US2377728A - Hydrogenation of hydrocarbonaceous materials - Google Patents

Hydrogenation of hydrocarbonaceous materials Download PDF

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Publication number
US2377728A
US2377728A US318099A US31809940A US2377728A US 2377728 A US2377728 A US 2377728A US 318099 A US318099 A US 318099A US 31809940 A US31809940 A US 31809940A US 2377728 A US2377728 A US 2377728A
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United States
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silica
coal
alumina
gasoline
oil
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US318099A
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Charles L Thomas
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Universal Oil Products Co
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Universal Oil Products Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—Characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent

Definitions

  • tars into valuable liquid products including gaso-' line of high antiknock characteristics which comprises subjecting the coal or slurries thereof to contact with catalysts comprising essentially a mixture of a major portion of a hydrogenating catalyst such as'an oxide or sulfide of molybdenum, tin, cobalt. nickel, etc., either alone or disposed on a relatively inert carrier such as silica.
  • a hydrogenating catalyst such as'an oxide or sulfide of molybdenum, tin, cobalt. nickel, etc.
  • diatomaceous earth, alumina, bauxite and the like in admixture with or impregnated in cracking catalyst compos tes such as silica-alumina, silica-zirconia, silica-titania, silica-magnesia, silica-alumina-zirconia, silica-aluminatitania, silica-alumina-boric oxide, boric oxidealumina, boric oxide-zirconia, boric oxide titania, etc., or mixtures of these compounds with one another.
  • cracking catalyst compos tes such as silica-alumina, silica-zirconia, silica-titania, silica-magnesia, silica-alumina-zirconia, silica-aluminatitania, silica-alumina-boric oxide, boric oxidealumina, boric oxide-zirconia, boric oxide titania, etc., or mixtures of these compounds with one another.
  • the reaction is relatively complete, but is more or less undirected and non-selective.
  • gasoline produced as one product of the reaction is of relatively low antiknock value, although it is saturated in character and is susceptible to octane number increases by the addition of tetraethyl lead or by reforming.
  • the advantage of the present catalyst lies in the fact that not only is the liquefication of the cOal carried out at least as completely and efiiciently as formerly, but the reactions are more selective so that gasoline of higher antiknock value may be obtained.
  • a premium grade of substantially saturated motor fuel useful for aviation purposes may be obtained directly from the process without necessity for subsequent treatment.
  • the process is carried out by mixing a slurry of coal in oil with a finely divided powdered cata-" lyst oi the present invention, heating the mixture to a temperature within the approximate range of SOD-550 C. and preferably approximately 400- 500 0., at a pressure f'1000-5000 pounds per antiknock square inch and passing the mixture together with hydrogen or hydrogen-containing gas into a reaction zone wherein substantial conversion occurs.
  • the liquefied products are removed, the gasoline is separated and the higher boiling oil may be recycled or converted into further yields of gasoline by catalytic or non-catalytic cracking. In some instances a part of the higher boiling oil is used as a carrying medium for the coal.
  • the hydrogenating component of the present catalytic material is selected fromknown hydro genating compounds such as the oxides or sulfides of molybdenum, tin, iron, cobalt, nickel, zinc, etc., which may be used alone or supported on relatively inert carriers such as alumina, silica, bentonite and the like. These materials, either singly or in mixtures, may be composited. with a second catalytic agent which in itself is not a particularly active hydrogenating catalyst, but which in combination with the hydrogenating component serves to direct and promote the desired reactions. These materials consist of a type known broadly as silica-alumina, silica-zirconia.
  • silica-alumina-zirconia, etc. and have been enumerated more fully above. They may be prepared by the separate or simultaneous precipitation of the components followed by washing and drying steps whereby alkali metal compounds are substantially eliminated.
  • the composites so formed may be admixed with the oxides or sulfides of the hydrogenating component; under conditions such that an intimate mixture of very fine particle size is obtained.
  • the hydrogenating component as a rule is the major component and may make up from approximately 80% of the finished catalyst composite.
  • the hydrogenating component may be impregnated in the other component of the catalyst by adding thereto a solution of a compound, for example, the nitrate or chloride followed by precipitation by the addition of a suitable volatile alkali such as ammonium hydroxide and the like, or in some. instances the final composite can be prepared simply by mixing the compounds and calcining.
  • a compound for example, the nitrate or chloride
  • a suitable volatile alkali such as ammonium hydroxide and the like
  • the finished catalyst is prepared by calcining at 500 F. or higher.
  • the finely divided catalytic agents may then be added to the coal in oil slurry, preferably at the time the slurry is made up and the mixture treated as previously described.
  • Example I A suitable catalyst comprises silica-alumina having deposited thereon an oxide of molybdenum at approximately equal amounts by weight. Approximately 12% by weight of the catalytic composite is added to a coal in oil slurry which is then treated in the presence of hydrogen at a temperature of 470 C. and a pressure of 2500 pounds per square inch resulting in the production of a liquid product consisting of approximately 48% by volume of 78 octane number olefin-free gasoline, and approximately 52% by volume of a higher boiling oil which may be converted by catalytic cracking into additional yields of high antiknock gasoline.
  • the octane number of the gasoline produced is 01 the order of '70 and approximately 40% of gasoline is contained in the product.
  • the catalyst powder may be filtered from the product and reactivated by treatment with an oxygen containing gas. Since it is mixed with ash from the coal it is necessary to remove a part of it and replace it with fresh catalyst.
  • Example 11 When treating the coal-in-oil mixture with a composite comprising tin oxide supported on a boron-zirconia composite and using a temperature of 450 C. and a pressure of 2000 pounds per square inch, approximately 46% of 79 octane number gasoline may be produced.
  • a conversionprocess which comprises mixing a slurry of coal in oil with a finely divided powdered composite of a hydrogenating catalyst and a cracking catalyst, passing the resultant mixture, together with hydrogen, through a reaction zone and therein subjecting the mixture to gasoline-producing conversion conditions of temperature and pressure and separating the gasoline from the reaction mass.
  • a conversion process which comprises mixing a slurry of coal in oil with a finely divided powdered composite comprising a major proportion of a hydrogenating catalyst and a minor proportion of a cracking catalyst, passing the resultant mixture, together with hydrogen, through a reaction zone and therein subjecting the mixture to conversion at a temperature in the approximate range of 300-550 C. under a pressure of about 1000-5000 pounds per square inch, removing the reaction mass from said zone and recovering low boiling hydrocarbons therefrom.

Description

Patented June 5, 1945 UNITED STATES [PATENT OFFICE HYDROGENATION OF HYDROCAR- BONACEOUS MATERIALS Charles L. Thomas, Chicago, 11]., assi'gnor to Universal Oil Products, Company, Chicago, 11]., a
corporation of Delaware No Drawing. Application February 9, 1940, Serial No. 318,099
12 Claims.
tars into valuable liquid products including gaso-' line of high antiknock characteristics which comprises subjecting the coal or slurries thereof to contact with catalysts comprising essentially a mixture of a major portion of a hydrogenating catalyst such as'an oxide or sulfide of molybdenum, tin, cobalt. nickel, etc., either alone or disposed on a relatively inert carrier such as silica. diatomaceous earth, alumina, bauxite and the like, in admixture with or impregnated in cracking catalyst compos tes such as silica-alumina, silica-zirconia, silica-titania, silica-magnesia, silica-alumina-zirconia, silica-aluminatitania, silica-alumina-boric oxide, boric oxidealumina, boric oxide-zirconia, boric oxide titania, etc., or mixtures of these compounds with one another.
Inthe hydrogenation of coal and coal in oil mixtures by means of the hydrogenating catalysts which may be used as a component; of the catalysts of the present invention, the reaction is relatively complete, but is more or less undirected and non-selective. As evidence of this the gasoline produced as one product of the reaction is of relatively low antiknock value, although it is saturated in character and is susceptible to octane number increases by the addition of tetraethyl lead or by reforming. The advantage of the present catalyst lies in the fact that not only is the liquefication of the cOal carried out at least as completely and efiiciently as formerly, but the reactions are more selective so that gasoline of higher antiknock value may be obtained. Thus a premium grade of substantially saturated motor fuel useful for aviation purposes may be obtained directly from the process without necessity for subsequent treatment.
The process is carried out by mixing a slurry of coal in oil with a finely divided powdered cata-" lyst oi the present invention, heating the mixture to a temperature within the approximate range of SOD-550 C. and preferably approximately 400- 500 0., at a pressure f'1000-5000 pounds per antiknock square inch and passing the mixture together with hydrogen or hydrogen-containing gas into a reaction zone wherein substantial conversion occurs. As a rule the liquefied productsare removed, the gasoline is separated and the higher boiling oil may be recycled or converted into further yields of gasoline by catalytic or non-catalytic cracking. In some instances a part of the higher boiling oil is used as a carrying medium for the coal. By the present process a higher percentage of the liquid products obtainable boil within the motor fuel range and a smaller amount of residual oil is left forconversion by other methods.
The hydrogenating component of the present catalytic material is selected fromknown hydro genating compounds such as the oxides or sulfides of molybdenum, tin, iron, cobalt, nickel, zinc, etc., which may be used alone or supported on relatively inert carriers such as alumina, silica, bentonite and the like. These materials, either singly or in mixtures, may be composited. with a second catalytic agent which in itself is not a particularly active hydrogenating catalyst, but which in combination with the hydrogenating component serves to direct and promote the desired reactions. These materials consist of a type known broadly as silica-alumina, silica-zirconia. silica-alumina-zirconia, etc., and have been enumerated more fully above. They may be prepared by the separate or simultaneous precipitation of the components followed by washing and drying steps whereby alkali metal compounds are substantially eliminated. The composites so formed may be admixed with the oxides or sulfides of the hydrogenating component; under conditions such that an intimate mixture of very fine particle size is obtained. The hydrogenating component as a rule is the major component and may make up from approximately 80% of the finished catalyst composite.
According to another method, the hydrogenating component may be impregnated in the other component of the catalyst by adding thereto a solution of a compound, for example, the nitrate or chloride followed by precipitation by the addition of a suitable volatile alkali such as ammonium hydroxide and the like, or in some. instances the final composite can be prepared simply by mixing the compounds and calcining.
Thus, for example, it silica-alumina is used and molybdenum nitrate solution is to be added thereto, the finished catalyst is prepared by calcining at 500 F. or higher.
The finely divided catalytic agents may then be added to the coal in oil slurry, preferably at the time the slurry is made up and the mixture treated as previously described.
The following examples are given to illustrate the usefulness and practicability of the catalysts and should not be construed as limiting them to the exact conditions or catalytic agents described therein.
Example I A suitable catalyst comprises silica-alumina having deposited thereon an oxide of molybdenum at approximately equal amounts by weight. Approximately 12% by weight of the catalytic composite is added to a coal in oil slurry which is then treated in the presence of hydrogen at a temperature of 470 C. and a pressure of 2500 pounds per square inch resulting in the production of a liquid product consisting of approximately 48% by volume of 78 octane number olefin-free gasoline, and approximately 52% by volume of a higher boiling oil which may be converted by catalytic cracking into additional yields of high antiknock gasoline. When using molybdenum oxide in the absence of the silica-alumina mass, the octane number of the gasoline produced is 01 the order of '70 and approximately 40% of gasoline is contained in the product. The catalyst powder may be filtered from the product and reactivated by treatment with an oxygen containing gas. Since it is mixed with ash from the coal it is necessary to remove a part of it and replace it with fresh catalyst.
Example 11 When treating the coal-in-oil mixture with a composite comprising tin oxide supported on a boron-zirconia composite and using a temperature of 450 C. and a pressure of 2000 pounds per square inch, approximately 46% of 79 octane number gasoline may be produced.
I claim as my invention:
1. A conversionprocess which comprises mixing a slurry of coal in oil with a finely divided powdered composite of a hydrogenating catalyst and a cracking catalyst, passing the resultant mixture, together with hydrogen, through a reaction zone and therein subjecting the mixture to gasoline-producing conversion conditions of temperature and pressure and separating the gasoline from the reaction mass.
2. A conversion process which comprises mixing a slurry of coal in oil with a finely divided powdered composite comprising a major proportion of a hydrogenating catalyst and a minor proportion of a cracking catalyst, passing the resultant mixture, together with hydrogen, through a reaction zone and therein subjecting the mixture to conversion at a temperature in the approximate range of 300-550 C. under a pressure of about 1000-5000 pounds per square inch, removing the reaction mass from said zone and recovering low boiling hydrocarbons therefrom.
3. The process as defined in claim 1 further characterized in that said cracking catalyst comprises silica and alumina.
4. The process as defined in claim 2 further characterized in that said cracking catalyst comprises silica and alumina.
5. The process as defined in claim 1 further characterized in that said cracking catalyst comprises silica andzirconia.
6. The process as defined in claim 2 further characterized in that said cracking catalyst comprises silica and zirconia.
7. The process as defined in claim 1 further characterized in that said cracking catalyst comprises silica and magnesia.
8. The process as defined in claim 2 further characterized in that said cracking catalyst comprises silica and magnesia.
9. The process as defined in claim 1 further characterized in that said cracking catalyst comprise boric oxide and zirconia.
10. The process as defined in claim. 2 further characterized in that said cracking catalyst comprises boric axide and zirconia.
11. The process as defined in claim 1 further characterized in that said cracking catalyst comprises boric oxide.
12. The process as defined in claim 2 further characterized in that said cracking catalyst comprises bor'ic oxide.
' CHARLES L. THOMAS.
US318099A 1940-02-09 1940-02-09 Hydrogenation of hydrocarbonaceous materials Expired - Lifetime US2377728A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2437531A (en) * 1942-12-24 1948-03-09 Union Oil Co Catalytic treatment of hydrocarbons
US2541317A (en) * 1948-07-09 1951-02-13 Phillips Petroleum Co Hydrogenolysis process for the production of gasoline and diesel oil from petroleum residue stocks
US2585337A (en) * 1949-02-15 1952-02-12 Gulf Research Development Co Destructive hydrogenation of hydrocarbon oils with molybdenum oxide catalyst
US2913388A (en) * 1954-11-30 1959-11-17 John H Howell Coal hydrogenation process
US3231486A (en) * 1960-12-16 1966-01-25 Union Carbide Corp Catalytic hydrogenation of carbonized coal vapors
US3527691A (en) * 1968-12-31 1970-09-08 Shell Oil Co Process for conversion of coal
US3532617A (en) * 1968-07-23 1970-10-06 Shell Oil Co Hydroconversion of coal with combination of catalysts
US3549512A (en) * 1968-07-23 1970-12-22 Shell Oil Co Process for conversion of coal
US4032429A (en) * 1975-11-28 1977-06-28 Gulf Research & Development Company Coal liquefaction process using an aluminum phosphate supported catalyst
US4176041A (en) * 1977-02-24 1979-11-27 Kobe Steel, Ltd. Method for reforming low grade coals
US4379045A (en) * 1981-05-06 1983-04-05 Mobil Oil Corporation Co-processing of residual oil and coal
US4948495A (en) * 1988-07-26 1990-08-14 The United States Of America As Represented By The United States Department Of Energy High liquid yield process for retorting various organic materials including oil shale

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2437531A (en) * 1942-12-24 1948-03-09 Union Oil Co Catalytic treatment of hydrocarbons
US2541317A (en) * 1948-07-09 1951-02-13 Phillips Petroleum Co Hydrogenolysis process for the production of gasoline and diesel oil from petroleum residue stocks
US2585337A (en) * 1949-02-15 1952-02-12 Gulf Research Development Co Destructive hydrogenation of hydrocarbon oils with molybdenum oxide catalyst
US2913388A (en) * 1954-11-30 1959-11-17 John H Howell Coal hydrogenation process
US3231486A (en) * 1960-12-16 1966-01-25 Union Carbide Corp Catalytic hydrogenation of carbonized coal vapors
US3532617A (en) * 1968-07-23 1970-10-06 Shell Oil Co Hydroconversion of coal with combination of catalysts
US3549512A (en) * 1968-07-23 1970-12-22 Shell Oil Co Process for conversion of coal
US3527691A (en) * 1968-12-31 1970-09-08 Shell Oil Co Process for conversion of coal
US4032429A (en) * 1975-11-28 1977-06-28 Gulf Research & Development Company Coal liquefaction process using an aluminum phosphate supported catalyst
US4176041A (en) * 1977-02-24 1979-11-27 Kobe Steel, Ltd. Method for reforming low grade coals
US4379045A (en) * 1981-05-06 1983-04-05 Mobil Oil Corporation Co-processing of residual oil and coal
US4948495A (en) * 1988-07-26 1990-08-14 The United States Of America As Represented By The United States Department Of Energy High liquid yield process for retorting various organic materials including oil shale

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