US2550531A - Reforming process and catalyst therefor - Google Patents

Reforming process and catalyst therefor Download PDF

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Publication number
US2550531A
US2550531A US135736A US13573649A US2550531A US 2550531 A US2550531 A US 2550531A US 135736 A US135736 A US 135736A US 13573649 A US13573649 A US 13573649A US 2550531 A US2550531 A US 2550531A
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Prior art keywords
catalyst
surface area
component
reforming
cracking
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US135736A
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Frank G Ciapetta
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Atlantic Richfield Co
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Atlantic Refining Co
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Priority to NL75000D priority Critical patent/NL75000C/xx
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Priority to US135736A priority patent/US2550531A/en
Priority claimed from GB442551A external-priority patent/GB686641A/en
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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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S252/00—Compositions
    • Y10S252/18—Activation-platinum
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/8995—Catalyst and recycle considerations
    • Y10S585/906—Catalyst preservation or manufacture, e.g. activation before use

Definitions

  • This invention relates to a reforming process and to a reforming catalyst having particular surface area characteristics. More particularly it relates to a silica alumina catalyst; having a surface area from about to about 65 square meters per gram, impregnated with platinum or palladium and to a process for reforming etrm leum hydrocarbons with said catalyst to obtain high yields of products having high anti-knock properties.
  • I 'he hydrocarbons to be treated in the invention comprise petroleum distillates, including naphthas, gasoline and kerosine, and particularly gasolinecfractions
  • the gasoline fraction may be a full boiling range -gasoline having an initial boiling point within the range of about 50 to about 90 F. and an end boiling point within the range of about 375 to about 425 F.) or it may be a selected fraction thereof which usually will be a higher boiling fraction, commonly referred to as naphtha, and generally having an initial boiling point of from about 150 to abbut 250 F. and an endboili-ng point within the range of 'about, 350 to about 425 F.
  • the petroleum hydrocarbons tobe reformed are mixtures containing for the most part paraffinic hydrocarbons which are usually straight chain or slightly branched chain structures and cyclic compounds (so-called naphthenic hydrocarbons), especial-1y cyclohexa'nes; as well as, in most cases; varying proportions of aromatic hydrocarbons.
  • naphthenic hydrocarbons paraffinic hydrocarbons
  • especial-1y cyclohexa'nes especial-1y cyclohexa'nes
  • aromatic hydrocarbons especial-1y cyclohexa'nes
  • Still another important series or reactions is the isoinerization of alkyl 'c'y'clopentanes to eyeio hexanes followed by the dehydrogenation of these cyclohexanes together with'those originally present in the mixture to aromatics.
  • An add i tional means of forming aromatics is the dehydrocyclization of acyclic paraifin's.
  • the presence of hydrogen during the reforming decreases the demethanation reaction and when a carbon to carbon bond is broken as when the higher molecular weight paraflins are cracked or when a methyl or ethyl group isbroken off the paraffin, the hydrogen saturates the carbon and in the case of the ethyl or methyl groups; form the corresponding gas and thereby prevent or greatly reduces the deposition of carbon.
  • a area-alanine catalyst having a particular surface area and impregnated with platinum or palladium displays a maximum isomer yield from open chain paraffins during the catalytic reforming of these compounds with such a catalyst. It has been dis covered further that the maximum isomer yield obtainable with such catalysts having certain surface areas is extremely sensitive to temperature when the surface area of the component upon which the platinum or palladium is composited is greater than about 65 square meters per gram of component, that with surface areas smaller than this value the catalyst is Substantially insensitive to temperature in so far as obtaining maximum isomer yield is concerned and that the change in sensitivity to temperature is so great at a surface area of about 65 square meters per gram of component as to be of critical importance in the reforming of hydrocarbons.
  • the invention relates to a catalyst containing a cracking component having a surface area from about 10 to about 65 square meters per gram impregnated with platinum or palladium, said component comprising silica and alumina and to a process for treating petroleum distillates under reforming conditions with such catalyst.
  • the invention in its narrower aspect, relates to a catalyst containing a cracking component having a surface area from about 10 to about 65 square meters per gram comprising silica and alumina impregnated with platinum or palladium in amount from 0.01 to 2.5% by weight of the final catalyst and to a process for reforming a gasoline fraction with such catalyst at temperatures in the range 600 to 1000 F., at pressures in the range 100 to 1000 pounds per square inch, at an hourly liquid space velocity of from 0.1 to 10 in the presence of from 1 to mols. of hydrogen per mol. of hydrocarbon. Larger or smaller amounts of platinum or palladium than in the range 0.01 to 2.5% by weight of the final catalyst may be used. Such larger or smaller amounts are not preferred, however, since amounts less than 0.01 result in too low an activity and in amounts larger than 2.5% result in excessive cracking.
  • the low surface area component upon which the platinum or palladium is deposited will have some activity to catalyze th cracking reaction; however, this activity is low compared with the high surface area catalyst normally used in the cracking art.
  • This component may be derived either from naturally occurring or synthetically produced materials. Naturally occurring materials include various aluminum silicates, particularly when acid treated to increase the activity, such as Super FiIbI'Ol, etc.
  • the synthetic materials may be made in any suitable manner including separate, successive 0r co-precipitation of silica and alumina.
  • the synthetic component may be manufactured by commingling an acid, such as hydrochloric acid, sulfuric acid, etc, with commercial water glass under conditions to precipitate silica, washing with acidulated water or otherwise to remove sodium ions, commingling With an aluminum salt such as aluminum chloride, aluminum sulfate, aluminum nitrate, and either adding a basic precipitant, such as ammoniumv hydroxide, to precipitate alumina or forming the desired oxide or oxides by thermal decomposition of the salt as the case may permit.
  • the cracking component may contain from 20-95 percent by weight of silica with the remainder alumina although amounts above and below this range may also be used.
  • the component may be in the form of regular beads or granules of irregular size and shape.
  • the granules may be ground and formed into pellets of uniform size and shape by pilling, extrusion or other suitable methods.
  • Components prepared in this manner have surface areas of the order of magnitude of 400 square meters or more per gram.
  • the surface area of the component at this point i. e., before compositing the platinum or palladium thereon, to the desired value in any suitable manner.
  • This may be accomplished by steaming the component at temperatures of from 900 to 1400" F. at steam pressures from atmospheric to pounds per square inch or higher for a sufficient time, usually for about 50 to 100 hours although longer or shorter periods may be used, to obtain the desired surface area or by heating the component at temperatures from 1600 to 1800 F. without the use of steam and for a sufficient time to obtain the desired surface area.
  • the term surface area as used herein means the surface area of the component as determined by the adsorption of nitrogen according to the method of Brunnauer, Emmett and Teller found in the Journal of the American Chemical Society, vol. 60, pages 309 et seq. (1938).
  • the platinum or palladium may be composited with the cracking component, prepared as above described, in any suitable manner.
  • the preferred method is to admix with the cracking component an aqueous solution of chloro-platinic acid or a chloro-palladic acid of suitable concentrations in the desired amounts. The mixture is then dried and treated with hydrogen at elevated temperatures to reduce the chloride to the metal and to activate the catalyst.
  • a particularly suitable manner of regeneration of the catalyst comprises effecting the regeneration at a temperature of about 900 to about 950 F.,
  • the catalyst is suspended by the gaseous hydrocarbon starting with a gas containing about 2% oxygen ever, it is important that the temperature of re- 5 generation should not exceed 1000 F. as it has been found that temperatures in excess of 1000" F. tend to impair the catalyst activity.
  • the process of the invention may be effected in any suitable equipment.
  • An especially suitable process comprises the fixed bed process in which the catalyst is deposited in a reaction zone or zones, the hydrocarbon, passing through such 1 zone or zones and in contact with the catalyst.
  • Another'suitable apparatus in which the process may be conducted is the fluid type in which the stream.
  • the moving bed type process in which the catalyst and hydrocarbon are passed either concurrently or countercurrently to each other and the suspensoid type process in which the catalyst is carried as a slurry in the hydrocarbon may also be used.
  • the products may be fractionated to separate excess hydrogen and to recover the desired fractions of reformed product.
  • suflicient hydrogen will be produced in the reforming reaction to maintain a hydrogen partial pressure sufficient to saturate'the hydrocarbon fragments formed therein.
  • hydrogen from an extraneous source is added at the beginning of the operation, and usually it is desirable to recycle hydrogen within the process after the starting operation in order to assure a sufficient hydrogen atmosphere in the reaction zone.
  • Hydrogen serves to maintain the catalyst activity by reducing or preventing carbon deposition.
  • the petroleum distillates may be treated to remove sulfur before they are reformed.
  • the silica-alumina component was prepared from a commercially available silica-alumina cracking catalyst.
  • This cracking catalyst is prepared by adding sulfuric acid to commercial water glass in proportions to precipitate silica hydrogel.
  • the silica hydrogel was washed with acidulated water to remove sodium ions, after which the hydrogel is dispersed in a sufficient amount of an aqueous solution of aluminum sulphate of suitable concentration and'ammonium hydroxide is added to precipitate alumina to form a silica-aluminacomposite containing 13% by weight of alumina.
  • the silica-alumina composite is then washed, dried, calcined at 600-900 F. and formedinto pellets.
  • This cracking catalyst had a surface area of 425 square meters per gram. Portions of the thus prepared silicaalumina were then treated with steam at 1050 to 1250 F. using steam pressure from 15 to pounds per square inch for varying times to obtain components having the surface areas indicated in Tables 1 and 2. Solutions of chloro platinic acid in suitable amounts and concentrations were added 'to the different samples of the silica-alumina composites and the thus impregnated material was dried at 220 F. and treated with a hydrogen containing gas at atmospheric pressure while the temperature was in- 7 Table I Constants: pressure:' 350 p. s. i. g.; L; S.
  • Figure 1 is a plot of yield of C7 isomers versus percent conversion of normal C7 fraction for a particular surface area.
  • Figure 2 is a plot of conversion of normal C7 fraction versus reaction temperature in .degrees Fahrenheit for the catalyst of Figure 1.
  • v Figure 3 is a plot similar to Figure 1 but with a surface area of catalyst different from that of Figure 1.
  • v Figure 4 is a plot similar to Figure 2 but with the catalyst of Figure 3.
  • Figure 5 is a plot of reaction temperature in degrees Fahrenheit versus surface area of catalyst.
  • Figure 6 is a plot of reaction temperature in degrees Fahrenheit versus percent aromatics.
  • Figure 1 is a plot of yield of isomerized 7 hydrocarbons versus conversion of the normal C7 fraction obtained from the mixture reformed in Example I.
  • the data for the curve of this figure is plotted for a catalyst having a surface area of 425 square meters per gram at pressures of 350 poundsper square inch (curve A) and 700 pounds per square inch (curve B).
  • the curves of Figure 3 are similar to those of Figure 1 but are plotted for catalysts having a surface area of 45 square meters per gram, curve C representing reforming at 350 pounds per square inch and curve 1), at 700 pounds per square inch.
  • each catalyst of a particular surface area exhibits a maximum yield of isomerized hydrocarbon with respect to conversion of the normal C7 fraction. Such maximums occur for each catalyst regardless of its surface area and pressure.
  • catalysts having surface areas M425 and 45 square meters per gram are shown in the curves.
  • Figure 1 the catalyst of Figure 1, curve E. representing reforming at 350 pounds per square inch and curve F, at 700 pounds per square inch.
  • Figure '4 is similar to Figure 2 but isa plot of ithecatalyst of Figure 3, e. g., a catalyst having a surface area of 45 square meters per gram.
  • Curve G of Figure 4 represents the conversion versus reaction temperature curve for a catalyst having a surface area of square meters per gram at both '350 pounds per-square inch and 7-00 pounds per square inch.
  • the curve H of Figure 5 is a ,plot of reaction tempera'ture's for the isomersyieldmaxima of the famil-y of-curves -of which curves -A andB of Figure 1 and C and D of Figure 3 are representative versus the surface area of the corresponding catalysts.
  • the manner in which this curve was plotted is illustrated as follows: In Figure 1 the percent total conversion at which maximum isomerization of the normal C7 hydrocarbons takes place, was determined from curve A by drawing the perpendicular line i. The point at which line I crosses the abscissa of Figure 1 wasnoted. This value was then taken to Figure 2 and the horizontal line 3 of Figure 2 was drawnand extended until -it intersected curve E of Figure 2.
  • curve H of Figure 5 is relatively flat and has a very low slope while on the other hand the left hand .portion of the same curve is-extremelysteep in slope and that the rate of change of slope of the curve increases rapidly at about a value of square meters per gram at which .point the inflection ,point .of curve H occurs as is illustrated by vertical Iine'il.
  • pounds persquare inch this temperature is about 860 F.
  • the significance of this curve is that in order to 'form aromatics during reforming, it is desirable to operate above these respective tem peratures for the respective pressure used. In .general, the higher the reaction temperature used during conversion above these equilibrium reaction temperatures, the greater the amount of aromatics formed.
  • a metal containin hydrogenation catalyst such as the metals, oxides and salts of the elements of groups VI and VIII of
  • a process for reforming a petroleum distillate fraction boiling within the gasoline-kerosine range to increase the anti-knock value thereof which comprises subjecting said fraction to contact at reforming conditions in the presence of hydrogen with a catalyst comprising a cracking component and a metal from the group consisting of platinum and palladium, said cracking component comprising silica and alumina and having a surface area in the range of about 10 to about 65 square meters per gram of said component.
  • a process for reforming a gasoline fraction to increase the anti-knock value thereof which comprises subjecting said fraction to contact at reforming conditions in the presence of hydro-- gen with a catalyst comprising a cracking component and a metal from the group consisting of platinum and palladium in an amount from 0.01 to 2.5% by weight of the final catalyst, said cracking component comprising silica and alumina and having a surface area in the range from about to about 65 square meters per gram of said component.
  • a process for reforming a gasoline fraction to increase the anti-knock value thereof which comprises subjectin said fraction to contact at a temperature within the range 600 to 1000 F., a pressure of from 100 to 1000 pounds per square inch, and an hourly space velocity of from 0.1 to 10, in the presence of from 1 to 20 mols. of hydrogen per mol. of hydrocarbon, with a catalyst comprising a cracking component and a metal from the group consisting of platinum and palladium in an amount from 0.01 to 2.5% by weight of the final catalyst, said cracking component comprising silica and alumina and having a surface area in the range from 10 to about 65 square meters per gram of said component.
  • a process for reforming a gasoline fraction to increase the anti-knock value thereof which comprises subjecting said fraction to contact at a temperature within the range 600 to 1000 F., a pressure of from 100 to 1000 pounds per square inch, and an hourly space velocity of from 0.1 to 10, in the presence of from 1 to 20 mols. of hydrogen per mol. of hydrocarbon, with a catalyst comprising a cracking component and metallic platinum in an amount from 0.01 to 2.5% by weight of the final catalyst, said cracking component comprising silica and alumina and having a surface area in the range from about 10 to about 65 square meters per gram of said component.
  • a catalyst comprising a component having a hydrocarbon cracking activity and a metal from the group consisting of platinum and palladium, said component comprising silica and alumina a and having a surface area in the range of about 10 to about square meters per gram of said component.
  • a catalyst comprising'a component having a hydrocarbon cracking activity and a metal from the group consisting of platinum and palladium in an amount from 0.01 to 2.5% by weight of the catalyst, said component comprising silica and alumina and having a surface area in the range from about 10 to about 65 square meters per gram of said component.
  • a catalyst comprising a component having a hydrocarbon cracking activity and metallic platinum in an amount from 0.01 to 2.5% by weight of the catalyst, said component comprising silica and alumina and having a surface area in the range from about 10 to about 65 square meters per gram of said component.
  • a process for preparing a catalyst comprising heating a synthetic silica-alumina cracking component at temperatures from 1600 to 1800 F. until its surface area is reduced to about 10 to 65 square meters per gram and compositing therewith a metal from the group consistin of platinum and palladium in an amount from 0.01 to 2.5% by weight of the catalyst.
  • a process for preparing a catalyst comprising heating a synthetic silica-alumina cracking component at temperatures from 900 to 1400 F. and in the presence of steam until its surface area is reduced to about 10 to 65 square meters per gram and compositing therewith a metal from the group consisting of platinum and palladium in an amount from 0.01 to 2.5% by weight of the catalyst.

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  • Organic Chemistry (AREA)
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Cited By (67)

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US2900425A (en) * 1956-08-10 1959-08-18 Universal Oil Prod Co Isomerization process
US2908656A (en) * 1956-11-05 1959-10-13 Houdry Process Corp Pretreatment of noble metal catalysts
US2910523A (en) * 1956-05-08 1959-10-27 Gulf Research Development Co Hydroisomerization process
US2911451A (en) * 1955-11-14 1959-11-03 Universal Oil Prod Co Production of benzene
US2913508A (en) * 1957-11-07 1959-11-17 Pure Oil Co Process for isomerizing hydrocarbons
US2917466A (en) * 1951-12-11 1959-12-15 Shell Dev Platinum metal catalysts
US2918509A (en) * 1957-10-31 1959-12-22 Pure Oil Co Process and catalyst for the isomerization of hydrocarbons
US2924629A (en) * 1956-10-19 1960-02-09 Universal Oil Prod Co Isomerization process
US2925453A (en) * 1957-12-16 1960-02-16 Pure Oil Co Process and catalyst for the isomerization of hydrocarbons
US2926207A (en) * 1956-12-31 1960-02-23 Pure Oil Co Isomerization catalysts and process
DE1078097B (de) * 1958-02-01 1960-03-24 Konink Zwavelzuurfabrieken V H Verfahren zur Verbesserung von Katalysatortraegern aus Aluminiumoxyd
US2939897A (en) * 1958-08-15 1960-06-07 Pure Oil Co Process and catalyst for the isomerization of light paraffin
US2939894A (en) * 1956-11-19 1960-06-07 Pure Oil Co Isomerization of light petroleum distillates employing catalyst comprising iron-group metal on lithium-modified acidic mixed oxides support
US2939896A (en) * 1957-12-09 1960-06-07 Phillips Petroleum Co Isomerization process and catalyst
US2943129A (en) * 1958-10-07 1960-06-28 Pure Oil Co Process and catalyst for isomerizing normal paraffins
US2943128A (en) * 1958-10-06 1960-06-28 Pure Oil Co Process and catalyst for isomerizing normal paraffins
US2945800A (en) * 1955-06-08 1960-07-19 Socony Mobil Oil Co Inc Multiple pass catalytic cracking
US2945909A (en) * 1955-12-30 1960-07-19 Standard Oil Co Isomerization process and catalyst therefor
US2947683A (en) * 1957-12-12 1960-08-02 Pure Oil Co Process for improving the octane number of naphthas
US2961414A (en) * 1957-11-15 1960-11-22 Kellogg M W Co Platinum and palladium catalysts
US2967207A (en) * 1957-11-27 1961-01-03 Pure Oil Co Silica-alumina catalyst copromoted with palladium and iron-group metal, and isomerization process catalyzed thereby
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US2854403A (en) * 1954-07-26 1958-09-30 Socony Mobil Oil Co Inc Catalytic reforming
DE1171892B (de) * 1955-05-17 1964-06-11 Gulf Research Development Co Verfahren zum hydrierenden Isomerisieren von naphthenfreien oder sehr naphthenarmen C- und C-Kohlenwasserstoffen ueber Platin-Traegerkatalysatoren
US2945800A (en) * 1955-06-08 1960-07-19 Socony Mobil Oil Co Inc Multiple pass catalytic cracking
US2882245A (en) * 1955-07-18 1959-04-14 Houdry Process Corp Process for production of a catalyst of the platinum-alumina type
US2911451A (en) * 1955-11-14 1959-11-03 Universal Oil Prod Co Production of benzene
US2945909A (en) * 1955-12-30 1960-07-19 Standard Oil Co Isomerization process and catalyst therefor
US3023159A (en) * 1956-03-09 1962-02-27 Socony Mobil Oil Co Inc Controlled hydrocracking process
US2910523A (en) * 1956-05-08 1959-10-27 Gulf Research Development Co Hydroisomerization process
US2900425A (en) * 1956-08-10 1959-08-18 Universal Oil Prod Co Isomerization process
US2924629A (en) * 1956-10-19 1960-02-09 Universal Oil Prod Co Isomerization process
US2908656A (en) * 1956-11-05 1959-10-13 Houdry Process Corp Pretreatment of noble metal catalysts
US2939894A (en) * 1956-11-19 1960-06-07 Pure Oil Co Isomerization of light petroleum distillates employing catalyst comprising iron-group metal on lithium-modified acidic mixed oxides support
US2969318A (en) * 1956-12-17 1961-01-24 Texaco Inc Spent catalyst seal for a catalytic reactor
US2926207A (en) * 1956-12-31 1960-02-23 Pure Oil Co Isomerization catalysts and process
US2888501A (en) * 1956-12-31 1959-05-26 Pure Oil Co Process and catalyst for isomerizing hydrocarbons
US2918509A (en) * 1957-10-31 1959-12-22 Pure Oil Co Process and catalyst for the isomerization of hydrocarbons
US2982802A (en) * 1957-10-31 1961-05-02 Pure Oil Co Isomerization of normal paraffins
US2913508A (en) * 1957-11-07 1959-11-17 Pure Oil Co Process for isomerizing hydrocarbons
US2961414A (en) * 1957-11-15 1960-11-22 Kellogg M W Co Platinum and palladium catalysts
US2967207A (en) * 1957-11-27 1961-01-03 Pure Oil Co Silica-alumina catalyst copromoted with palladium and iron-group metal, and isomerization process catalyzed thereby
US2939896A (en) * 1957-12-09 1960-06-07 Phillips Petroleum Co Isomerization process and catalyst
US2947683A (en) * 1957-12-12 1960-08-02 Pure Oil Co Process for improving the octane number of naphthas
US2925453A (en) * 1957-12-16 1960-02-16 Pure Oil Co Process and catalyst for the isomerization of hydrocarbons
DE1078097B (de) * 1958-02-01 1960-03-24 Konink Zwavelzuurfabrieken V H Verfahren zur Verbesserung von Katalysatortraegern aus Aluminiumoxyd
US2939897A (en) * 1958-08-15 1960-06-07 Pure Oil Co Process and catalyst for the isomerization of light paraffin
US2943128A (en) * 1958-10-06 1960-06-28 Pure Oil Co Process and catalyst for isomerizing normal paraffins
US2943129A (en) * 1958-10-07 1960-06-28 Pure Oil Co Process and catalyst for isomerizing normal paraffins
US3047645A (en) * 1959-12-07 1962-07-31 Pure Oil Co Process for the catalytic hydroisomerization of crude normal-pentane
US3116259A (en) * 1960-03-30 1963-12-31 Pure Oil Co Method of preparing isomerization catalyst
US3153627A (en) * 1960-04-04 1964-10-20 Gulf Research Development Co Catalytic process
US3151180A (en) * 1960-07-15 1964-09-29 Phillips Petroleum Co Production of normally liquid olefins
US3202724A (en) * 1961-07-17 1965-08-24 Norton Co Dehydrogenation of hydrocarbons
US3177136A (en) * 1961-08-24 1965-04-06 Socony Mobil Oil Co Inc Reforming with steamed platinum catalyst
US3264207A (en) * 1961-09-08 1966-08-02 Sinclair Research Inc Controlling hydrogen partial pressure in a reforming process

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