US2324073A - Treating hydrocarbons - Google Patents
Treating hydrocarbons Download PDFInfo
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- US2324073A US2324073A US369758A US36975840A US2324073A US 2324073 A US2324073 A US 2324073A US 369758 A US369758 A US 369758A US 36975840 A US36975840 A US 36975840A US 2324073 A US2324073 A US 2324073A
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- benzene
- catalyst
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- 229930195733 hydrocarbon Natural products 0.000 title description 6
- 150000002430 hydrocarbons Chemical class 0.000 title description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- 239000003054 catalyst Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- -1 e. g. Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OIGPMFVSGDDYHS-UHFFFAOYSA-N copper sulfanylidenemolybdenum Chemical compound [S].[Cu].[Mo] OIGPMFVSGDDYHS-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- MPHPXCZQUJPPBJ-UHFFFAOYSA-N [W+2]=O.[O-2].[Cr+3] Chemical compound [W+2]=O.[O-2].[Cr+3] MPHPXCZQUJPPBJ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 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
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/74—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition with simultaneous hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/04—Sulfides
- C07C2527/047—Sulfides with chromium, molybdenum, tungsten or polonium
- C07C2527/051—Molybdenum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the main object of the invention is to produce cyclohexane and/or benzene and/or alkyl derivatives thereof from lower mono-olefins of .less than five carbon atoms.
- lower olefins are polymerized catalytically, according to present practice, good yields of liquid products are obtained, but these products contain only substantially olefin polymers and no aromatics.
- high temperature non-catalytic polymerization does result in the formation of some cyclic hydrocarbons, but this is accompanied by excessive formation of methane and other low molecular weight by-products which seriously afiect the cyclic hydrocarbon yield, making the process uneconomical.
- a catalytic method may be employed to obtain cyclic hydrocarbons directly in high yields and without substantial loss in waste lay-product gases.
- a lower olefin preferably of 3-4 carbon atoms, may be made to undergo, by catalytic directing influence, a direct cyclo-polymerization in accordance with an overall mechanism which may be illustrated by the following equations:
- CQHQ 3H Benzene 0.115013; Toluene C eHn C H: Methyl cyclohcxane
- a mixed catalyst comprising a volatile halide of the Friedel- CaHo C4Ha 2 CsHu C4Ha Crafts type, e. g.-AlCl3, BFa, HgClz, etc., and a cyclizing metal or metal compound, e. g., compounds of Mo, W, Al, V, U, Cr, Cu, Ni, etc.
- Examples of such latter cyclizing compounds are molybdenum sulfide or oxide, chromic oxide or sesquioxide, aluminum oxide or fluoride, tin oxide, copper, etc. Combinations of the latter are preferable, and as examples, the following have been found suitable: aluminum fluorideni'ckel, molybdenum sulfide-copper, aluminasilica-tin oxide, alumina-chromium oxide, alumina-nickel, chromium oxide-tungsten oxide alumina, and the like.
- the volatile inorganic halide be added to the olefin feed stock in amounts of 0.3-2% by weight of the charge, more or less, prior to contacting with the substantially non-volatile, solid cyclizing catalyst. It is also desirable that the reactants be substantially in the anhydrous condition, since small amounts of moisture have been found to gradually inactivate the solid catalyst mass. However, hydrogen may be added to the reacting mixture and in many cases, e. g., with the chromium combination catalysts, its use is desirable to suppress carbon formation on the catalyst surface.
- the reaction temperature and pressure depend more or less upon the pe of cyclic product desired. If cyclohexane or its derivatives are to be produced, the temperature is preferably low, below about 200 (3., and preferably. below C. but above about room temperature, and the pressure is at least that suificient to maintain a liquid reaction phase.
- the pressure should preferably be above about 100 lbs/sq. in. and up to about 1000 lbs/sq. in, although pressures up to about 5000 lbs. or even higher may be employed. With butene, the pressure is preferably above 30 lbs/sq. in.
- benzene or its derivatives are desired, it is preferable to operate at substantially atmospheric pressure and higher temperatures, say 200-350 C. and possibly higher, this, oi course, depending on the rate of flow of the reactant over the catalyst, the higher rate requiring a 'higher temperature for satisfactory conversion.
- the olefinic materials to be employed are the aliphatic olefins of three or four carbon atoms, alone, or in admixture with each other. Ethylene may be added, but preferably not over amounts in excess of equimolecular quantities necessary to produce six carbon ring compounds with the heavier olefins by cyclo-copolymerization.
- Alkylation of the aromatic products by means of the olefin feed stock may be suppressed by the introduction of small amounts of sulfur or sulfur compound such as sulfur dioxide, or any other condensation inhibitor. These, of course, cannot be employed with catalysts such as nickel or copper which are readily poisoned by such materials. Condensation reactions can be suppressed to a minimum, however, by adjusting temperature and time conditions so as to remove the aromatics as soon as they are formed followed by rapid hydrolysis of the halide catalyst by introduction of steam, water, alcohol, and the like to the stream immediately after leaving the actor.
- Example 1 Substantially anhydrous liquid propylene is placed in a bomb provided with a stirrer and a finely divided mixture of nickel and aluminum fluoride is added in an amount of about 2% by weight of the charge.
- the bomb is heated to about 100 F. (the pressure being about 190 lbs.) and boron fluoride is gradually bled into the bomb. The reaction is exothermic and overheating must be avoided.
- 0.5% BF; (based on the weight of the charge) has been added, the contents are cooled, washed with water or alcohol, (after filtering out the cyclizing catalyst) and the cyclohexane recovered by distillation.
- Example 2 Substantially anhydrous propylene is admixed with 0.3% BFr. and immediately passed into a tube containing a molybdenum sulfide-cop er mixture maintained at 325 C. and atmospheric pressure. The rate is adjusted so that not more than 2% to 5% of the propylene is converted to lower hydrocarbons. The product is immediately quenched with water and the benzene and other 'cyclic hydrocarbons are separated by cooling the washed gases or by scrubbing with a heavy oil.
- Example 3 Liquefied propylene is mixed with a small amount, about 1% to 2% by weight of finely divided nickel and about 0.3% BF: is gradually added to the mixture while stirring.
- the temperature in the reaction zone is maintained around 20 C., and the pressure prevailing within the reaction zone is about 150 lbs/sq. in.
- the liquid mixture is filtered, sprayed through water to hydrolyze the BFa, and then fractionated, and the product boiling at -85 C. is passed'over a catalyst consisting of chromium oxide and alumina, at such a rate that the hydrocarbon is in contact with the catalyst for a period of time within the range of from about 1-30 seconds.
- the temperature conditions prevailing in this second stage are in the neighborhood of about 450" C.
- the products are then conducted to a fractionating column from which the aromatic constituents are removed.
- reaction mixture materials which may be added to the reaction mixture are acetylene, carbonyls of chromium, molybdenum, nickel, and the like.
- Method for producing mono-cyclic hydro carbons comprising subjecting an aliphatic mono-olefin of 3 to 4 carbon atoms to the action of a volatile halide of the Friedel-Crafts type and a cycllzing catalyst comprising molybdenum sulfide and copper at a temperature between 20 C.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented July 13, 1943 UNITED STATES PATENT OFFICE TREATING HYDROCARBONS Peter J. Gaylor, Union, and Edward J. Mahler, Jersey City, N. J., assignors to Standard Oil Development Company, a corporation of Delaware No Drawing. Application December 12, 1940, Serial No. 369,758
3 Claims.
number thereof, and many commercial gasolines,
contain substantial quantities of this hydrocarbon. However, the amount of benzene available in this country is too limited to permit its full use as a blending agent in gasoline. That is to say, while it would be desirable to market commercial gasolines containing about 40% to 50% benzene, the total national benzene production is too low to permit its use to, this extent.
A number of methods for producing benzene from petroleum raw materials have been developed by prior art processes, but none of these processes is able to manufacture this aromatic hydrocarbon at a price competitive with that of the coal tar product. Since petroleum is available in this country in large quantities, an inexpensive and efficient process making it possible to produce large quantities of benzene from petroleum derivatives would have considerable value. Of course, in addition to its uses in the manufacture of motor fuels, benzene enjoys a large number of other commercial uses. Cyclohexane likewise finds wide commercial uses in the fuel, solvent and other fields.
The main object of the invention is to produce cyclohexane and/or benzene and/or alkyl derivatives thereof from lower mono-olefins of .less than five carbon atoms. When lower olefins are polymerized catalytically, according to present practice, good yields of liquid products are obtained, but these products contain only substantially olefin polymers and no aromatics. On the other hand, high temperature non-catalytic polymerization does result in the formation of some cyclic hydrocarbons, but this is accompanied by excessive formation of methane and other low molecular weight by-products which seriously afiect the cyclic hydrocarbon yield, making the process uneconomical.
According to the present invention, a catalytic method may be employed to obtain cyclic hydrocarbons directly in high yields and without substantial loss in waste lay-product gases.
According to the present invention, a lower olefin, preferably of 3-4 carbon atoms, may be made to undergo, by catalytic directing influence, a direct cyclo-polymerization in accordance with an overall mechanism which may be illustrated by the following equations:
CQHQ 3H: Benzene 0.115013; Toluene C eHn C H: Methyl cyclohcxane The process involves the use of a mixed catalyst comprising a volatile halide of the Friedel- CaHo C4Ha 2 CsHu C4Ha Crafts type, e. g.-AlCl3, BFa, HgClz, etc., and a cyclizing metal or metal compound, e. g., compounds of Mo, W, Al, V, U, Cr, Cu, Ni, etc. Examples of such latter cyclizing compounds are molybdenum sulfide or oxide, chromic oxide or sesquioxide, aluminum oxide or fluoride, tin oxide, copper, etc. Combinations of the latter are preferable, and as examples, the following have been found suitable: aluminum fluorideni'ckel, molybdenum sulfide-copper, aluminasilica-tin oxide, alumina-chromium oxide, alumina-nickel, chromium oxide-tungsten oxide alumina, and the like.
It is preferable that the volatile inorganic halide be added to the olefin feed stock in amounts of 0.3-2% by weight of the charge, more or less, prior to contacting with the substantially non-volatile, solid cyclizing catalyst. It is also desirable that the reactants be substantially in the anhydrous condition, since small amounts of moisture have been found to gradually inactivate the solid catalyst mass. However, hydrogen may be added to the reacting mixture and in many cases, e. g., with the chromium combination catalysts, its use is desirable to suppress carbon formation on the catalyst surface.
The reaction temperature and pressure depend more or less upon the pe of cyclic product desired. If cyclohexane or its derivatives are to be produced, the temperature is preferably low, below about 200 (3., and preferably. below C. but above about room temperature, and the pressure is at least that suificient to maintain a liquid reaction phase. For example, in the case of propene, as a raw material, the pressure should preferably be above about 100 lbs/sq. in. and up to about 1000 lbs/sq. in, although pressures up to about 5000 lbs. or even higher may be employed. With butene, the pressure is preferably above 30 lbs/sq. in.
If benzene or its derivatives are desired, it is preferable to operate at substantially atmospheric pressure and higher temperatures, say 200-350 C. and possibly higher, this, oi course, depending on the rate of flow of the reactant over the catalyst, the higher rate requiring a 'higher temperature for satisfactory conversion.
It is possible to prepare cyclohexane or its derivatives by the process previously outlined and then to dehydrogenate the product in a separate step to benzene or its derivatives in the presence of dehydrogenating catalysts at about 300-500 C.
The olefinic materials to be employed are the aliphatic olefins of three or four carbon atoms, alone, or in admixture with each other. Ethylene may be added, but preferably not over amounts in excess of equimolecular quantities necessary to produce six carbon ring compounds with the heavier olefins by cyclo-copolymerization.
Alkylation of the aromatic products by means of the olefin feed stock may be suppressed by the introduction of small amounts of sulfur or sulfur compound such as sulfur dioxide, or any other condensation inhibitor. These, of course, cannot be employed with catalysts such as nickel or copper which are readily poisoned by such materials. Condensation reactions can be suppressed to a minimum, however, by adjusting temperature and time conditions so as to remove the aromatics as soon as they are formed followed by rapid hydrolysis of the halide catalyst by introduction of steam, water, alcohol, and the like to the stream immediately after leaving the actor.
In order to illustrate the present invention, the following specific examples are set forth, with the understanding that the precise details enumerated therein are purely illustrative and do not impose a limitation on our invention.
Example 1 Substantially anhydrous liquid propylene is placed in a bomb provided with a stirrer and a finely divided mixture of nickel and aluminum fluoride is added in an amount of about 2% by weight of the charge. The bomb is heated to about 100 F. (the pressure being about 190 lbs.) and boron fluoride is gradually bled into the bomb. The reaction is exothermic and overheating must be avoided. After 0.5% BF; (based on the weight of the charge) has been added, the contents are cooled, washed with water or alcohol, (after filtering out the cyclizing catalyst) and the cyclohexane recovered by distillation.
Example 2 Substantially anhydrous propylene is admixed with 0.3% BFr. and immediately passed into a tube containing a molybdenum sulfide-cop er mixture maintained at 325 C. and atmospheric pressure. The rate is adjusted so that not more than 2% to 5% of the propylene is converted to lower hydrocarbons. The product is immediately quenched with water and the benzene and other 'cyclic hydrocarbons are separated by cooling the washed gases or by scrubbing with a heavy oil.
Example 3 Liquefied propylene is mixed with a small amount, about 1% to 2% by weight of finely divided nickel and about 0.3% BF: is gradually added to the mixture while stirring. The temperature in the reaction zone is maintained around 20 C., and the pressure prevailing within the reaction zone is about 150 lbs/sq. in. After four hours, the liquid mixture is filtered, sprayed through water to hydrolyze the BFa, and then fractionated, and the product boiling at -85 C. is passed'over a catalyst consisting of chromium oxide and alumina, at such a rate that the hydrocarbon is in contact with the catalyst for a period of time within the range of from about 1-30 seconds. The temperature conditions prevailing in this second stage are in the neighborhood of about 450" C. The products are then conducted to a fractionating column from which the aromatic constituents are removed.
Other materials which may be added to the reaction mixture are acetylene, carbonyls of chromium, molybdenum, nickel, and the like.
What we claim is:
1. Method for producing mono-cyclic hydro carbons comprising subjecting an aliphatic mono-olefin of 3 to 4 carbon atoms to the action of a volatile halide of the Friedel-Crafts type and a cycllzing catalyst comprising molybdenum sulfide and copper at a temperature between 20 C.
and 350 C.
2. The process of producing cyclic hydrocarbons from one 01' the class consisting of propylene and butylene which comprises admixing the olefin with a small amount of boron fluoride, passing the mixture into a zone containing a molybdenum sulfide-copper mixture, the said zone be ing maintained at a temperature of about C. and under a substantially atmospheric pressure, maintaining the reactant in the reaction zone for a period of from 1-30 seconds, thereafter quenching the reaction products and recovering cyclic hydrocarbons therefrom.
3. The process of producing cyclohexane compounds asset forth in claim 2, in which the temperature is from 20 C. to 200 0., and the pressure is greater than 30 lbs/square inch.
PETER J. GAYLOR. EDWARD J. MAKER.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US369758A US2324073A (en) | 1940-12-12 | 1940-12-12 | Treating hydrocarbons |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US369758A US2324073A (en) | 1940-12-12 | 1940-12-12 | Treating hydrocarbons |
Publications (1)
Publication Number | Publication Date |
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US2324073A true US2324073A (en) | 1943-07-13 |
Family
ID=23456794
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US369758A Expired - Lifetime US2324073A (en) | 1940-12-12 | 1940-12-12 | Treating hydrocarbons |
Country Status (1)
Country | Link |
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US (1) | US2324073A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2420030A (en) * | 1943-04-13 | 1947-05-06 | Standard Oil Dev Co | Motor fuels and preparation thereof |
US2425991A (en) * | 1945-12-07 | 1947-08-19 | Du Pont | Preparation of difluoroethane |
US2850546A (en) * | 1955-10-10 | 1958-09-02 | Texas Co | Production of cyclic hydrocarbons from hydrocarbon gases using a catalyst containingchromia, alumina and silica |
US2953610A (en) * | 1958-06-02 | 1960-09-20 | Monsanto Chemicals | Condensation processes |
US2971035A (en) * | 1958-01-07 | 1961-02-07 | Exxon Research Engineering Co | Process for the dethydrogenation of hydrocarbons in the presence of sulfur dioxide and a calcium nickel phosphate catalyst |
US3272877A (en) * | 1963-05-16 | 1966-09-13 | Monsanto Co | Olefin conversion to alicyclic hydrocarbons |
US4002577A (en) * | 1972-08-07 | 1977-01-11 | Toa Nenryo Kogyo Kabushiki Kaisha | Copper carbonyl-containing catalytic solutions |
US10322942B2 (en) | 2009-12-08 | 2019-06-18 | University Court Of The University Of St Andrews | Silicon phosphate and membrane comprising the same |
-
1940
- 1940-12-12 US US369758A patent/US2324073A/en not_active Expired - Lifetime
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2420030A (en) * | 1943-04-13 | 1947-05-06 | Standard Oil Dev Co | Motor fuels and preparation thereof |
US2425991A (en) * | 1945-12-07 | 1947-08-19 | Du Pont | Preparation of difluoroethane |
US2850546A (en) * | 1955-10-10 | 1958-09-02 | Texas Co | Production of cyclic hydrocarbons from hydrocarbon gases using a catalyst containingchromia, alumina and silica |
US2971035A (en) * | 1958-01-07 | 1961-02-07 | Exxon Research Engineering Co | Process for the dethydrogenation of hydrocarbons in the presence of sulfur dioxide and a calcium nickel phosphate catalyst |
US2953610A (en) * | 1958-06-02 | 1960-09-20 | Monsanto Chemicals | Condensation processes |
US3272877A (en) * | 1963-05-16 | 1966-09-13 | Monsanto Co | Olefin conversion to alicyclic hydrocarbons |
US4002577A (en) * | 1972-08-07 | 1977-01-11 | Toa Nenryo Kogyo Kabushiki Kaisha | Copper carbonyl-containing catalytic solutions |
US10322942B2 (en) | 2009-12-08 | 2019-06-18 | University Court Of The University Of St Andrews | Silicon phosphate and membrane comprising the same |
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