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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 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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Description

April 24, 1951 F. G. CIAPETTA 2,550,531
REFORMING PROCESS AND CATALYST THEREFOR CON VERSION 0F/167 REA6770/V TEMPERATURE fT EST INVENTOR.
9 M FRANK a. CYAPETTA AT TORNEY April 24, 1951 F. G. CIAPETTA REFORMING PROCESS AND CATALYST THEREFOR 4 Sheets-Sheet 2 Filed Dec. 29, -1949 CONVERSION OF 61 REACT/0N TEMPERATURE "1? wwmwwww Qwwi RMQQQ G R INVENTOR. FRANK G C/APETTA Ml/ BY W Z ATTORNEY ATTEST April 24, 1951 F. G. CIAPE' I'TA 2,550,531
\ REFORMING PROCESS AND CATALYST THEREFOR Filed Dec. 29, 1949 4 Sheets-Sheet 3 J00 400. TER5"PER GRAN 200 V SURFACE AREA //v SQUARE ME Q Q Q a a Q u Q Q g a a *e g a a a? a 12 0 35019213671411 IVO/lQVJb AWEST INVENTOR.
, ATTORNEY April 24, 1951 F. G. CIAPETTA REFORMING PROCESS AND CATALYST THEREFOR 4 Sheets- Sheet 4 Filed Dec. 29, 1949 y, AROMA r/cs m M M 6W N Y M B F. QMI/ T m T T, .A
ATTORNEY Patented Apr. 24,1951
UNITED STATES PATENT omcs 2,550,531 REFO'RMTN'G income s, CATALYST THEREFOR Frank G Ciane'tta, Llanerch Hills, Pa, assigno'r to The Atlantic Refining Comiia'ny, Philadel phia, Pa.-, a corporation of Pennsylvania Apblica'tion December 29, 1949, serial No. rssnst 11 Glaims. i
- 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. To obtain best results in reforming such hydrocarbons it is desirable to cause max-' keep at a minimum or to obtain substantially-no demethanation of the paraffins during iso'r'neriza tio'n; hydrogenation of aromatics to naphthenic hydrocarbons and indiscriminate-or uncontrolledcracking, particularly of the paraflin's.
All the reactions during reforming are to a greater or lesser degree reversible depending onthe' various e'quilibriainvolved. The reversal of the dehydrogenation reaction of the cyclo compounds to aromatics takes place most readily and the reversar of the cracking reaction is most difiiiflt' partieman if carbon is formed the cracking. The isomeri'zation of" the iiarafiins" 2 in such hydrocarbon mixtures is one of the important factors in reforming them. During 1st;- merization methyl and to a lesser eirtent ethyl groups are shifted from the straight chain to side chain positions and this should be done with a minimum of demethanat'ion and/ or carbon pro auction. The carbon to carbon bonds instead of being broken are merely put under a strain which condition, particular- 1y in the presence of the instant catalyst,- they shift to the side chain position or positions to produce an isomer in which the carbon atoms are more centralized as com-pared to a straight chain compound. Such isomers have higher anti-knock characteristics than their corresponding straight chainparaifins. 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. These reactiohs result in an increase in the anti-knock char acteristics of the reformed products since the octane rating of aromatics is Very high compared to that of the saturated cycle compounds; selecti've cracking of the long chain parafiinsinto low boiling fractions'particularly wh'ehthe 01mg: ing stock contains components boiling above about 400 F. is also importantboth because such lower boiling fractions by virtue of their lower molecular weights have higher octane numbers and because such lower boiling components may be further increased in anti-knock value by the above described reactions;
The isomerizat-ion; however; should be accom plished with a minimum of demethanat'ion' and carbon deposition both because" demethanation reduces yields and carbon deposition affects catalytic activity further reducing yield. 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. These reactions are in reality hydrogenation reactions and' take place simultaneously with the dehydrogenat'ion that occurs' withthe dehydrocy'clization 0f the paramns and the jalor'natifia'tion' 0f the saturated cycle compounds.
It has been discovered that 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. These'discoveries, together with the fact that increased temperature during reforming increases the aromatizations of saturated cyclohexanes and the dehydrocyclization of acyclic paraffins to aromatics permit the reforming of hydrocarbons to obtain reformed products which are high in yield and anti-knock value. By controlling the surface area of the catalyst high isomer yields at high temperatures can be accomplished during reforming regardless of pressure, since isomerization is independent of the pressure. This permits the use of high reaction temperatures which in turn favors maximum production of aromatic hydrocarbons. Moreover, since isomerization is independent of the pressure, higher hydrogen partial pressures at higher pressure may be used to reduce the amount of demethanation and carbon deposition, thus further contributing to the high yield of high octane products and increased life of the catalyst Without regeneration. The applicant has also discovered that at surface areas of square meters per gram of silica alumina component and below, the activity of the catalyst drops off rapidly and therefore surface areas from about 10 to about 65 square meters per gram of component should be used in practicing the invention.
Broadly 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.
In its narrower aspect, the invention 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 is an important feature of the invention. 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, the area of which is preferably subsequently reduced, 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.
It is preferable to adjust 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.
After a period of service, it may be desirable to reactivate the catalyst and this may be accomplished readily by passing air or other oxygencontaining gases therethrough in order to burn carbonaceous deposits from 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.,,
amounts from 1 to 20 mole. of hydrogen per mol.
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.
In carrying out reforming in accordance with this invention, to 1000 F. and preferably 700 to1000 F. may be used. The process may also be conducted at pressures from 100-to 1000 pounds per square inch and preferably at 500 to 800 pounds per square inch. Hourly space velocities (meaning the liquid volume of hydrocarbon per hour per volume of catalyst) may be in the range of 0.1 to 10, preferany in' the'range of 0.5 to 4. The reaction may be'carried out in the presence of hydrogen in of hydrocarbon. Under these circumstances, using the instant novel catalyst it is possible to obtain from petroleum distillates, particularly gasoline fractions, yields on the order of magnitude of 88-90%. or higher having motor method vclear o'ctane numbers of 71-74 or higher.
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. After reforming, the products may be fractionated to separate excess hydrogen and to recover the desired fractions of reformed product.
In one manner of operation of the process, suflicient hydrogen will be produced in the reforming reaction to maintain a hydrogen partial pressure sufficient to saturate'the hydrocarbon fragments formed therein. However, 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. Also,
if desired, the petroleum distillates may be treated to remove sulfur before they are reformed.
temperatures in the range of 600 10 I weight 46.3% of normal heptane, 44% ofcyclo 6 The invention will be further illustrated in the following examplesand drawings. It should be understood, however, that the examples and the drawings are given for purposes of illustration and the invention in its broader aspects is not limited thereto.
EXAMPLE 1 A mixture of hydrocarbons containing by hexane and 9.7% benzene was prepared by mix;
'ingtogether suitable amounts of these consti-f per square inch pressure and that of Table 2 was obtained at 700 pounds per square inch pressure. The data in both tables was obtained usin a liquid space velocity of 1. and a molar ratio of hydrogen to hydrocarbon of 4 to 1.
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. V.=1.0; HzzHC =4=1 Charge: n0 (normal heptane) .3; eyclohexane 44.0; benzene=9.7 Wt. Per Cent Pt0.5% by Wt. Pt-0.25% by Wt. Pt0.l% by Wt. Pt-0.25% by Wt. Pt-0.125% by wt. S. A.=425 sq. m./g. S. A.=200 sq. m./g. S. A.=82 sq. m./g. S. A.=45 sq. m./g. S. A.=22 sq. m./g. i
o Reaction Conv. Yield Yield Conv Yield Yield Conv. Yield Yield Conv. Yield Yield Conv. Yield Yield of of C1 of of of 01 of of of C of of of C1 of of of C1 of isomers Arom. n01 Isomers Arom n0 Isomers AlOm. nC'l Isomers Arom n01 Isomers Arom.
Table II Constants: pressure: 700 p. s. i.-'g.; Lxs. V.=1; H7:HO=4:1 Charge: nO7 (normall1eptane) 46.3; cycloh xane 44.0; benzene=9.7 Wt. Per Cent Pt, =0.5% Pt0.1 Pt 0.05% S. A.=425 sq. m./g. S. .A.=82sq. m./g. S. A.=45 sq. m./g. Temp F.
Ream Conv. 3 Yield of Conv. Yleld Yield of Conv Yield Yield of.
0f 07 0f C7 0f 07 of 110 Isomers Atom. of 1107 Isomers Arom. of M37 Isomers Arom.
In the accompanying drawings,
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.
The data for the various figures were taken from Tables I and II of Example 1. Referring to the drawings, 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. It will be noted from the curves of these figures that 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. For convenience and clarity in illustration catalysts having surface areas M425 and 45 square meters per gram are shown in the curves.
In Figure 2 conversion'of the normal C7 fraction versus reaction temperature is plotted for.
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. Vertical line 4 was then drawn from this point of intersection and extended to cross the abscissa of Figure 2; The point of intersection of line 4 with the abscissa of this figure was noted. This value represents the reaction .temperature at which maximum yield of isomer occurs for the catalyst of curve A of Figure 1, i. e., 425 square metersper gram'using 350 pounds per square inch pressure. This surface area and this temperature were then plotted in curve H of Figure 5. In a similar 'manner the reaction temperature for maximum isomer yield was obtained for curve B of Figure l and curvesC and D of Figure 3 from curve F of Figure 2 and curve G of Figure .4, respectively. The other values necessary to 'draw curve H of Figure 5 were obtained by drawing curves similar to Figures '1 through 4 for catalysts having various surface areas. Asstated earlier, for clarity and convenience ,of illustration, such additional curves are n'ot'sho'wn.
It will be noted that the right hand portion of 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.
The formation of aromatics versus reaction temperature is plotted in Figure 6. The curve J "representing the formation of such aromatics at 350 pounds per square inch and the curve K for 7700 pounds :per square inch pressure under the reforming conditions .and with the catalyst tabulated in Tables I :and II. .Since the mixture reformed contained 937% benzene all values on these curves to the right of vertical line 5-represent the production'offaromatics during the "conversion while'those points :on the-curve to the left-of line-5 of this figureirepresent destruction of aromatics substantially entirely by hyldrogenation to form saturated 'cyclo :compounds. :The
pointstat which curves J :and rKzintersect the iline :5 represent the temperatures at which the hydrogenation 0f aromatics: and Lthe dehydrogenation of saturated cyc1o=conipounds -is-in equilibarson-s 1 irium. These temperatures are determined by drawing horizontal lines 6 and I. It will be seen,
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.
In re-examining Figure '5 in the light of the foregoing remarks with reference to Figure 6, it isseen that a catalyst having a base, the surface area of which is greater than about 65 square meters per gram is very sensitive to temperatures insofar as maximum isomer yield is concerned and that with surface areas below about square meters per gram, the catalyst is substantially insensitive to temperature changes insofar as max,- imum isomer yield is concerned. Stated in an- .other way, it is seen from a comparison of Figure 5 and Figure 6 that inthe range of surface areas above 65 square meters per gram the tempera.- .ture .levels at which maximum isomer-ization occurs will not permit any substantial yields of arcmatics, whereas in the range below 05 square meters per gram, a range of reaction temperatures exists which permits the simultaneous production of maximum yields of isomers and aromatics.
v For catalysts having a high surface area the high temperatures which are desirable to obtain high yields of aromatics result in excessive, indiscriminate cracking as is illustrated by curve H of Figure 5. Such cracking largely results in demethanation or carbon deposition depending uponthe amount of hydrogen present during the reforming and the pressure of such hydrogen. In general, the more hydrogen that is present and the higher the pressure that is used, the less carbon will be deposited. The advantage then of the presence of hydrogen at high pressure where cracking occurs is to reduce or substantially eliminate the deposition of carbon and to cause such cracking as occurs to be of the demethanation type. The use of high pressures,
howevenwill require the use of even higher temperatures in order to obtain the desired amount of aromatic hydrocarbons in the reformed product. High temperatures, however, cannot be used with a catalyst having a surface area in excess of about 65 square meters per gram since with such catalysts, even in the presence of high amounts of hydrogen at high pressures, excessive cracking of the demethanatlon type takes place and must result in a low yield of desired liquid product due to high gas losses. Where, however, a catalyst has a low surface area, not exceeding 65 square meters per gram, high temperatures may be used to obtain high yields of aromatics and maximum yield of isomers without causing indiscriminate cracking since catalysts with such surface characteristics do not produce large amounts of gas at high temperatures.
EXAMPLE II A naphtha from an Arabian crude oil having the following properties was reformed in accordance with the invention:
API gravity at 60 degrees 57 10. ASTM distillation:
Overpoin't 1"' 167 50% F 27s Endpoint 'F 400 Clear octane number (m'otormethod) 37.3 Sulphur per cent 0.03
Y A silica-alumina catalyst having a surface area of 45 square meters per gram was prepared as'described inExample I. After steamin the pellets toadjust their surface area to the 45 square meters per gram, a part of them was treated as set forth in Example; to deposit thereon 025% of metallic platinum, the remaining 'portionwas not so treated and contained no platinum: Both portions of catalyst were then used to reform the above identified naphthaunder the following reforming conditions to give the results tabulated in Table III: 350 pounds per square inch pressure, liquid space velocity of 1, hydrogen to hy- The flexibility of the instant catalyst in reforming hydrocarbons by virtue of its reduced sensitivity to temperature at low surface areas of the cracking component and the importance of this discovery is therefore apparent. The present novel catalyst and process of reforming hydrocarbons with such catalyst, therefore permits the reforming of hydrocarbons to obtain high yields of a reformed product having high anti-- knock characteristics.
The cracking component may also comprise low surface area silica-'zirconia, silica-aluminazirconia, silica magnesia, silica=alumina-magnesi'a, silica-thoria, silic'a-alumina-thoria, alumina-boria, etc., in addition to silica-alumina and such components may be impregnated with a metal containin hydrogenation catalyst such as the metals, oxides and salts of the elements of groups VI and VIII of the periodic system such as, for example, the oxides of chromium, molybdenum, tungsten and uranium, the metals, nickel, cobalt, iron and the salts thereof such as the molybdates, thiomolybdates, phosphates, tungstates, chromates and borates in addition to platinum and palladium.
I claim:
1. 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.
2. 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.
3. 'A process for reforming a gasoline fraction to increase the anti-knock value thereof which amount from 0.01 to 2.5% by weight of the final catalyst, said cracking component having a surface area in the range of about 10 to about 65 square meters per gram of said component.
4. 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.
5. 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.
6. 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.
7. 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.
8. 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.
9. 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.
10. 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.
11. A process according to claim 10 in which the metal composited with the cracking component is platinum.
- FRANK G. CIAPETTA.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS

Claims (1)

  1. 6. 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 AND HAVING A SURFACE AREA IN THE RANGE OF ABOUT 10 TO ABOUT 65 SQUARE METERS PER GRAM OF SAID COMPONENT.
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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
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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
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US2888501A (en) * 1956-12-31 1959-05-26 Pure Oil Co Process and catalyst for isomerizing hydrocarbons
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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
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US2943128A (en) * 1958-10-06 1960-06-28 Pure Oil Co Process and catalyst for isomerizing normal paraffins
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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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