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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/24—Chromium, molybdenum or tungsten
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/652—Chromium, molybdenum or tungsten
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
• • 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
• • 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
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
  • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
  • C07C2521/04—Alumina
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • C07C2521/08—Silica
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
  • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
  • C07C2523/42—Platinum
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
  • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
  • C07C2523/44—Palladium
• • 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

Definitions

• the present invention relates to the preparation of arylnaphthenes and/ or alkyl substituted arylnaphthenes from aromatic hydrocarbons and/ or alkyl substituted aromatic hydrocarbons.
• Naphthenes are defined herein as hydrocarbons the molecule of which contains at least one saturated hydrocarbon ring.
• heteropolyacid is defined herein as an acid belonging to the group of "complex acids composed of more than one metallic oxide or metalloid oxide.
• Another object is to reduce the amount of hydrogenation catalyst required in converting aromatic hydrocarbons (including alkyl substituted aromatic hydrocarbons) into arylnaphthenes (including alkarylnaphthenes).
• arylnaphthenes and/ or alkyl substituted arylnap'hthenes can be obtained from aromatic hydrocarbons (including alkyl aromatic hydrocarbons) if the aromatic hydrocarbon in the liquid phase is hydrogenated with hydrogen at a hydrogen pressure below 100 atmospheres and at a temperature not over 250 C. while using a mixture of a hydrogenation catalyst and a heteropolyacid as cocatalysts.
• the hydrogen pressure can be as low as 5 atmospheres and the temperature can be as low as 125 C.
• the invention can be employed for example to prepare phenylcyclohexane from benzene tolyl methylcyclohexane from toluene dimethylphenyl dimethyl cyclohexane from xylene (any of the isomers o-xylene, p-xylene or m-xylene or a mixture thereof can be employed) butylphenyl butylcyclohexane from n-butylbenzene naphthyl decahydronaphthalene from naphthalene decylphenyl decylcyclohexane from decylbenzene phenyl decahydronaphthalene from a mixture of benzene and naphthalene -(e.g.
• methylnaphthyl methyldecahydronaphtha'lene from methyl naphthalene methylphenyl decahydronaphthalene from a mixture of toluene and xylene (e.g. a 1:2 molar mixture).
• Suitable heteropolyacid catalysts according to the invention include silicotungstic acid, borotungstic acid, phosphotungstic acid, phosphomolybdic acid, boronmolybdic acid, silicomolybdic acid, phosphotungstomolybdic acid, arsenomolybdic acid, antimonotungstic acid and phosphovanadic acid.
• hydrogenation catalysts are metals such as nickel, cobalt, iron, platinum, palladium, iridium, osmium, rhodium, ruthenium and tungsten, oxides such as chromium oxide e.g. chromic oxide, molybdenum oxide and tungsten oxide and selenium oxide as Well as sulfides such as molybdenum sulfide, nickel sultide, tungsten sulfide and iron sulfide.
• metals such as nickel, cobalt, iron, platinum, palladium, iridium, osmium, rhodium, ruthenium and tungsten
• oxides such as chromium oxide e.g. chromic oxide, molybdenum oxide and tungsten oxide and selenium oxide as Well as sulfides such as molybdenum sulfide, nickel sultide, tungsten sulfide and iron sulfide.
• the amount of hydrogenation catalyst in the catalyst combination can be varied.
• One of the advantages of the invention is that it can be quite small, e.g. 0.1-2.5 of the hydrogenation catalyst by Weight of the heteropolyacid is suificient to give good results in the reaction. It is possible to employ larger amounts of the hydrogenation catalyst, e.g. 3, 5, 15 or 20% by weight of the heteropolyacid. In fact there can be used as much as 35% of the hydrogenation catalyst based on the weight of the heteropolya'cid.
• one of the advantages of the present invention is that only very small amounts of the costly hydrogenation catalyst suifice to obtain satisfactory yields of the low boiling arylnaphthenes.
• the carrier can be 40 to 90% by weight based on the total weight of the hydrogenation catalyst, heteropolyacid and carrier.
• suitable carriers include thorium oxide, aluminum oxide, magnesium oxide, zirconium oxide, silicon dioxide, silicic acid gel, diatomaceous earth, kieselguhr, pumice and carbon. These can also be used as the carrier substances which are suitable for promoting the cracking of hydrocarbons to liquid and/or gaseous products.
• cracking catalysts include acid metal silicates composed of silicon dioxide and metal oxides such as aluminum oxide, calcium oxide, zirconium oxide, magnesium oxide, rare earth metal oxides, e.g. hafnium oxide and cerium oxide, and zinc oxide. Other inorganic oxides such as barium oxide can also be present.
• the cocatalysts can be employed in an amount of /2 to 10% based on the weight of the aromatic hydrocarbon reactant.
• the combination of the hydrogenation catalyst and heteropolyacid can be obtained in several ways.
• an intimate mixture of the two materials can be made simply by mixing the preformed materials.
• An alternative procedure is to prepare the hydrogenation catalyst in the presence of the heteropolyacid.
• One way of carrying out the latter procedure is to distribute a heteropolyacid in a solution of a compound of the metal which is to serve as the hydrogen catalyst and to complete the wgen pressure should be below atmospheres.
• the hydrogen employed need not be pure but it can be diluted with inert gases such as nitrogen, argon and saturated hydrocarbons such as methane, ethane, propane, butane and tetramethylmethane. Saturated hydrocarbons can also be added in the liquid phase as diluents. lllustra tive of such materials are cyclohexane, decahydronaphthalene, n-heptane, n-decane, Z-methylhexane.
• inert gases such as nitrogen, argon and saturated hydrocarbons such as methane, ethane, propane, butane and tetramethylmethane.
• saturated hydrocarbons such as methane, ethane, propane, butane and tetramethylmethane.
• Saturated hydrocarbons can also be added in the liquid phase as diluents. lllustra tive of such materials are cyclohexane, decahydronaphthalene
• Example 1 The catalyst employed consisted of 0.7% platinum, 20% silicotungstic acid and 79.3% of powdered silicic acid gel. The catalyst was prepared bp impregnating silicic acid gel with an aqueous solution of silicotungstic acid and chloroplatinic acid, evaporating the water and finally reducing the dry product with hydrogen.
• Example 2 The procedure of Example 1 was followed except that the temperature was raised to 185-190 C. and the pressure was raised to 30 atmospheres. The product analyzed 25.1% phenylcyclohexane, 12.7% cyclohexane, 57.1% benzene and 5.1% higher boiling products. Thus raising the temperature and pressure while reducing the total amount of conversion of the aromatic hydrocarbon increased the yield of the desired arylnaphthene while reducing the amount of by-products.
• Example 3 There were distributed 35 grams of a catalyst mixture consisting of 0.2% palladium, 20% silicotungstic acid and 79.8% silicic acid gel in 700 cc. of toluene in the autoclave used in Example 1. Then hydrogen was introduced and the reaction mixture heated at 150 C. for 4 hours while keeping the pressure at 10 atmospheres. After cooling to room temperatures the liquid reaction product was separated from the catalyst and fractionally dis tilled to give a product analyzing 16.4% tolyl methylcyclohexane, 20.6% methylcyclohexane, 53% toluene and 10% higher boiling products.
• a catalyst mixture consisting of 0.2% palladium, 20% silicotungstic acid and 79.8% silicic acid gel in 700 cc. of toluene in the autoclave used in Example 1. Then hydrogen was introduced and the reaction mixture heated at 150 C. for 4 hours while keeping the pressure at 10 atmospheres. After cooling to room temperatures the liquid reaction product was separated from the catalyst and fractionally dis tilled to give
• Example 4 Aluminum oxide was impregnated with an aqueous solution of nickel nitrate and silicotungstic after which the water was evaporated and the dry substance reduced with hydrogen.
• the catalyst thus obtained was composed of p Example 5
• the procedure of Example 3 was repeated but the catalyst was replaced by 35 grams of one having an aluminum silicate cracking catalyst (A1 0 content 13%) as a carrier.
• the activity of the cracking catalyst was reduced by passing a mixture of 80% by Volume of air and 20% by volume of steam over it for 2 hours at 800 C.
• the catalyst employed for treating the benzene thus contained 1% nickel, 10% silicotungstic acid and 89% of the aluminum silicate. After a reaction time of 8 hours at 185- 190 C.
• a process for preparing a member of the group consisting of arylnaphthenes and alkaryl naphthenes comprising treating a member of the group consisting of aromatic hydrocarbons and alkyl substituted aromatic hydrocarbons in the liquid phase with hydrogen at a hydrogen pressure or" less than atmosphere and at a temperature not over 25 0 C. while in. contact with a catalyst containing (1) a heteropolyacid and (2) a second hydrogenation catalyst.
• a process according to claim 3 wherein the carrier is selected from the group consisting of acid metal silicate cracking catalysts, acid clay, silicon dioxide, silicic acid gel, kieselguhr, diatomaceous earth, pumice, carbon and metal oxides.
• the second hydrogenation catalyst is selected from the group consisting of metals, metal oxides and metal sulfides and the heteropolyacid is selected from the group consisting of silicotungstic acid, borontungstic acid, phosphotungstic acid, phosphomolybdic acid, boronmo-lybdic acid, silicomolybdic acid, phosphotungstomolybdic acid, arsenomo lybdic acid, antimonotungstic acid and phosphovanadic acid.
• a process for preparing an aryl naphthene comprising treating benzene in the liquid phase with hydrogen at a hydrogen pressure of less than 100 atmospheres and at a temperature not over 250 C. while in contact with a catalyst containing (1) a heteropolyacid and (2) a second hydrogenation catalyst.
• the second hydrogenation catalyst is a metal and the heteropolyacid is a member of the group consisting of silicotungstic acid, borontungstic acid, phosphotungstic acid, phosphomolybdic acid, boronrnolybdic acid, silicomolybdic acid, phosphotungstomolybdic acid, arsenomolybdic acid, antimonotungstic acid and phosphovanadic acid.
• the catalyst includes a carrier selected from the group consisting of acid metal silicate cracking catalysts, acid clay, silicon dioxide, silicic acid gel, kieselguhr, diatomaceous earth, pumice, carbon and metal oxides.
• heteropolyacid is silicotungstic acid and the second hydrogenation catalyst is a metal.
• a process for preparing an alkyl substituted aryl naphthene comprising treating a lower alkyl substituted benzene in the liquid phase with hydrogen at a hydrogen pressure of less than 100 atmospheres and at a temperature not over 250 C. While in contact with a catalyst containing (1) a heteropolyacid and (2) a second hydrogenation catalyst.
• the catalyst includes a carrier selected from the group consisting of acid metal silicate cracking catalysts, acid clay, silicon dioxide, silicic acid gel, kieselguhr, diatomaceous earth pumice, carbon and metal oxides.
• a process according to claim 1 wherein there is empolyacid is s-ilicotungstic acid and the second hydrogenaployed an aluminum oxide carrier with the catalyst.
• tion catalyst is a metal.
• a process according to claim 15 wherein the metal ployed an alurm'num silicate cracking catalyst as a carrier is platinum. 5 for the mixed catalyst.

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• 1962
  • 1962-06-12 DE DEST19356A patent/DE1241824B/de active Pending
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