US2426665A - Alkylation of aromatic hydrocarbons - Google Patents
Alkylation of aromatic hydrocarbons Download PDFInfo
- Publication number
- US2426665A US2426665A US436314A US43631442A US2426665A US 2426665 A US2426665 A US 2426665A US 436314 A US436314 A US 436314A US 43631442 A US43631442 A US 43631442A US 2426665 A US2426665 A US 2426665A
- Authority
- US
- United States
- Prior art keywords
- alkylation
- mixture
- catalyst
- aromatic hydrocarbons
- hydrocarbons
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title description 20
- 238000005804 alkylation reaction Methods 0.000 title description 12
- 230000029936 alkylation Effects 0.000 title description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 23
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 17
- 150000002430 hydrocarbons Chemical class 0.000 description 17
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 229910001507 metal halide Inorganic materials 0.000 description 9
- 150000005309 metal halides Chemical class 0.000 description 9
- 230000002152 alkylating effect Effects 0.000 description 8
- 235000005074 zinc chloride Nutrition 0.000 description 8
- 239000011592 zinc chloride Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000001555 benzenes Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011833 salt mixture Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum halide Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000000374 eutectic mixture Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen 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
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 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
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- C07C2/54—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
-
- 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
-
- 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
- C07C2527/138—Compounds comprising a halogen and an alkaline earth metal, magnesium, beryllium, zinc, cadmium or mercury
Definitions
- This invention is concerned with the interaction of aromatic hydrocarbons with olefins in I in producing molten metal halide mixtures em- 7 the presence of a catalyst. It is more specifically v concerned with a. simple and easily regulated process involving the use of a, catalyst which is altered only slightly in the course of the reaction but which catalyzes the desired conversion with a high degree of efllciency.
- Processes for the formation of more highly alkylated aromatic hydrocarbons from less highly alkylated aromatic hydrocarbons are of importance 'not only from the standpoint of producing high antiknock motor fuel fractions but for preparing alkylated aromatic hydrocarbons useful as intermediates in the production of synthetic organic chemicals.
- the present invention comprises a process for' alkylating aromatic hydrocarbons with olefinic hydrocarbons in the presence of a hydrogen halide and of a molten mixture of metal halides of the Friedel-Crafts type.
- Aromatic hydrocarbons such as benzene, toluene, other aflrylated be'nzenes, naphthalene, alkylated naphthalenes, other poly-nuclear aromatics, etc., which are alkylated by olefinic hydrocarbons as hereinafter set forth, may be obtained by the distillation of coal, by the dehydrogenation of naphthenic hydrocarbons, by the dehydrogenation and/or cyclization of aliphatic hydrocarbons, alkylated aromatic hydrocarbons, and alkylated naphthenic hydrocarbons, and by other means.
- the olefins utilized for alkylating the aromatic hydrocarbons may be either normally gaseous or normally liquid.
- Typical gaseous oleflns comprise ethylene, propene, and the butenes, while normally liquid olefins may consist of pentenes, hexenes, and higher boiling olefins.
- Olefinic hydrocarbons suitable for use in alkylation of benzene and its homologs and polynuclear aromatic hydrocarbons may be obtained from gaseous and liquid products formed from" the cracking of hydrocarbon oils, by dehydrogenation of paraflins in the presence of catalysts, by the dehydration of alcohols, 01 from any other source.
- the catalyst employed in the process of the present invention comprisesmolten mixtures of metal halides of the Friedel-Crafts type. These mixtures of metal halides have relatively low melting points and may comprise eutectic mixtures having minimum melting points in case such mixtures have fusion points corresponding to optimum temperatures for the alkylation reaction, but the usable catalysts are not limited merely to these eutectic mixtures.
- Catalysts oi the Friedel-Crafts type utilizable ployed in the process of the present invention include the halides and particularly the chlorides and bromides, of such metals as aluminum, zirconium, zinc, tin, antimony, boron, cadmium,
- molten catalysts include a mixture of aluminum chloride and zinc chloride and also a 3-component catalyst comprising essentially 'a molten mixture of the chlorides of aluminum, zinc, and sodium.
- solidification point is used in reference to that temperature at which complete solidification of the salt mixture occurs and in most cases the temperature of solidification is lower than the reaction temperatures found to give good results in the alkylation of an aromatic hydrocarbon by an olefin in the presence of the particular metal halide mixture employed.
- molten mixture of metal halides is used. in referring to a mixture of metal halides containing a. substantial proportion of a Friedel-Crafts type catalyst and employed at temperatures above the solidification points of said mixtures.
- Alkylation operations may be conducted by passing the aromatic and olefinic hydrocarbons upwardly through stationary pools of a molten catalyst salt mixture or by similarly passing the hydrocarbons upwardly coun'tercurrent to a descending molten salt mixture in a substantially vertical reactor which may or may not contain filling or spacing materials such as crushed tragments of relatively inert packing material as for ed to fractionation and the separated salt mixexample silica, or which may contain regularly spaced pans or trays, Alkylation treatment may also be carried out by passing liquid or liquefied hydrocarbons and a proportioned amount of molten salt mixture through tubular elements preferably under conditions of turbulent flow, after which the products from the tubular reactors are discharged into separating chambers from which the hydrocarbon products are directi 01 more.
- suitable alkylation temperoperating pressure may vary from substantially atmospheric to approximately 100 atmospheres the particular type of operation employed as well as with the characteristics 01 the charging stock.
- a hydrogen halide as hydrogen chloride or hydrogen bromide present in a reaction zone so as to promote the catalytic activity of the molten metal halide catalyst.
- the presence of hydrogen is advantageous in minimizing undesirable side reactions leading. to the-formation of relatively high molecular weight compounds.
- Atures are above the solidification point of the catalyst mixture but below about 150 C.
- V :l The character of the inventionand the type of results obtained by its use in practice ar evident from the preceding specification and example given, although they are not to be considered as imposingundue limitations upon its generally acting an aromatic hydrocarbon with an olefinic hydrocarbon at an alkylatin'g temperature below about 150 C. in the presence of a catalyst comprising a mixture of a major mol proportion of an aluminum halide and a minor mol proportion of a zinc halide, said halides being so proportioned that the mixture thereof is in molten condition at said alkylating temperature.
- An alkylation process which comprises reacting an aromatic hydrocarbon with an olefinic hydrocarbon at an alkylating temperature below about C. in the presence of a catalyst comprising a mixture of aluminum chloride and zinc chloride in the ratio of about 2 mols of aluminum chloride per mol of zinc chloride. said mixture being in a molten conditior at said alkylating temperature.
- An alkylation process which comprises reacting benzene with propylene at an alkylating temperature below about 150 C. in the presence of a catalyst comprising a mixture of aluminum chloride and zinc chloride in the ratio of about 2 mols of aluminum chloride per mol of zinc chloride, said mixture being in a molten condition at said alkylating temperature.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
Patcnted Sept. 2, 1947 2,426,665 NT OFFICE ALK YLATION- F AROMATIC HYDRO: CARBON S Herman S. Bloch, Chicago, Ill., assignor to Universal Oil Products Company, Chicago, 111., a corporation oi Delaware No Drawing. Application Marches, 1942, Serial Nit-436,314.
Claims.
' This is a continuation-in-part of my co-pending application Serial No. 398,194, allied June 16, 1941.
This invention is concerned with the interaction of aromatic hydrocarbons with olefins in I in producing molten metal halide mixtures em- 7 the presence of a catalyst. It is more specifically v concerned with a. simple and easily regulated process involving the use of a, catalyst which is altered only slightly in the course of the reaction but which catalyzes the desired conversion with a high degree of efllciency.
Processes for the formation of more highly alkylated aromatic hydrocarbons from less highly alkylated aromatic hydrocarbons are of importance 'not only from the standpoint of producing high antiknock motor fuel fractions but for preparing alkylated aromatic hydrocarbons useful as intermediates in the production of synthetic organic chemicals.
In one specific embodiment the present invention comprises a process for' alkylating aromatic hydrocarbons with olefinic hydrocarbons in the presence of a hydrogen halide and of a molten mixture of metal halides of the Friedel-Crafts type.
Aromatic hydrocarbons, such as benzene, toluene, other aflrylated be'nzenes, naphthalene, alkylated naphthalenes, other poly-nuclear aromatics, etc., which are alkylated by olefinic hydrocarbons as hereinafter set forth, may be obtained by the distillation of coal, by the dehydrogenation of naphthenic hydrocarbons, by the dehydrogenation and/or cyclization of aliphatic hydrocarbons, alkylated aromatic hydrocarbons, and alkylated naphthenic hydrocarbons, and by other means.
The olefins utilized for alkylating the aromatic hydrocarbons may be either normally gaseous or normally liquid. Typical gaseous oleflns comprise ethylene, propene, and the butenes, while normally liquid olefins may consist of pentenes, hexenes, and higher boiling olefins. Olefinic hydrocarbons suitable for use in alkylation of benzene and its homologs and polynuclear aromatic hydrocarbons may be obtained from gaseous and liquid products formed from" the cracking of hydrocarbon oils, by dehydrogenation of paraflins in the presence of catalysts, by the dehydration of alcohols, 01 from any other source.
The catalyst employed in the process of the present invention comprisesmolten mixtures of metal halides of the Friedel-Crafts type. These mixtures of metal halides have relatively low melting points and may comprise eutectic mixtures having minimum melting points in case such mixtures have fusion points corresponding to optimum temperatures for the alkylation reaction, but the usable catalysts are not limited merely to these eutectic mixtures.
Catalysts oi the Friedel-Crafts type utilizable ployed in the process of the present invention include the halides and particularly the chlorides and bromides, of such metals as aluminum, zirconium, zinc, tin, antimony, boron, cadmium,
chromium, iron,-etc., although it is recognized that they are not interchangeable in any given type of reaction and that not allwill catalyze certain alkylation reactions. Ofthe metal halides mentioned, aluminum chloride is generally the.
most applicable and zirconium chloride and zinc chloride follow in approximate order of decreasing activity. The low melting point mixtures,
which are preferably used in accordance with the I present invention, may include combinations of any of the known'catalysts of the Friedel-Crafts type which have definite activity as catalysts for the alkylation' of aromatic hydrocarbons. It may also be desirable to composit proportioned amounts of two Friedel-Crafts type catalysts with another metal salt Of lesser catalytic activity to form a mixture with a relatively low solidification point. Preferred molten catalysts include a mixture of aluminum chloride and zinc chloride and also a 3-component catalyst comprising essentially 'a molten mixture of the chlorides of aluminum, zinc, and sodium. I
The term solidification point is used in reference to that temperature at which complete solidification of the salt mixture occurs and in most cases the temperature of solidification is lower than the reaction temperatures found to give good results in the alkylation of an aromatic hydrocarbon by an olefin in the presence of the particular metal halide mixture employed. In this specification and in the claims the term molten mixture of metal halides is used. in referring to a mixture of metal halides containing a. substantial proportion of a Friedel-Crafts type catalyst and employed at temperatures above the solidification points of said mixtures.
Alkylation operations may be conducted by passing the aromatic and olefinic hydrocarbons upwardly through stationary pools of a molten catalyst salt mixture or by similarly passing the hydrocarbons upwardly coun'tercurrent to a descending molten salt mixture in a substantially vertical reactor which may or may not contain filling or spacing materials such as crushed tragments of relatively inert packing material as for ed to fractionation and the separated salt mixexample silica, or which may contain regularly spaced pans or trays, Alkylation treatment may also be carried out by passing liquid or liquefied hydrocarbons and a proportioned amount of molten salt mixture through tubular elements preferably under conditions of turbulent flow, after which the products from the tubular reactors are discharged into separating chambers from which the hydrocarbon products are directi 01 more.
rate of flow which are utilizable for carrying out the desired alkyl'ation reaction will vary with the compounds undergoing treatment and with the nature and composition of the catalyst used, and accordingly only relatively broad ranges can be given. In general suitable alkylation temperoperating pressure may vary from substantially atmospheric to approximately 100 atmospheres the particular type of operation employed as well as with the characteristics 01 the charging stock.
In order to favor the production of mono-alkylated aromatic hydrocarbons and to substantially avoid olefin polymerization, it is advisable to charge from about 1 to about molecular proportions of aromatic hydrocarbon per 1 molecular proportion of olefinic hydrocarbon introduced to the alkylation reaction.- It is preferable, however, to maintain a substantial molar excess of aromatic hydrocarbon to olefinic hydrocarbon throughout the entire reaction.
It is often desirable to have small but definite amounts of a hydrogen halide as hydrogen chloride or hydrogen bromide present in a reaction zone so as to promote the catalytic activity of the molten metal halide catalyst. The presence of hydrogen is advantageous in minimizing undesirable side reactions leading. to the-formation of relatively high molecular weight compounds.
The following example is introduced'as characteristic of the practical operation of the process, althoughit is not presented with the intention of limiting the scope of the invention in exact correspondence with the numerical data presented.
80 parts by weight of benzene, 21 parts by weight of propene, and 8.2 parts by weight of a catalyst consisting of 65% by weight of aluminum chloride and by weight of zinc chloride having a solidification point of 117 C.. were placed in an autoclave and heated with stirring at 125 C. for 1.5 hours. The liquid hydrocarbon product, after separation from the catalyst, was washed, dried and distilled to separate unconverted benzene from alkylated benzene. The 89.2 parts by weight of washed and dried reaction product obtained was thus separated into the following fractions represented in terms of. the weight per cent based upon the benzene charged and also upon the propene charged. It is noted that mono-isopropyl benzene was the major product.
, atures are above the solidification point of the catalyst mixture but below about 150 C. The
Flow rates will obviously vary with The bromine number of the entire hydrocare bon product was 1, thus indicating that substantially no propene polymers were present and that nearly all of the propene had. been utilized to form alkylated benzenes. Inspite or the rather large mechanical loss/which amounted to about 15 'parts by weight of the total 101 parts by weight of benzene and propene charged, the alkylated benzenes recovered represented approximately 180% of the propene charged. Of the alkylated benzenes formed and recovered, approximately '7 5% by weight was mono-isopropylbenzene. V :l The character of the inventionand the type of results obtained by its use in practice ar evident from the preceding specification and example given, although they are not to be considered as imposingundue limitations upon its generally acting an aromatic hydrocarbon with an olefinic hydrocarbon at an alkylatin'g temperature below about 150 C. in the presence of a catalyst comprising a mixture of a major mol proportion of an aluminum halide and a minor mol proportion of a zinc halide, said halides being so proportioned that the mixture thereof is in molten condition at said alkylating temperature.
2. The process of claim 1 further characterized in that said aromatic hydrocarbon comprises a mono-nuclear aromatic hydrocarbon.
' 3. The process of claim 1 further characterized in that said aromatic hydrocarbon comprises benzene. I I
4. The process of claim 1 further characterized in that said aromatic hydrocarbon comprises a polynuclear aromatic hydrocarbon.
5. The process of claim 1 further characterized in that said olefinic hydrocarbon comprises a normally gaseous olefin.
. 6. The process of claim 1 further characterized hydrocarbon at an alkylatingtemperatur below about 150 C. in the presence of a catalyst comprising a mixture of a major mol proportion of aluminum chloride and a minor mol proportion of zinc chloride, said chlorides being so proportioned that the mixture thereof is in molten condition at said alkylating temperature.
8. The process of claim 7 further characterized in that said catalyst also contains sodium chloride.
9. An alkylation process which comprises reacting an aromatic hydrocarbon with an olefinic hydrocarbon at an alkylating temperature below about C. in the presence of a catalyst comprising a mixture of aluminum chloride and zinc chloride in the ratio of about 2 mols of aluminum chloride per mol of zinc chloride. said mixture being in a molten conditior at said alkylating temperature.
10. An alkylation process which comprises reacting benzene with propylene at an alkylating temperature below about 150 C. in the presence of a catalyst comprising a mixture of aluminum chloride and zinc chloride in the ratio of about 2 mols of aluminum chloride per mol of zinc chloride, said mixture being in a molten condition at said alkylating temperature.
' HERMAN s. BLOCH.
(References on followingpage) 5 i 6 REFERENCES CITED I FOREIGN PATENTS The following references are of record in the Number Country Date file of this patent: 699,607 Germany Nov. 7, 1940 UNITED STATES PATENTS 5 OTHER REFERENCES Number 1 Name Date Thomas, Anhydrous Aluminum Chloride 1n 1,878,963 Michel Sept. 20, 1932 Organic Chemistry," pub. Reinhold Pub. Co 'p 1,953,702 Davidson Apr. 3, 1934 New York (1941), page 45. (1 page). Copy in 2,001,907 Ipatiefl May 21, 1935 Division 31. 2,028,472 Rabe Jan. 21. 1936 Grosse et 21., New Metal Halid Catalysts, 2,143,493 Stanley et a] Jan. 10, 1939 Jour. Org. Chem. (1937), pages 559-566 (7 pages, 2,271,299 Ipatiefl' et a1 Jan. 27, 1942- page 581 especially pertinent). Patent Omee 2,286,129 Veltman June 9, 1942 Library 260-671.
2,009,108 Eglofl' July 23, 1935 2,370,195 Ross et a1 Feb. 27, 1945 18
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US436314A US2426665A (en) | 1942-03-26 | 1942-03-26 | Alkylation of aromatic hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US436314A US2426665A (en) | 1942-03-26 | 1942-03-26 | Alkylation of aromatic hydrocarbons |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2426665A true US2426665A (en) | 1947-09-02 |
Family
ID=23731953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US436314A Expired - Lifetime US2426665A (en) | 1942-03-26 | 1942-03-26 | Alkylation of aromatic hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2426665A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3420909A (en) * | 1967-08-21 | 1969-01-07 | Universal Oil Prod Co | Alkylation process |
| US4045504A (en) * | 1968-10-23 | 1977-08-30 | The Lummus Company | Coupling process |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1878963A (en) * | 1927-12-01 | 1932-09-20 | Ig Farbenindustrie Ag | Manufacture of condensation products |
| US1953702A (en) * | 1928-01-26 | 1934-04-03 | Carbide & Carbon Chem Corp | Method of making alkyl benzenes |
| US2001907A (en) * | 1932-10-26 | 1935-05-21 | Universal Oil Prod Co | Treatment of motor fuel |
| US2009108A (en) * | 1933-02-08 | 1935-07-23 | Universal Oil Prod Co | Treatment of hydrocarbon oil |
| US2028472A (en) * | 1932-12-02 | 1936-01-21 | Ig Farbenindustrie Ag | Fluorescent substance |
| US2143493A (en) * | 1936-10-30 | 1939-01-10 | Stanley Herbert Muggleton | Production of condensation products of aromatic hydrocarbons with unsaturated aliphatic hydrocarbons |
| DE699607C (en) * | 1936-11-12 | 1940-12-03 | Benzol Verband G M B H | Process for the alkylation of benzene or its homologues |
| US2271299A (en) * | 1939-07-12 | 1942-01-27 | Universal Oil Prod Co | Manufacture of catalysts |
| US2286129A (en) * | 1940-08-02 | 1942-06-09 | Texas Co | Catalysis |
| US2370195A (en) * | 1940-10-31 | 1945-02-27 | Shell Dev | Catalytic agents |
-
1942
- 1942-03-26 US US436314A patent/US2426665A/en not_active Expired - Lifetime
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1878963A (en) * | 1927-12-01 | 1932-09-20 | Ig Farbenindustrie Ag | Manufacture of condensation products |
| US1953702A (en) * | 1928-01-26 | 1934-04-03 | Carbide & Carbon Chem Corp | Method of making alkyl benzenes |
| US2001907A (en) * | 1932-10-26 | 1935-05-21 | Universal Oil Prod Co | Treatment of motor fuel |
| US2028472A (en) * | 1932-12-02 | 1936-01-21 | Ig Farbenindustrie Ag | Fluorescent substance |
| US2009108A (en) * | 1933-02-08 | 1935-07-23 | Universal Oil Prod Co | Treatment of hydrocarbon oil |
| US2143493A (en) * | 1936-10-30 | 1939-01-10 | Stanley Herbert Muggleton | Production of condensation products of aromatic hydrocarbons with unsaturated aliphatic hydrocarbons |
| DE699607C (en) * | 1936-11-12 | 1940-12-03 | Benzol Verband G M B H | Process for the alkylation of benzene or its homologues |
| US2271299A (en) * | 1939-07-12 | 1942-01-27 | Universal Oil Prod Co | Manufacture of catalysts |
| US2286129A (en) * | 1940-08-02 | 1942-06-09 | Texas Co | Catalysis |
| US2370195A (en) * | 1940-10-31 | 1945-02-27 | Shell Dev | Catalytic agents |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3420909A (en) * | 1967-08-21 | 1969-01-07 | Universal Oil Prod Co | Alkylation process |
| US4045504A (en) * | 1968-10-23 | 1977-08-30 | The Lummus Company | Coupling process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2804489A (en) | Conversion of olefinic hydrocarbons to isomers containing a more centrally located double bond | |
| US2349458A (en) | Reaction of paraffinic hydrocarbons | |
| US2413384A (en) | Production of branched chain paraffinic hydrocarbons | |
| US2426665A (en) | Alkylation of aromatic hydrocarbons | |
| US2366736A (en) | Alkylation of isoparaffins | |
| US2361355A (en) | Alkylation process | |
| US2737536A (en) | Method of synthesizing tert-alkyl substituted aromatic compounds | |
| US2308560A (en) | Alkylation of hydrocarbons | |
| US2306253A (en) | Manufacture of motor fuel | |
| US2357978A (en) | Alkylation of aromatic hydrocarbons | |
| US2721885A (en) | Condensation of aromatic compounds with unsaturated organic compounds in the presence of composite catalysts | |
| US2541882A (en) | Alkylation of polynuclear aromatic hydrocarbons | |
| US3153677A (en) | Alkylation of aromatics in the presence of w2o5 catalyst | |
| US2567848A (en) | Alkylation of phenolic compounds with olefins | |
| US2410107A (en) | Alkylation process | |
| US2406634A (en) | Isomerization of saturated hydrocarbons | |
| US2419632A (en) | Alkylation of cyclic hydrocarbons | |
| US2858349A (en) | Process for averaging hydrocarbons | |
| US2391148A (en) | Process for reacting propane with olefins | |
| US2356190A (en) | Novel isomerization process | |
| US2849505A (en) | Alkylation catalyst comprising a tin halide and metallic aluminum | |
| US2436484A (en) | Isomerization of saturated hydrocarbons | |
| US2410108A (en) | Alkylation | |
| US2411047A (en) | Alkylation of aromatics | |
| US2824154A (en) | Alkylation process |