US3456027A - Aromatic hydrocarbons alkylated with normal butene polymers and the method of preparing the same - Google Patents
Aromatic hydrocarbons alkylated with normal butene polymers and the method of preparing the same Download PDFInfo
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- US3456027A US3456027A US565731A US3456027DA US3456027A US 3456027 A US3456027 A US 3456027A US 565731 A US565731 A US 565731A US 3456027D A US3456027D A US 3456027DA US 3456027 A US3456027 A US 3456027A
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- aromatic hydrocarbons
- benzene
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- butene
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- 229920000642 polymer Polymers 0.000 title description 41
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title description 21
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 title description 19
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title description 15
- 238000000034 method Methods 0.000 title description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 63
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 26
- 238000005804 alkylation reaction Methods 0.000 description 24
- 230000029936 alkylation Effects 0.000 description 21
- 239000000203 mixture Substances 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 17
- 150000002430 hydrocarbons Chemical class 0.000 description 16
- -1 monocyclic aromatic hydrocarbons Chemical class 0.000 description 14
- 229940063656 aluminum chloride Drugs 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical class CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 150000004996 alkyl benzenes Chemical class 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920001083 polybutene Polymers 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- BQDDBKCKVZMJAT-UHFFFAOYSA-K aluminum;azane;trichloride Chemical compound N.[Al+3].[Cl-].[Cl-].[Cl-] BQDDBKCKVZMJAT-UHFFFAOYSA-K 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910000286 fullers earth 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
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/107—Monocyclic hydrocarbons having saturated side-chain containing at least six carbon atoms, e.g. detergent alkylates
-
- 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
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- 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
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
- C07C2/68—Catalytic processes with halides
-
- 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
- C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
- C07C2527/126—Aluminium chloride
Definitions
- This invention relates to the alkylation of aromatic hydrocarbons. More particularly, it relates to the alkylation of aromatic hydrocarbons with olefinic hydrocarbons of high molecular weight to yield alkylates whose sulfonates are preferentially soluble in hydrocarbon oils.
- the present invention finds its preferred application in the alkylation of aromatic hydrocarbons, particularly monocyclic aromatic hydrocarbons, with aluminum chloride.
- aromatic hydrocarbons particularly monocyclic aromatic hydrocarbons
- aluminum chloride e.g., aluminum chloride
- olefinic hydrocarbons having less than about 15 carbon atoms in the molecule react quite smoothly, rapidly, and in good yields, and require the employment of a relatively small proportion of an aluminumchloride catalyst, e.g., in the range of about 0.5 to about percent by weight based on olefinic hydrocarbons.
- Failure to improve the alkylation reaction by the selection of relatively severe operating conditions may be attributed primarily to the fact that these conditions induce decomposition of such higher olefinic hydrocarbons to produce products having both more and less carbon atoms in the molecule than the olefinic feedstock, and these degradation products may then alkylate the aromatic hydrocarbon to produce nondescript alkylates of wide boiling range containing a greatly reduced proportion of the desired alkylation product. Also, severe operating conditions tend to destroy the alkylate produced from the feedstocks.
- This invention is concerned primarily with the production of alkyl aromatic hydrocarbons, particularly monocyclic aromatic hydrocarbons, having one or more side chains containing at least 15 carbon atoms.
- Alkyl aromatic hydrocarbons of this description are eminently suitable for sulfonation to yield sulfonic acids whose salts, i.e., soaps, are either preferentially soluble in hydrocarbon oils or highly soluble in hydrocarbon oils and quite insoluble in water at ordinary temperatures.
- soaps are capable of specialized applications which necessitate the placement of rigid specifications on the soaps, one of the specifications being the absence of preferentially water soluble soaps.
- this invention relates to the alkylation of an aromatic hydrocarbon, particularly a monocyclic aromatic hydrocarbon with a selected mixture of normal olefinic hydrocarbons to produce alkylates of relatively narrow boiling range and restricted variation in the number of carbon atoms in the molecule. More particularly, the invention relates to the alkylation of benzene or similar hydrocarbons with a mixture of normal butene polymers having a molecular weight in the range of from about 200 to about 800. Such polymers are preferably prepared by the polymerization of a petroleum refinery stream containing normal butenes and essentially free of isobutylenes.
- a typical such refinery stream essentially free of isobutylenes contains from about 11% to about 13% butene-l, from about 8.5% to about 10.5% cis-2- butene and from about 13.5% to about 16% trans-Z-butone, the remaining components being substantially C to C aliphatic hydrocarbons.
- a method of preparing butene polymers essentially free of isobutylene polymers from a refinery stream containing butenes as well as isobutylenes is described and claimed in copending U.S. application Serial No. 564,218, filed July 11, 1966, of John C. Heidler and Robert J. Lee, entitled Process For Producing Normal Butene Polymers, and assigned to the assignee of this application.
- Polymers having molecular Weights of from about 200 to about 800, prepared by the polymerization of a mixture of olefinic and alkyl hydrocarbons containing from about 11% to about 13% butene-1, from about 8.5% to about 10.5% cis-Z-butene and from about 13.5% to about 16% trans-Z-butene, and essentially free of isobutylenes, are referred to hereinafter as normal butene Polymers.
- Suitable aromatic hydrocarbons are monocyclic aromatic hydrocarbons, particularly benzene and alkylsubstituted benzenes, such as toluene, xylene, cumene, npropyl benzene, and the like.
- the alkylation is carried out in the presence of well known Friedel-Crafts catalysts, and preferably aluminum chloride. If desired, in conjunction with the catalyst there may be used a minor amount of a promoter such as hydrogen chloride or an alkyl chloride, such as, for example, isopropyl chloride. From about 0.5% to about 5% of the catalyst, e.g., aluminum chloride, based on the normal butene polymers, are used.
- Alkylation of the aromatic hydrocarbons with the aforesaid normal butene polymers is effected, in the liquid phase, at temperatures in the range of from about 0 F. to about 100 F., and preferably from about 30 F. to about F.
- the alkylation is usually conducted at atmospheric pressure, although higher pressures, e.g., about 50 to 500 psi. may sometimes be necessary or convenient.
- the alkylation is carried out by introducing a portion of the aromatic hydrocarbon, e.g., benzene, and the catalyst, e.g., aluminum chloride, into a suitable reactor, and slowly adding thereto a blend of the remaining portion of the artomatic hydrocarbon and the normal butene polymer, while vigorously stirring the reaction mixture. After completion of the reaction, the reaction mixture is allowed to settle, preferably in a settling zone, to permit the separation of aluminum chloride and aluminum chloride-hydrocarbon complex formed during the alkylation. If desired, after the removal of the bulk of the complex, the alkylation product may be freed of any occluded complex by treatment with anhydrous ammonia in accordance with the teachings in U.S.
- the aromatic hydrocarbon e.g., benzene
- the catalyst e.g., aluminum chloride
- Patent 3,121,125 issued Feb. 11, 1964, to Gus Nichols.
- Treatment with the anhydrous ammonia forms a solid aluminum chloride-ammonia complex which can be settled and separated from the alkylation product.
- the alkylation product after removal of the complex, is filtered through a suitable filtering medium, such as fullers earth or a diatomaceous earth, to remove any solid materials which may be occluded therein, and the filtrate heated to distill off excess unreacted hydrocarbons.
- the alkylate bottoms are then fractionated at suitable temperatures to obtain fractions of the desired molecular weights.
- the alkylates may be filtered through a suitable medium, such as Celite.
- the polymers obtained were normal butene polymers essentially free of isobutylene polymers, and had molecular weights of about 336 and about 415.
- the 336 molecular weight polymer is referred to hereinafter as No. 1 Polybutene, and the 415 molecular weight polymer as N o. 2 Polybutene,
- Step 2 A blend of 150 grams (0.45 mole) No. 1 Polybutene and 195 grams (2.5 moles) benzene was slowly added to the mixture of Step 1, and the reactor contents vigorously stirred at a temperature of 70 F. Addition of the blend was completed in 30 minutes and the mixture stirred for an additional 30 minutes.
- Step 3 At the end of one hour the product in the reactor was transferred to a separator or settler and permitted to settle for 45 minutes and the AlCl -hydrocarbon complex, formed in the reaction of Step 2, settled out and removed.
- Step 5 The filtrate of Step 4, containing alkylate and unreacted benzene, was heated to 250-300 F. and the unreacted benzene distilled off.
- Step 6 After removal of the unreacted benzene, the bottoms were heated to a temperature of 450 F. while blowing with nitrogen to strip off low molecular weight alkyl benzenes (29 grams, 19.3% based on polymer charged) formed as by-products in the alkylation step;
- Step 7 The recovered alkyl benzene bottoms had a molecular weight of 361 with a yield of 88% EXAMPLE II Step 1.-One hundred and ninety-five grams (2.5 moles) of benzene and 4.1 grams (2.0% based 'on polymer) of AlCl were added to a reactor.
- Step 2 A blend of 207 grams (0.5 mole) of No. 2 Polybutene and grams (2.5 moles) benzene was slowly added to the mixture of Step 1 and the reactor contents vigorously stirred at a temperature of 70 .F. Addition of the blend was completed in 30 minutes and the mixture stirred for an additional 30 minutes, and 3.0 grams (1.45% based on the polymer) of water were added to the reactor to deactivate the AlCl catalyst.
- Step 3 The product in the reactor was transferred to a separator and permitted to settle for 45 minutes, and the AlC l -hydrocarbon complex, formed in the reaction of Step 2, settled out and removed.
- Step 4.-Occluded A101 still in the reaction product, after removal of the AlCl -hydrocarbon complex, was removed by blowing the reaction product with anhydrous ammonia to form a solid AlCl -NH complex, and the mixture filtered to remove the complex.
- Step 5 The filtrate of Step 4, containing alkylate and unreacted benzene, was heated to 250-300 F. and the unreacted benzene distilled off.
- Step 6 After removal of the unreacted benzene, the bottoms were heated to a temperature of 450 F. while blowing with nitrogen to strip ofi? low molecular weight alkyl benzenes (4.3% based on polymer formed as byproducts; the maximum overhead temperature was 260- 270 F.
- Step 7 The benzene alkylate bottoms was filtered while hot through Celite. Eighty-seven percent of the desired alkyl benzene having a molecular weight of 373 was recovered.
- the present invention provides an improved process for the alkylation of aromatic hydrocarbons, particularly to produce higher alkyl aromatic hydrocarbons suitable for sulfonation to form oil-soluble or preferentially oil-soluble sulfonates.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
United States Patent 3 456,027 AROMATIC HYDROCARBONS ALKYLATED WITH NORMAL BUTENE POLYMERS AND THE METH- OD OF PREPARING THE SAME George S. Cnlbertson, Whiting, and Albert R. Sabol and Robert E. Karll, Munster, Ind., assiguors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Filed July 18, 1966, Ser. No. 565,731
' Int. Cl. C07c 3/56, 3/18 U.S. Cl. 260-671 2 Claims ABSTRACT OF THE DISCLOSURE Alkyl-substituted aromatic hydrocarbons prepared by reacting aromatic hydrocarbon and normal butene polymers having a molecular weight of about 200-800 under liquid phase alkylation conditions in the presence of aluminium chloride.
This invention relates to the alkylation of aromatic hydrocarbons. More particularly, it relates to the alkylation of aromatic hydrocarbons with olefinic hydrocarbons of high molecular weight to yield alkylates whose sulfonates are preferentially soluble in hydrocarbon oils.
The present invention finds its preferred application in the alkylation of aromatic hydrocarbons, particularly monocyclic aromatic hydrocarbons, with aluminum chloride. In this type of alkylation reaction, olefinic hydrocarbons having less than about 15 carbon atoms in the molecule react quite smoothly, rapidly, and in good yields, and require the employment of a relatively small proportion of an aluminumchloride catalyst, e.g., in the range of about 0.5 to about percent by weight based on olefinic hydrocarbons. However, higher branched chain olefinic hydrocarbons, by which we mean branced chain olefinic hydrocarbons having at least 15 carbon atoms, especially 20 or more carbon atoms, e.g., 25, 30, 40, or 40 carbon atoms in the molecule, do not alkylate well, that is to say, they require relatively gross amounts of aluminum chloride catalyst, long reaction periods and afford relatively poor yields. Attempts to overcome the sluggish behavior of such higher olefinic hydrocarbons in these alkylation reactions by the employment of more severe operating conditions, such as high alkylation temperatures, high proportions of catalysts, or long reaction periods are unsuccessful. Failure to improve the alkylation reaction by the selection of relatively severe operating conditions may be attributed primarily to the fact that these conditions induce decomposition of such higher olefinic hydrocarbons to produce products having both more and less carbon atoms in the molecule than the olefinic feedstock, and these degradation products may then alkylate the aromatic hydrocarbon to produce nondescript alkylates of wide boiling range containing a greatly reduced proportion of the desired alkylation product. Also, severe operating conditions tend to destroy the alkylate produced from the feedstocks.
This invention is concerned primarily with the production of alkyl aromatic hydrocarbons, particularly monocyclic aromatic hydrocarbons, having one or more side chains containing at least 15 carbon atoms. Alkyl aromatic hydrocarbons of this description are eminently suitable for sulfonation to yield sulfonic acids whose salts, i.e., soaps, are either preferentially soluble in hydrocarbon oils or highly soluble in hydrocarbon oils and quite insoluble in water at ordinary temperatures. These soaps are capable of specialized applications which necessitate the placement of rigid specifications on the soaps, one of the specifications being the absence of preferentially water soluble soaps.
It is an object of the present invention to provide a "ice method of preparing butene polymer alkylated aromatic hydrocarbons without obtaining undesirable degradation products. It is another object of this invention to provide a process for the alkylation of monocyclic aromatic hydrocarbons with butene polymers having a molecular weight from about 200 to about 800 to produce alkylated aromatic hydrocarbons whose alkyl side chains have molecular weights substantially the same as the molecular Weights of the polymer reactants. A further object of the invention is to provide a stable butene polymer alkylated benzene suitable for sulfonation to yield sulfonic acids, the salts of which are preferentially oil-soluble. Other objects and advantages of the invention will become apparent as the description thereof proceeds.
In the preferred embodiment, this invention relates to the alkylation of an aromatic hydrocarbon, particularly a monocyclic aromatic hydrocarbon with a selected mixture of normal olefinic hydrocarbons to produce alkylates of relatively narrow boiling range and restricted variation in the number of carbon atoms in the molecule. More particularly, the invention relates to the alkylation of benzene or similar hydrocarbons with a mixture of normal butene polymers having a molecular weight in the range of from about 200 to about 800. Such polymers are preferably prepared by the polymerization of a petroleum refinery stream containing normal butenes and essentially free of isobutylenes. A typical such refinery stream essentially free of isobutylenes, contains from about 11% to about 13% butene-l, from about 8.5% to about 10.5% cis-2- butene and from about 13.5% to about 16% trans-Z-butone, the remaining components being substantially C to C aliphatic hydrocarbons. A method of preparing butene polymers essentially free of isobutylene polymers from a refinery stream containing butenes as well as isobutylenes is described and claimed in copending U.S. application Serial No. 564,218, filed July 11, 1966, of John C. Heidler and Robert J. Lee, entitled Process For Producing Normal Butene Polymers, and assigned to the assignee of this application.
Polymers having molecular Weights of from about 200 to about 800, prepared by the polymerization of a mixture of olefinic and alkyl hydrocarbons containing from about 11% to about 13% butene-1, from about 8.5% to about 10.5% cis-Z-butene and from about 13.5% to about 16% trans-Z-butene, and essentially free of isobutylenes, are referred to hereinafter as normal butene Polymers.
Suitable aromatic hydrocarbons are monocyclic aromatic hydrocarbons, particularly benzene and alkylsubstituted benzenes, such as toluene, xylene, cumene, npropyl benzene, and the like.
The alkylation is carried out in the presence of well known Friedel-Crafts catalysts, and preferably aluminum chloride. If desired, in conjunction with the catalyst there may be used a minor amount of a promoter such as hydrogen chloride or an alkyl chloride, such as, for example, isopropyl chloride. From about 0.5% to about 5% of the catalyst, e.g., aluminum chloride, based on the normal butene polymers, are used.
Alkylation of the aromatic hydrocarbons with the aforesaid normal butene polymers is effected, in the liquid phase, at temperatures in the range of from about 0 F. to about 100 F., and preferably from about 30 F. to about F. The alkylation is usually conducted at atmospheric pressure, although higher pressures, e.g., about 50 to 500 psi. may sometimes be necessary or convenient.
Briefly, the alkylation is carried out by introducing a portion of the aromatic hydrocarbon, e.g., benzene, and the catalyst, e.g., aluminum chloride, into a suitable reactor, and slowly adding thereto a blend of the remaining portion of the artomatic hydrocarbon and the normal butene polymer, while vigorously stirring the reaction mixture. After completion of the reaction, the reaction mixture is allowed to settle, preferably in a settling zone, to permit the separation of aluminum chloride and aluminum chloride-hydrocarbon complex formed during the alkylation. If desired, after the removal of the bulk of the complex, the alkylation product may be freed of any occluded complex by treatment with anhydrous ammonia in accordance with the teachings in U.S. Patent 3,121,125, issued Feb. 11, 1964, to Gus Nichols. Treatment with the anhydrous ammonia forms a solid aluminum chloride-ammonia complex which can be settled and separated from the alkylation product. The alkylation product, after removal of the complex, is filtered through a suitable filtering medium, such as fullers earth or a diatomaceous earth, to remove any solid materials which may be occluded therein, and the filtrate heated to distill off excess unreacted hydrocarbons. The alkylate bottoms are then fractionated at suitable temperatures to obtain fractions of the desired molecular weights. If desired, the alkylates may be filtered through a suitable medium, such as Celite.
The following specific examples illustrate the process of the present invention. In these examples, the normal butene polymers employed were obtained, as described and claimed in the aforesaid co-pending application, by the aluminum chloride polymerization of a petroleum refinery stream having the following approximate composition:
Percent Propane 2.7 Propylene 0.7 n-Butane 18.3 Isobutane 40.4 Butene-l 12.0 cis-Z-butene 9.4 trans-2-butene 14.7 Isobutylene 0.6 Pentane 1.2
The polymers obtained were normal butene polymers essentially free of isobutylene polymers, and had molecular weights of about 336 and about 415. The 336 molecular weight polymer is referred to hereinafter as No. 1 Polybutene, and the 415 molecular weight polymer as N o. 2 Polybutene,
EXAMPLE I Step 1.One hundred and ninety-five grams (2.5 moles) of benzene and 3 grams (2.0% based on polymer) or A101 were added to a reactor.
Step 2.A blend of 150 grams (0.45 mole) No. 1 Polybutene and 195 grams (2.5 moles) benzene was slowly added to the mixture of Step 1, and the reactor contents vigorously stirred at a temperature of 70 F. Addition of the blend was completed in 30 minutes and the mixture stirred for an additional 30 minutes.
Step 3.At the end of one hour the product in the reactor was transferred to a separator or settler and permitted to settle for 45 minutes and the AlCl -hydrocarbon complex, formed in the reaction of Step 2, settled out and removed.
Step 4.Occluded AlCl still in the reaction product, after removal of the AlCl -hydrocarbon complex, was removed by glowing the reaction product with anhydrous ammonia to form a solid AlCl -NH complex, and the mixture filtered to remove the complex.
Step 5.The filtrate of Step 4, containing alkylate and unreacted benzene, Was heated to 250-300 F. and the unreacted benzene distilled off.
Step 6.After removal of the unreacted benzene, the bottoms were heated to a temperature of 450 F. while blowing with nitrogen to strip off low molecular weight alkyl benzenes (29 grams, 19.3% based on polymer charged) formed as by-products in the alkylation step;
the maximum overhea temp ratu e was 260270 F.
Step 7.The recovered alkyl benzene bottoms had a molecular weight of 361 with a yield of 88% EXAMPLE II Step 1.-One hundred and ninety-five grams (2.5 moles) of benzene and 4.1 grams (2.0% based 'on polymer) of AlCl were added to a reactor.
Step 2.A blend of 207 grams (0.5 mole) of No. 2 Polybutene and grams (2.5 moles) benzene was slowly added to the mixture of Step 1 and the reactor contents vigorously stirred at a temperature of 70 .F. Addition of the blend was completed in 30 minutes and the mixture stirred for an additional 30 minutes, and 3.0 grams (1.45% based on the polymer) of water were added to the reactor to deactivate the AlCl catalyst.
Step 3.The product in the reactor was transferred to a separator and permitted to settle for 45 minutes, and the AlC l -hydrocarbon complex, formed in the reaction of Step 2, settled out and removed.
Step 4.-Occluded A101 still in the reaction product, after removal of the AlCl -hydrocarbon complex, was removed by blowing the reaction product with anhydrous ammonia to form a solid AlCl -NH complex, and the mixture filtered to remove the complex.
Step 5.The filtrate of Step 4, containing alkylate and unreacted benzene, was heated to 250-300 F. and the unreacted benzene distilled off.
Step 6.-After removal of the unreacted benzene, the bottoms were heated to a temperature of 450 F. while blowing with nitrogen to strip ofi? low molecular weight alkyl benzenes (4.3% based on polymer formed as byproducts; the maximum overhead temperature was 260- 270 F.
Step 7.The benzene alkylate bottoms was filtered while hot through Celite. Eighty-seven percent of the desired alkyl benzene having a molecular weight of 373 was recovered.
- EXAMPLE III The alkylation in this example, carried out as described in Example II, except that 3.1 grams (1.5% based on polymer) AlCl was used, yielded 9.6% (based on polymer) of undesired low molecular weight benzene alkylate, and'79% of the desired alkyl benzne having a molecular weight of 413.
Similar alkylations using isobutylene polymers, instead of the normal butene polymers of comparable molecular weights, leads to substantially greater yields of undesired low molecular weight alkyl benzenes and poor yields of alkyl benzenes of desired usable higher molecular weight. Aluminum chloride in the presence of benzene rapidly depolymerizes isobutylene polymer into polymers of :relatively low molecular weight and monomer molecules, thus resulting in excessive amounts of benzene alkylates of undesired low molecular Weight.
It will be apparent that the present invention provides an improved process for the alkylation of aromatic hydrocarbons, particularly to produce higher alkyl aromatic hydrocarbons suitable for sulfonation to form oil-soluble or preferentially oil-soluble sulfonates.
Percentages given herein are Weight percentages unless otherwise stated.
While particular embodiments of the invention have been described, it is to be understood that the invention is not limited thereto, but covers such modifications and variations as come within the spirit and scope of the appended claims.
We claim:
1. The process of alkylating benzene with olefin polymers having a molecular Weight of from about 200 to about 800 in the presence of aluminum chloridecatalyst, whereby the yield of undesired low molecular weight alkylates is minimized and the yield of desired high molecular weight alkylates maximized, which process comprises reacting benzene in the presence of an aluminum chloride catalyst with normal butene polymers having molecular weights in the range of from about 200 to about 800, and recovering high molecular weight alkyl benzene from said reaction, said normal butene polymers being obtained by the polymerization, in the presence of a Friedel-Crafts catalyst, of a hydrocarbon mixture, essentially free of isobutylene and consisting essentially of from about 11% to about 13% butene-l, from about 8.5% to about 10.5% cis-2-butene, from about 13.5% to about 16% trans-2- butene, and the remainder C3"C5 aliphatic hydrocarbons.
2. The process of claim 1 wherein the normal butene polymers are obtained by the aluminum chloride polymerization of a hydrocarbon mixture having the following approximate composition:
Percent Isobutane 40,4 Butene-l 12.0 cis-Z-butene 9.4 trans-2-butene 14.7 Isobutylene 0.6 Pentane 1.2
References Cited UNITED STATES PATENTS 3,104,267 9/ 1963 Antonsen et al 260671 3,108,145 10/1963 Antonsen 260-671 3,315,009 4/1967 Englebrecht et al. 260671 DELBERT E. GANTZ, Primary Examiner CURTIS R. DAVIS, Assistant Examiner "H050 I UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 5 7 Dated July 15, 1969 Inventor(s) George S. Culbertson, Albert R. Sabol, and Robert E. Karll It is certified that error appears in the above-identified petent and that said Letters Patent are hereby corrected as shown below:
r- Column 1, line 3 "eluminumchloride" should read aluminum chloride line 39, +0" (second occurrence) should read 5O Column 3, line 50, "or" should read of Column line 31, "polymer formed" should read polymer) formed line 4-1, "A1012" should read A101 line +3, "benzne" should read benzene line 51, "polymer" (first occurrence) should read polymers SIGNED AND SEALED MAR 2 41970 Attest:
Edward Matcher WILLIAM E. scauxm. Aumfing ()ffi gg Commissioner of Pat n
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US56573166A | 1966-07-18 | 1966-07-18 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3758624A (en) * | 1971-05-26 | 1973-09-11 | Ethyl Corp | Gasoline compositions |
WO1980000894A1 (en) * | 1978-10-26 | 1980-05-01 | Gulf Research Development Co | Insulation of electrical apparatus with a synthetic transformer oil |
US4238343A (en) * | 1978-10-26 | 1980-12-09 | Gulf Research & Development Company | High fire point alkylaromatic insulating fluid |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3104267A (en) * | 1960-09-12 | 1963-09-17 | Sun Oil Co | Preparing of long chain alkyl aromatic hydrocarbons |
US3108145A (en) * | 1960-11-29 | 1963-10-22 | Sun Oil Co | Preparation of olefin polymers |
US3315009A (en) * | 1963-07-12 | 1967-04-18 | Monsanto Co | Polymerization process |
-
1966
- 1966-07-18 US US565731A patent/US3456027A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3104267A (en) * | 1960-09-12 | 1963-09-17 | Sun Oil Co | Preparing of long chain alkyl aromatic hydrocarbons |
US3108145A (en) * | 1960-11-29 | 1963-10-22 | Sun Oil Co | Preparation of olefin polymers |
US3315009A (en) * | 1963-07-12 | 1967-04-18 | Monsanto Co | Polymerization process |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3758624A (en) * | 1971-05-26 | 1973-09-11 | Ethyl Corp | Gasoline compositions |
WO1980000894A1 (en) * | 1978-10-26 | 1980-05-01 | Gulf Research Development Co | Insulation of electrical apparatus with a synthetic transformer oil |
US4238343A (en) * | 1978-10-26 | 1980-12-09 | Gulf Research & Development Company | High fire point alkylaromatic insulating fluid |
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