages, etc. made of glass can be used; and (3) it is the strongest protonic acid known and fective.
- the catalyst composition of the presentinvention comprises trifluoromethanesulfonic acid alone or trifluoromethanesulfonic acid with a metal fluoride of aGroup Vb element. Specific examples of these metal paraffinic hydrocarbon stream, it is also contemplated.
- reaction conditions for isomerization of the feed can be in the range of 0 to 100 C, usually 15 to C, and pressures sufficient to maintain the hydrocarbon reactants and catalysts as liquid in the reaction zone,
- the temperatures and pressures should be chosen accordingly.
- the time of contact is subject to wide variation, the length of residence time dependent in part upon the temperature and catalyst concentration employed. In general, reaction times ranging from about 5 minutes to 48 hours, preferably 15 minutes to about
- the mole ratio of paraffinic hydrocarbon to Group Vb metal fluoride forming the catalyst of the invention will generally be in the range 50:1 to 0.221, preferably 1:1 to 20: l
- the mole ratio of trifluoromethanesulfonic acid to Group Vb metal fluoride catalyst will generally hence smaller amounts of acid are efbe in the range 100:1 to 02:1, preferably 1:1 to 20:1.
- the mole ratio of trifluoromethanesulfonic acid to paraffinic hydrocarbon when trifluoromethanesulfonic acid alone is used as the catalyst will generally be in the into a polyethylene separatory funnel.
- the upper hy- .drocarbon layer was drained under nitrogen into a Fischer-Porter Aerosol compatibility bottle containing about five grams of potassium carbonate and cooled in range 0121 to 50:1, preferably 0.5:1 to 20:1. 5 a dry ice-acetone bath.
- the bottle was quickly capped
- the process of the invention is conducted as a batch with a heafl hg a Pressure g and a Slhcohe D" or a continuous operation.
- Phg analyses- Results can be ofa conventional nature and can comprise a sinare reported In terms of selechvmes based on the glc gle reactor equipped with sufficient stirring devices. analyses- Good agitation is important because the less dense par- EXAMPLE affinic hydrocarbon layer is not miscible with the dense liqui ac phase.
- the reactor can be a Monel lined re- 7 EXAMPLE I] actor. It is preferred that the reaction be carried out o mal exane was isomerized to its branched isounder anhydrous conditions in an inert gas atmosphere. y Contacting with a mixture of antimony P Trifluoromethanesulfonic acid fumes copiously upon fluoride (SbF and trifluoromethanesulfonic acid.
- EXAMPLE 111 Normal hexane was isomerized to its branched isomers by contacting with a mixture of trifluoromethanesulfonic acid and phosphorus pentafluoride at 25 C for 2 hours. In the run 12.6-grams (0.1 mole) of phosphorus pentafluoride, 50 ml g, 0.56 mole) trifluoromethanesulfonic acid, and 17.2 g (0.2 mole) of n-hexane were used. Results of the isomerization of n-hexane are given below in Table 111.
- a process for the'isomerization of paraffinic hywith a n-hexane conversion of 1.9 percent. drocarbons which comprises contacting a feed cornprising paraffinic hydrocarbons in a conversion zone at EXAMPLE IV isomerization conditions with a catalyst consisting of Hexane was isomerized to branched products by conifluo methanesulfonic acid.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Paraffinic hydrocarbons are converted to other hydrocarbons by contacting with a catalyst comprising trifluoromethanesulfonic acid. In another embodiment, normal paraffins are isomerized with high selectivity to skeletal isomers containing the same number of carbon atoms by contacting same with a catalyst comprising trifluoromethanesulfonic acid and a Group Vb metal fluoride.
Description
United States Patent [191 Norell [111 3,855,346 8 [451 Dec. 17, 1974 ISOMERIZATION OF PARAFFI NIC HYDROCARBONS WITH TRIFLUOROMETHANESULFONIC ACID [75] Inventor: John R. N0rell, Bart1esville,' Okla.
[73] Assignee: Phillips Petroleum Company,
- Bartlesville, Okla.
[22] Filed-: Jan. 28, 1972 [21] App]. N0.: 221,777
[52] US. Cl. 260/683.68
[51] Int. Cl.; C070 5/30 [58] Field of Search..... 260/683,68, 683.47, 683.58, 260/668 A, 683.65, 666 P; 252/439, 441
[56] References Cited UNITED STATES PATENTS 3.594.445 7/1971 Parker 260/68368 3,636,129 1/1972 Parker et a1. 260/683.58 3,678,120 7/1972 Bloch 260/683.65 3,766,286 10/1973 Olah 260/683.68
Primary Examiner-Delbert E. Gantz Assistant Examiner-G. J. Crasanakis 57 ABSTRACT Paraffinic hydrocarbons are converted to other hydrocarbons by contacting with a catalyst comprising trifluoromethanesulfonic acid.- In another embodi- Vb metal fluoride.
3 Claims, N0 Drawings ISOMERIZATION OF PARAFFINIC I-IYDROCARBONS WITH TRIFLUOROMETHANESULFONIC AClID a catalyst comprising trifluoromethanesulfonic acidand a Group Vb metal fluoride. In accordance with a further aspect, normal paraffims are isomerized with high selectivity to skeletal isomers containing the same number of carbon atoms by contacting the parafflns with a catalyst comprising trifluoromethanesulfonic acid and a Group Vb metal fluoride.
It is well known that the more highly branched, isomers of the paraffinic hydrocarbons occurring in petroleum gasoline fractions are more valuable than the corresponding slightly branched or straight chain hydrocarbons because of their higher octane ratings. The demand for motor fuels of greater octane number has-increased markedly as the automotive industry has provided gasoline engines with increasingly higher compression ratios to attain greater efficiency. One of the economically important ways in which the increased demands for high octane fuels can be-met is through the isomerization of the light naphtha components of such fuels.
It may be generally stated that the isoparaffinic and branched chain'paraffin hydrocarbons are of greater commercial value to the petroleum industry than the corresponding straight chain hydrocarbons. Thus, for example, 2.2-.dimethylbutane has a higher octane rat: ing than the isomeric normal hexane. Isobutane is more valuable than normal butane since the former can be used as a basis for the preparation of 8-carbon-atom, branched chainhydrocarbons by alkylation with butylene.
The isomerization of normal paraffinhydrocarbons I into the corresponding branched chain homologsis well known. For effecting the isomerization, it is ,customary to employ certain metal halides, particularly aluminum chloride or aluminum bromide, in conjunction with certain promoters such as hydrogen chloride, hydrogen bromide, or boron fluoride. Recently, strong acid systems such as solutions of fluorosulfonic acid and antimony pentafluoride have also been disclosed'as useful isomerization catalysts. An important problem arising with the use of these highly active catalysts is that they promote side reactions such as cracking and disproportionation. These side reactions are particularly evident at high conversion conditions and lead to the formation of substantial amounts of undesirable light and/or heavy side products.
Accordingly,'an object of this invention is to provide an improved hydrocarbon conversion process.
Another object of this invention is to provide an isomerization process whereby high selectivity to skeletal isomers is achieved.
Another object of this invention is to provide an improved isomerization process for the conversion of paraffmic hydrocarbons.
' .2 hours, are .employed.
A further object of this invention is to provide an improved catalyst for hydrocarbon conversion and isomerization.
Other objects and aspects as well as the several advantages of the invention will be apparent tothose skilled in the art upon further consideration of the specification and the appended claims.
In accordance with the invention, a process for the conversion of paraffinic hydrocarbons to other hydrocarbons is provided which comprises contacting the hydrocarbons with a catalyst comprising trifluoromethanesulfonic acid. It has been found that trifluoromethanesulfonic acid alone effects the isomerization and cracking of paraffinic hydrocarbons such as normal hexane.
Further in accordance with the invention, it has been found that normalparaffins can be isom'erized with high selectivity to branched isomers containing the 7 same number of carbon atoms by contacting the hydrocarbons with a catalyst comprising trifluoromethanesulfonic acid and a Group Vb metal fluoride.
In accordance with one specific embodiment, nhexane isomerizes to predominantly neohexane in the presence of a catalyst comprising trifluoromethanesulfonic acid and at least one of phosphorus pentafluoride, antimonypentafluoride.and arsenic pentafluoride.
Trifluoromethanesulfonic acid has various advantages not possessed by known superacid catalyst systems including (1) it has a much higher boiling point, hence less is loston recycle in continuous operation; (2) it does not attack glass so sight gages, etc. made of glass can be used; and (3) it is the strongest protonic acid known and fective.
The catalyst composition of the presentinvention comprises trifluoromethanesulfonic acid alone or trifluoromethanesulfonic acid with a metal fluoride of aGroup Vb element. Specific examples of these metal paraffinic hydrocarbon stream, it is also contemplated.
that mixtures. of various paraffinic hydrocarbons can be employed. I
The reaction conditions for isomerization of the feed can be in the range of 0 to 100 C, usually 15 to C, and pressures sufficient to maintain the hydrocarbon reactants and catalysts as liquid in the reaction zone,
-and the temperatures and pressures should be chosen accordingly. The time of contact is subject to wide variation, the length of residence time dependent in part upon the temperature and catalyst concentration employed. In general, reaction times ranging from about 5 minutes to 48 hours, preferably 15 minutes to about The mole ratio of paraffinic hydrocarbon to Group Vb metal fluoride forming the catalyst of the invention will generally be in the range 50:1 to 0.221, preferably 1:1 to 20: l The mole ratio of trifluoromethanesulfonic acid to Group Vb metal fluoride catalyst will generally hence smaller amounts of acid are efbe in the range 100:1 to 02:1, preferably 1:1 to 20:1. The mole ratio of trifluoromethanesulfonic acid to paraffinic hydrocarbon when trifluoromethanesulfonic acid alone is used as the catalyst will generally be in the into a polyethylene separatory funnel. The upper hy- .drocarbon layer was drained under nitrogen into a Fischer-Porter Aerosol compatibility bottle containing about five grams of potassium carbonate and cooled in range 0121 to 50:1, preferably 0.5:1 to 20:1. 5 a dry ice-acetone bath. The bottle was quickly capped The process of the invention is conducted as a batch with a heafl hg a Pressure g and a Slhcohe D" or a continuous operation. The apparatus employed m for wlthclrawmg Samples Phg analyses- Results can be ofa conventional nature and can comprise a sinare reported In terms of selechvmes based on the glc gle reactor equipped with sufficient stirring devices. analyses- Good agitation is important because the less dense par- EXAMPLE affinic hydrocarbon layer is not miscible with the dense liqui ac phase. U re cte reactants, ly Trifluoromethanesulfonic acid was used alone as the and other Pf 0f the macho can be separated catalyst to effect the isomerization and cracking of nfrom the desired product and from one another such as hexane i accordance i h h procedure Set f h by dist llation and returned in whole or in part to the above. The isomerization was effected at a temperature isomerization zone. The resultant product can be furof C for two hours. In both runs 25 ml (42.5 g, 0.28 ther processed as by alkylation and the like or be emmole) of trifluoromethanesulfonic acid and 17.2 g (0.2 ployed directly as a high octane gasoline blending mole n-hexane were used. The results of the normal agent. The reaction zone is preferably constructed of hexane isomerization are given below in Table 1.
TABLE 1 Selectivity Hexane to Cracked Light Products Run Conv.,% Products (C C 'S,C 's) Heavies 2,2-DMB DlP+2-MP 3-MP materials which are resistant to corrosion by the catalyst. For example, the reactor can be a Monel lined re- 7 EXAMPLE I] actor. It is preferred that the reaction be carried out o mal exane was isomerized to its branched isounder anhydrous conditions in an inert gas atmosphere. y Contacting with a mixture of antimony P Trifluoromethanesulfonic acid fumes copiously upon fluoride (SbF and trifluoromethanesulfonic acid. In exposure to air and the Group Vb metal halides are also n 3 and m1 gmole) trlflllOrOmethanehydrolyzed on exposure to atmospheric moisture. sulfonic acid and 17.2 g (0.2 mole) n-hexane were used. In runs 3 and 4, 6.6 and 12.3 grams of antimony SPECIFIC EXAMPLES pentafluoride were used, respectively. Paraffinic hydrocarbons were isomerized to isoparaf- The results of the normal hexane isomerization are fins with liquid phase catalyst systems of the invention 40 given below in Table II.
TABLE I1 lsomcrization of n-Hexanc with SbF /CF SO H at 25C/2 Hrs.
Hexanc Selectivity to Products Run Conv.,/r Cracked Products* Hca- VlCS utilizing a Monel reactor. The procedure for carrying out the isomerization in a Monel reactor is set forth below.
The process runs were carried out in a 300 ml Monel reactor. The trifluoromethanesulfonic acid was charged under nitrogen to the reactor and cooled therein to approximately 40C. In Examples 11, 111 and 1V hereinbelow the Group Vb metal halide was then added to the cold trifluoromethanesulfonic acid until the desired weight was obtained, followed by addition of the paraffin. The reactor was then capped and placed in a thermostated Eberbach reciprocating shaker for any desirable time at a specified tempera ture.
Workup involved cooling the Monelreactor in dry ice-acetone and then rapidly pouring the cold mixture It can be seen from the above tabulated data that antimony pentafluoride and trifluoromethanesulfonic acid in the liquid phase effect hexane isomerization in 95 percent conversion to branched C isomers with only three percent selectivity to cracked (C C15 and C s) products. Neohexane formed in approximately the thermodynamic equilibrium quantity of 55 percent.
EXAMPLE 111 Normal hexane was isomerized to its branched isomers by contacting with a mixture of trifluoromethanesulfonic acid and phosphorus pentafluoride at 25 C for 2 hours. In the run 12.6-grams (0.1 mole) of phosphorus pentafluoride, 50 ml g, 0.56 mole) trifluoromethanesulfonic acid, and 17.2 g (0.2 mole) of n-hexane were used. Results of the isomerization of n-hexane are given below in Table 111.
TABLE 111 Selectivities* Mole Ratio n-C C l-C. n-C; 1-C5 2.2-DMB DIP & Run n-C JPB, "/1 Conv. 2-MP 3-MP Heavies *2.2 DMB represents 2.2 3-methylpentzmc.
It will be noted from the above table that trifluoromethanesulfonic acid in admixture with phosphorus pentafluoride effected hexane isomerization in approximately 95 percent selectivity to branched C isomers -dimethylbutune. DIP represents diisopropyl (2.3-dimethylbutanc). 2-MP represents Z-methylpcntune. and 3-MP represents 2-MP dimethylbutane than the use of trifluoromethanesulfonic acid alone.
1 claim:
1. A process for the'isomerization of paraffinic hywith a n-hexane conversion of 1.9 percent. drocarbons which comprises contacting a feed cornprising paraffinic hydrocarbons in a conversion zone at EXAMPLE IV isomerization conditions with a catalyst consisting of Hexane was isomerized to branched products by conifluo methanesulfonic acid.
tacting with trifluoromethanesulfonic acid in admixture 2. A process according to claim 1 wherein the parafwith arsenic pe'ntafluoride at 25 C for two hours. In the finic hydrocarbon is normal hexane. run 10.2 g (0.06 mole) of arsenic pentafluoride, 50 rnl 3. A process according to claim 1 wherein said feed (85 g, 0.56 mole) trifluoromethanesulfonic acid, and comprises paraffinic hydrocarbons having from 4 to 7, 17.2 g (0.2 mole) of n-hexane were used. The results inclusive, carbon atoms per molecule and said contactof the isomerization are given below in Table IV. ing is effected at a temperature in the range of 0-100C TABLE IV Hexane I Selectivity to Li ht Products ,C s,C s) Heavies 2,2-DMB DlP-l-Z-MP 3-MP Run Conv.,% Cracked Products g and a pressuresufficient to maintain the reactants and catalyst in the liquid phase.
Claims (3)
1. A PROCESS FOR THE ISOMERIZATION OF PARAFFINIC HYDROCARBONS WHICH COMPRISES CONTACTING A FEED COMPRISING PARAFFINIC HYDROCARBONS IN A CONVERSION ZONE AT ISOMERIZATION CONDITIONS WITH A CATALYST CONSISTING OF TRIFLUOROMETHANESULFONIC ACID.
2. A process according to claim 1 wherein the paraffinic hydrocarbon is normal hexane.
3. A process according to claim 1 wherein said feed comprises paraffinic hydrocarbons having from 4 to 7, inclusive, carbon atoms per molecule and said contacting is effected at a temperature in the range of 0-100*C and a pressure Sufficient to maintain the reactants and catalyst in the liquid phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00221777*A US3855346A (en) | 1972-01-28 | 1972-01-28 | Isomerization of paraffinic hydrocarbons with trifluoromethanesulfonic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00221777*A US3855346A (en) | 1972-01-28 | 1972-01-28 | Isomerization of paraffinic hydrocarbons with trifluoromethanesulfonic acid |
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| US3855346A true US3855346A (en) | 1974-12-17 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3925194A (en) * | 1973-11-21 | 1975-12-09 | Mobil Oil Corp | Hydrocarbon conversion with catalyst of sbf' 5 'on silica |
| US4044069A (en) * | 1973-09-26 | 1977-08-23 | Societe Nationale Elf Aquitaine | Catalytic composition for the isomerization and alkylation of hydrocarbons |
| US5256277A (en) * | 1991-07-24 | 1993-10-26 | Mobil Oil Corporation | Paraffin isomerization process utilizing a catalyst comprising a mesoporous crystalline material |
| 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 |
| WO2018044592A1 (en) * | 2016-08-29 | 2018-03-08 | Exxonmobil Chemical Patents Inc. | Production of neopentane |
| US10487023B2 (en) | 2016-08-29 | 2019-11-26 | Exxonmobil Chemical Patents Inc. | Production of neopentane |
| US10626064B2 (en) | 2018-05-30 | 2020-04-21 | Exxonmobil Chemical Patents Inc. | Processes to make neopentane using shell and tube reactors |
| US10654770B2 (en) | 2016-08-29 | 2020-05-19 | Exxonmobil Chemical Patents Inc. | Production of neopentane |
| US10870610B2 (en) | 2016-08-29 | 2020-12-22 | Exxonmobil Chemical Patents Inc. | Production of neopentane |
| US10994264B2 (en) | 2018-05-30 | 2021-05-04 | Exxonmobil Chemical Patents Inc. | Catalysts and processes for making catalysts for producing neopentane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3594445A (en) * | 1969-10-30 | 1971-07-20 | Exxon Research Engineering Co | Isomerization of paraffinic hydrocarbons employing hydrogen with an olefin and/or an alkyl fluorosulfonate |
| US3636129A (en) * | 1970-02-18 | 1972-01-18 | Exxon Research Engineering Co | Normal paraffin alkylation using fluorosulfonic acid and group v metal fluoride catalyst |
| US3678120A (en) * | 1970-01-29 | 1972-07-18 | Universal Oil Prod Co | Hydrocarbon conversion catalyst and process |
| US3766286A (en) * | 1971-06-25 | 1973-10-16 | Exxon Research Engineering Co | Process for the isomerization of hydrocarbons |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3594445A (en) * | 1969-10-30 | 1971-07-20 | Exxon Research Engineering Co | Isomerization of paraffinic hydrocarbons employing hydrogen with an olefin and/or an alkyl fluorosulfonate |
| US3678120A (en) * | 1970-01-29 | 1972-07-18 | Universal Oil Prod Co | Hydrocarbon conversion catalyst and process |
| US3636129A (en) * | 1970-02-18 | 1972-01-18 | Exxon Research Engineering Co | Normal paraffin alkylation using fluorosulfonic acid and group v metal fluoride catalyst |
| US3766286A (en) * | 1971-06-25 | 1973-10-16 | Exxon Research Engineering Co | Process for the isomerization of hydrocarbons |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4044069A (en) * | 1973-09-26 | 1977-08-23 | Societe Nationale Elf Aquitaine | Catalytic composition for the isomerization and alkylation of hydrocarbons |
| US3925194A (en) * | 1973-11-21 | 1975-12-09 | Mobil Oil Corp | Hydrocarbon conversion with catalyst of sbf' 5 'on silica |
| US5256277A (en) * | 1991-07-24 | 1993-10-26 | Mobil Oil Corporation | Paraffin isomerization process utilizing a catalyst comprising a mesoporous crystalline material |
| 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 |
| WO2018044592A1 (en) * | 2016-08-29 | 2018-03-08 | Exxonmobil Chemical Patents Inc. | Production of neopentane |
| US10487023B2 (en) | 2016-08-29 | 2019-11-26 | Exxonmobil Chemical Patents Inc. | Production of neopentane |
| US10654770B2 (en) | 2016-08-29 | 2020-05-19 | Exxonmobil Chemical Patents Inc. | Production of neopentane |
| US10870610B2 (en) | 2016-08-29 | 2020-12-22 | Exxonmobil Chemical Patents Inc. | Production of neopentane |
| US10626064B2 (en) | 2018-05-30 | 2020-04-21 | Exxonmobil Chemical Patents Inc. | Processes to make neopentane using shell and tube reactors |
| US10994264B2 (en) | 2018-05-30 | 2021-05-04 | Exxonmobil Chemical Patents Inc. | Catalysts and processes for making catalysts for producing neopentane |
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