WO1984002663A1

WO1984002663A1 - Platinum group metal and phosphorous catalyst compositions

Info

Publication number: WO1984002663A1
Application number: PCT/US1982/001823
Authority: WO
Inventors: George J Antos; Tai-Hsiang Chao
Original assignee: Uop Inc
Priority date: 1982-12-30
Filing date: 1982-12-30
Publication date: 1984-07-19
Also published as: EP0130976A1

Abstract

A new catalyst composition for converting hydrocarbons. Also disclosed is a method for making the catalyst. The catalyst comprises a platinum group component and a phosphorous component with a porous support material. Preferably, the catalyst is made by compositing a platinum group component with a porous support material and then contacting that composite with phosphorus or a compound of phosphorus. In a preferred embodiment of the invention a catalyst comprising platinum, cobalt, tin, phosphorus and chlorine with alumina is utilized in the catalytic reforming of hydrocarbons boiling in the gasoline range to produce a high octane reformate suitable for gasoline blending or a high aromatics content reformate suitable as a petrochemical feedstock.

Description

PLATINUM GROUP METAL AND PHOSPHOROUS CATALYST COMPOSITIONS

TECHNICAL FIELD

This invention pertains to solid catalysts for the conversion of hydrocarbons, especially reforming of hydrocarbons boiling in the gasoline range to produce high octane reformate for gasoline blending or high aromatics content reformate for petrochemical feedstocks.

BACKGROUND ART

U.S. Patent No. 2,349,827 discloses the phosphates of metals like aluminum and magnesium, for example, as catalysts for reforming hydrocarbons.

U.S. Patent No. 2,441,297 discloses adding an aluminum salt of a pentavalent phosphorous compound to a catalyst support material for improved heat stability and catalyst life in a wide variety of reactions, including reforming of hydrocarbons. The preferred phosphorous compound is aluminum orthophosphate which is precipitated with the preferred alumina support.

U.S. Patent No. 2,890,167 discloses a reforming catalyst comprising a metal or mixtures of metals from Group VIII of the periodic table, a compound of phosphorus and a cracking component. The cracking component is a support material which may be at least two refractory inorganic oxides together or a refractory inorganic oxide and halogen.

U.S. Patent No. 3,224,831 discloses treating a porous support material and platinum composite with a compound of phosphorus selected from the group consisting of the acids of phosphorus and ammonium phosphate. Catalysts prepared by the method disclosed in this patent are useful in the catalytic oxidation of hydrocarbon and carbon monoxide constituents which are present in the exhaust gas of internal combustion engines.

U.S. Patent No. 3,227,658 discloses contacting a catalyst containing a Group VIII metal and alumina at elevated temperatures with an activating agent selected from the group consisting of the volatile chlorides and bromides of boron and phosphorus and the mixed chlorobromides thereof. The catalysts disclosed is this patent are useful in the isomerizaton of hydrocarbons. This treatment with the gaseous boronic or phosphorous halides adds halide to the catalyst for increased isomerization activity.

U.S. Patent No. 3,642,658 discloses contacting a Group VIII metal surface, especially nickel or platinum, with a Group V compound of the general formula X3M, where X is an organic radical, hydrogen or a halogen atom and M is an atom of phosphorus, arsenic or antimony so that the atomic ratio of the Group-V component to the Group VIII component is from 0.01 to 0.5. The catalysts disclosed in this patent are useful in the hydrogenation of diolefins to mono-olefins.

U.S. Patent No. 3,706,815 discloses depositing the chelates of a Group VIII noble metal and a polyphosphoric acid on a porous support material. The catalysts disclosed in this patent are useful in the isomerizing of hydrocarbons.

U.S. Patent No. 3,792,086 discloses a catalyst comprising phosphoric acid and palladium metal. The catalyst disclosed in this patnent is useful in the vapor phase oxidation of propylene or isobutylene to produce acrylic or methacrylic acids.

U.S. Patent No. 4,356,338 discloses a method for extending cyrstalline zeolite catalyst life by pretreatment of the catalyst with steam and a phosphorus containing compound.

U.S. Patent No. 4,359,406 discloses highly dispersed Group VIII metal-phosphorus or Group VIII metal- arsenic compounds on high surface area supports. After low temperature air calcination or decomposition in water at room temperature, the supported and dispersed compounds disclosed in this patent are useful as electrodes in electrochemical fuel cells.

DISCLOSURE OF INVENTION

(a) Description

This invention pertains to a new catalyst composition for converting hydrocarbons and to a process for converting hydrocarbons using the new catalyst. This invention also pertains to a method for making the new catalyst. The catalyst comprises a platinum group component and a phosphorous component with a porous support material. Preferably the catalyst is made by compositing a platinum group component with a porous support material and then contacting that composite with phosphorus or a compound of phosphorus. Addition of the phosphorous component according to our invention provides a platinum group metal-containing reforming catalyst with improved selectivity characteristics as exhibited by increased or stabilized C5+ yields of constant octane reformate product or more hydrogen production per barrel of feedstock. Preferably in the final catalyst composite of our invention the phosphorus to platinum group component atomic ratio is greater than 0.5; preferably this atomic ratio is from about^' 0.5 to about 20.0. After our composite is contacted with phosphorus or a compound of phosphorus it is preferably reduced prior to its first use in the conversion of hydrocarbons without an intermediate oxidation step. Preferably the final catalyst is reduced with a substantially pure and dry hydrogen stream at a temperature of about 400° to about 1600°F (200°-870°C) and a gas hourly space velocity (GHSV - calculated as the volume of the reducing gas contacted with the catalyst per hour at standard conditions divided by the bulk volume of the catalyst particles) of about 10 to 10,000 for about 0.5 to 10 hours. Preferably the catalyst contains, on an elemental basis, about 0.01 to about 5 wt. % platinum group component and about 0.01 to about 5 wt.% phosphorus. Preferably the catalyst also contains, on an elemental basis, about 0.01 to about 15 wt. % of a halogen component. The catalyst may also contain, on an elemental basis, about 0.01 to about 10 wt. % sulfur.

Optionally, the catalyst may also contain catalytically effective amounts of other, additional components which act alone or in concert as catalyst modifiers to improve catalyst activity, selectivity or stability. For hydrocarbon conversion catalysts some well-known modifiers include antimony(Sb), arsenic(As), beryl!ium(Be), bismuth(Bi), cadmium(Cd), calcium(Ca), chromium(Cr), cobalt(Co), copper(Cu), gallium(Ga), germanium(Ge), gold(Au), indium(In), iron(Fe), lead(Pb), lithium(Li), anganese(Mn), molybdenu (Mo), nickel(Ni), rhenium(Re), scandium(Sc), silver(Ag), tantalum(Ta), thallium(Tl), tin(Sn), titaniu (Ti), tungsten(W), uranium(U), zinc(Zn) and zirconium(Zr). Specific catalysts within the scope of this invention which we have made and tested include Pt/P, Pt/Ga/P, Pt/Re/P, Pt/Co/P, Pt/Ni/P, Pt/Ir/P, Pt/Re/Co/P, Pt/Re/Ni/P, Pt/Re/Ir/P, Pt/Re/Sn/P, Pt/Co/Sn/P, Pt/Co/In/P, Pt/Co/U/P, Pt/Rh/Ga/P, Pt/Sn/P, and Pt/Ge/P, all on chlorided gamma alumina.

The catalyst of our invention is useful for the conversion of hydrocarbons, especially reforming of naphtha feedstocks boiling in the basoline range. Reforming reactions include dehydrogenation of naphthenes to aromatics, dehydrocyclization of paraffins to aromatics and hydrocracking and isomerization of naphthenes and paraffins, and the like reactions, to produce an octane-rich or aromatics-rich product stream. Reforming conditions include a ^•temperature of about 500° to about 1100°F_f (260°-600^OC), a pressure of about 50 to 1000 psig (345-6,900 kPa-gage), a liquid hourly space velocity (LHSV - calculated as liquid volume of the feedstock contacted with the catalyst per hour at standard conditions divided by the bulk volume of the catalyst particles) of about 0.1 to about 10 and a mole ratio of hydrogen to hydrocarbon of from about 0.5:1 to about 20:1.

To be commercially successful a reforming catalyst must satisfy three essential requirements, namely, high activity, high selectivity and good stability. Activity is a measure of the catalyst's ability to help convert reactants into products at a specified severity level where severity level means the reaction conditions used, that is, temperature, pressure, contact time and presence of diluents such as hydrogen, if any. For refoming catalyst activity we measure the reactor heater temperature in degrees Fahrenheit required to maintain a target research octane number of 101.5 for the reformate product. Selectivity is a measure of the catalyst's ability to help produce a high amount of desired product or products relative to the amount of reactants charged or converted. For catalyst selectivity we measure C5+ yield, or the amount of hydrocarbons with 5 or more carbon atoms recovered, in liquid volume percent, relative to the total volume of the hydrocarbon charged. Stability means the rate of change with time of the activity and selectivity parameters - the smaller rate implying the more stable catalyst.

Regarding the platinum group component of our catalyst composite, it may be selected from the group of platinum or palladium or iridium or rhodium or osmium or ruthenium or mixtures thereof. Platinum, however, is the preferred platinum group component. We believe that substantially all of the platinum group component exists within the final catalyst composite in the elemental metallic state.

Preferably the platinum group component is well dispersed throughout the catalyst composite. The platinum group component can be used in any catalytically effective amount, with good results being obtained with about 0.01 to about 5 wt. % platinum, for example, calculated on an elemental bais, of the final catalyst composite. Preferably the catalyst comprises about 0.4 wt. % platinum.

The platinum group component may be incorporated in the catalyst composite in any suitable manner such as by coprecipitation or cogelation or coextrusion, ion exchange or impregnation either before, while or after other catalytic components are incorporated. Preferably the platinum group component is composited with the porous support material before the phosphorous component is composited. The particular method of incorporating the platinum group component is not deemed to be an essential feature of this invention. The preferred method of incorporating the platinum group component is to impregnate the support material with a solution or suspension of a decomposable compound of a platinum group metal. For example, platinum is preferably added to the support by commingling the latter with an aqueous solution of chloroplatinic acid. Hydrochloric acid or nitric acid or other optional components may be added to the impregnating solution to further assist in dispersing or fixing the platinum group component in the final catalyst composite.

Regarding the phosphorous component of our catalyst composite, it may exist in any catalytically active form such as the element or as a compound of phosphorus. At this time we do not know the precise form of phosphorous component. Preferably this phosphorous component is also well dispersed throughout the catalyst composite. The phosphorous component can be used in any catalytically effective amount, with good results being obtained with about 0.01 to about 5 wt. % phosphorus, calculted on an elemental basis, of the final catalyst composite. Preferably the catalyst comprises about 0.5 wt. % phosphorus.

Preferably, for the catalysts of our invention, the platinum group component is first composited with the porous support material. Then, the porous support material and platinum group component composite is contacted with phosphorus or a compound of phosphorus to incorporate the phosphorous component on or in the catalyst composite. The phosphorous component may be incorporated with the porous support material and platinum group componment composite in any suitable manner. The particular method of incorporating the phosphorous component is not deemed to be an essential feature of this invention. A preferred method for incorporating the phosphorous component is to impregnate the porous support material and platinum group component composite with a solution or suspension of a decomposable compound of phosphorus. Suitable phosphorous compounds for use in this impregnation method include hypophosphorous acid, dimethylphosphite, triphenylphosphine, cyclohexylphosphine, phosphorous trichloride, phosphoric acid, tributylphosphine oxide, tributyl phosphite, phosphorous tribromide, phosphorous triiodide, phosphorous oxychloride and the like compounds. The preferred impregnation solution comprises an aqueous solution of hypophosphorous acid.

Regarding the porous support material of our catalyst composite, it is preferably a porous, absorptive support with high surface area of from about 25 to about 500m²/g. The porous support material should be relatively refractory to the conditions utilized in the hydrocarbon conversion, process. It is intended to include within the scope of our invention the use of support materials which have

OMPI traditionally been utilized in hydrocarbon conversion catalysts such as, for example; (1) activated carbon, coke, or charcoal; (2) silica or silica gel, silicon carbide, clays, and silicates including those synthetically prepared and naturally occurring, which may or may not be acid treated, for example attapulgus clay, china clay, diatomaceous earth, fuller's earth, kaolin, kieselguhr, etc.; (3) ceramics, porcelain, crushed firebrick, bauxite; (4) refractory inorganic oxides such as alumina, titanium dioxide, zirconium dioxide, chromium oxide, beryllium oxide, vanadium oxide, cesium oxide, hafnium oxide, zinc oxide, magnesia, boria, thoria, silica-alumina, silica-magnesia, chromia-alumina, alumina-boria, silica-zirconia, etc.; (5) crystalline zeolitic alu ino-silicates such as naturally occurring or synthetically prepared mordenite, faujasite or other zeolites, either in the hydrogen form or in a form which has been exchanged with metal cations; (6) spinels such as gAl2θ4, ZnAl2U4 and other like compounds having the formula M0-A1 03 where M is a metal having a valence of 2; and (7) combinations of materials from one or more of these groups. The preferred support material for our catalyst is alumina, especially gamma- or eta-alumina.

The preferred alumina support material may be prepared in any suitable manner from synthetically prepared or naturally occurring raw materials. The support may be formed in any desired shape such as spheres, pills, cakes, extrudates, powders, granules, etc., and it may be utilized in any particle size. One preferred shape of alumina is the sphere. Another preferred shape of alumina is the cylinder. A preferred particle size is about 1/16 inch (.16 cm) in diameter, though particles as small as about 1/32 inch (.08 cm), and smaller, may also be utilized.

To make alumina spheres aluminum is converted into an alumina sol by reacting aluminum powder with a suitable peptizing acid and water, and then dropping a mixture of

OMPI the resulting sol and a gelling agent into an oil bath to form spherical particles of an alumina gel which are easily converted into the gamma-alumina support material by known methods including aging, drying and calcining. To make alumina cylinders, an alumina powder is mixed with water and a suitable peptizing agent such as nitric acid, for example, until an extrudable dough is formed. The dough is then extruded through a suitably sized die to form extrudate particles. Other shapes of the alumina support material may also be prepared by conventional methods. After the alumina particles are shaped generally they are dried and calcined. The alumina support material may be subjected to intermediate treatments during its preparation, including washing with water or contacting with ammonium hydroxide, for example, or with other compounds^", but these treatments are generally well-known in the art, and they are not unique to the preparation of our new catalyst. Other catalyst components, including catalyst modifiers discussed above, may be added to the preferred alumina carrier material during or after its preparation.

Preferably the catalyst composite of our invention also contains a halogen component. The halogen component may be either fluorine, chlorine, bromine or iodine or mixtures thereof. Chlorine and bromine are the preferred halogen components. The halogen component is generally present, we believe, in a combined state with the porous support material. Preferably the halogen component is also well dispersed throughout the catalyst composite. The halogen component generally will comprise about 0.01 to about 15 wt. %, on an elemental basis, of the final catalyst composite. Preferably the catalyst comprises about 1.0 wt. % chlorine.

The halogen component may be added to the support material in any suitable manner, either during the preparation of the support or before, while or after other

_^ OMPI

. catalyst components are incorporated. For example, the alumina hydrosol utilized to form the preferred alumina support material may contain halogen and thus contribute at least some portion of the halogen content in the final catalyst composite. Also, the halogen component or a portion thereof may be added to the catalyst composite during the incorporation of the support material with another catalyst component, for example, by using chloroplatinic acid to impregnate the platinum componment. Also, the halogen component may be added to the catalyst composite by contacting the catalyst with the halogen or a compound, solution or suspension containing the halogen after the other catalyst components have been incorporated with the support material. Suitable compounds containing the halogen include, for example, acids containing the halogen such as hydrochloric acid and the like. Or, the halogen component may also be incorporated by contacting the catalyst with the halogen or a compound, solution or suspension containing the halogen in a subsequent regeneration step. In the regeneration step carbon deposited on the catalyst as coke during use of the catalyst in the hydrocarbon conversion process is burned off the catalyst and the agglomerated platinum group component on the catalyst is redistributed to provide a regenerated catalyst with performance characteristics much like the fresh catalyst. The halogen component may be added during the carbon burn step or during the platinum group component redistribution step, for example, by contacting the catalyst with hydrogen chloride gas. Also the halogen component may be added to the catalyst composite by adding the halogen or a compound, solution or suspension containinmg the halogen, such as propylene dichloride, for example, to the hydrocarbon feed stream or to the process recycle gas during operation of the hydrocarbon conversion process. Optionally the catalyst composite of our invention can also contain a sulfur component. Generally the sulfur component will comprise about 0.01 to about 10 wt. %, calculated on an elemental basis, of the final catalyst composite. The sulfur component may be incorporated on or in the catalytic composite in any suitable manner. Preferably sulfur or a compound containing sulfur such as hydrogen sulfide, for example, is contacted with the catalyst composite in the presence of nitrogen at ambient temperature, preferably under water-free conditons, to incorporate the sulfur component.

After the platinum group componment has been combined with the porous support material, the porous support material and platinum group component composite generally will be dried at a temperature of about 200° to about 400°F (90°- 200°C) for about 1 to about 24 hours or more, and then calcined or oxidized at a temperature of about 600° to about 1200°F (320°-650°C) or more in an air or oxygen atmosphere for about 0.5 to about 10 hours in order to convert substantially all of the platinum group component to the oxide or oxyhalide form. When a halogen component is utilized in the catalyst, the halogen content of the catalyst is best adjusted during the oxidation step by including a halogen or halogen-containing compound such as hydrochloric acid, for example, in the air or oxygen oxidizing atmosphere. In particular, when the halogen component of the catalyst is chlorine it is preferred to use a mole ratio of water to chlorine of about 5:1 to about 100:1 in air during at least a portion of the calcination step in order to adjust the final chlorine content of the catalyst to a range of from about 0.1 to about 5 wt. %. Preferably the duration of this halogenation step is about 1 to 5 hours.

The calcined or oxidized porous support material and platinum group component composite is then preferably subjected to a reduction step prior to incorporation of the phosphorous component. This reduction step is designed to reduce the platinum group component to the elemental metallic state and to ensure a uniform and finally divided dispersion of it throughout the support material. Preferably a substantially pure and dry hydrogen stream is used as the reducing agent in this step. The reducing agent is contacted with the catalyst at conditions including a reduction temperature of about 400° to about 1200°F, (200° -650°C) a GHSV of about 10 to 10,000, sufficient to a rapidly dissipate any local concentration of water formed during the reduction step, for about 0.5 to 10 hours, effective to reduce substantially all of the platinum group component to the elemental metallic state. When the phosphorous component is incorporated after the other catalyst components, best results have been obtained by contacting a reduced platinum-containing composite with an impregnation solution or suspension containing a compound of phosphorous and then drying and re-reducing the final composite without an intermediate oxidation step.

For the purposes of this application "drying" means contacting the catalyst composite with an environment at a temperature intended to make the composite more free from water or fluid. For example, after the phosphorous component has been impregnated on the composite from an aqueous solution of hypophosphorous acid, the composite is dried in air at about 225°F (110°C) to evaporate the excess impregnation solution. "Oxidizing", on the other hand, means contacting the catalyst composite with an environment at a temperature intended to increase the oxidation state of a catalyst component. For example, after the platinum group component has been impregnated on the porous support material, the composite is oxidized in air at about 975°F (525°C) to convert substantially all of the platinum group component to the oxide form. "Reducing" means contacting the catalyst composite with an environment at a temperature intended to decrease the oxidation state of a catalyst component. For example, after the platinum group component has been impregnated on the porous support material and the composite oxidized, it is then reduced in dry hydrogen at about 1050°F (560°C) to convert the oxide form of the platinum group component to the elemental metallic state.

According to the process of this invention the hydrocarbon feedstock is contacted with the catalyst composition of this invention in a hydrocarbon conversion zone. This contacting may be accomplished with the catalyst being in a fixed, moving, ebullated or fluidized type catalyst bed, either in a continuous or a batch type operation, with either continuous or batch type regeneration of the catalyst between operational cycles. The hydrocarbon conversion zone may be one or more separate reactors, and the hydrocarbons may be contacted with the catalyst bed in an upward, downward or radial flow type fashion. The hydrocarbons may be in either the liquid, mixed liquid- vapor or vapor phase when they contact the catalyst.

The catalyst composition of this invention is best used for reforming hydrocarbons boiling in the gasoline range.

For reforming operations where the reactions of dehydrogenation, dehydrocyclization, hydrocracking, and isomerization occur simultaneously to varying extents, the preferred catalyst composition of this invention comprises, on an elemental basis, about 0.01 to about 5 wt.% platinum group component, about 0.01 to about 5 wt.% phosphorus and about 0.01 to about 5 wt.% chlorine on alumina. Best results have been obtained with a catalyst comprising about 0.4 wt.% platinum, 0.5 wt.% phosphorus, and 1.0 wt.% chlorine on gamma-alumina of about 0.5 g/ml apparent bulk density (ABD - calculated as the weight of the alumina particles in a full container divided by the volume of the container). In a reforming process the hydrocarbon and hydrogen are contacted with- the catalyst in a reforming zone at a temperature of about 775° to about 1100°F (415° - 590°C), a pressure of about 0 to about 1000 psig (0 - 6,900 kPa - gage), an LHSV of about 0.1 to about 10 hr.-l, and a mole ratio of hydrogen to hydrocarbon of about 0.5:1 to about 20:1. Preferably the pressure is about 50 to about 450 psig (345 - 3,105 kPa -gage). For reforming operations it is generally preferred to maintain the reforming zone substantially water-free, that is, with less than 20 ppm, and preferably less than 5 ppm, calculated as weight of water in the feedstock, entering the reforming zone from any source. The reforming zone may be one or more separate reactors with suitable heat exchange means therebetween to maintain the desired temperature at the inlet to each reactor. The effluent stream from the reforming zone is generally passed through a cooling means to- a_.separation zone, typically maintained at about 25° to 150°F (4° - 65°C), wherein a hydrogen-rich-gas stream is separated from the high octane or high aromatics content liquid product stream, commonly called an unstabilized reformate. The separated hydrogen stream may be recycled back to the reforming zone or utilized in other refinery processes, or both. The unstabilized reformate is typically passed to a fractionation zone wherein a stabilized reformate is recovered as the product of the reforming process.

The hydrocarbon charged to the reforming zone will comprise hydrocarbons, including naphthenes and paraffins, boiling in the gasoline range. Suitable feedstocks include straight run or natural gasoline, thermally or catalytically cracked gasolines, synthetic gasolines, partially reformed gasolines, and the like. The hydro¬ carbon feedstocks may be a full boiling gasoline having an initial boiling point of from about 50°F to about 150°F

Olv.PI (10° - 66°C) and an end boiling point of from about 325°F to about 425°F (163°-219°C). The feedstock may be pure hydrocarbons or mixtures thereof. Also, the feedstock may be pretreated by conventional methods such as by hydro- treating, including hydrodesulfurization and the like, to remove substantially all sulfurous, nitrogenous, and other contaminants therefrom or to saturate any olefins therein.

The catalyst of this invention may be utilized also for catalyzing many reactions besides the_reforming reactions discussed above, including for example, alkylation, dealkylation, transalkylation, cracking, hydrocracking, cyclization, dehydrocyclization, isomerization, denitro- genation, desulfurization, hydrogenation, dehydrogenation, hydrogenolysis, and polymerization reactions.

For dehydrogenating operations the preferred catalyst composition of this invention will comprise, on an elemental basis, about 0.01 to about 5 wt.% platinum group component, about 0.01 to about 5 wt.% phosphorus and about .01- to about 15 wt.% alkali or alkaline earth component on alumina. The alkali or alkaline earth component may be selected from the group of cesium, rubidium, potassium, sodium, and lithium or from the group of barium, strontium, calcium, and magnesium or mixtures of metals from either or both of these groups. The alkali or alkaline earth component may be incorporated with the catalyst composite in any conven¬ tional manner, either before, while or after other catalyst components are incorporated, with impregnation of it from an aqueous solution or suspension of a decomposable compound of the alkali or alkaline earth component being preferred. In a dehydrogenation process naphthenes are dehydrogenated to aromatics and normal paraffins are dehydrogenated to the corresponding normal olefins. Dehydrogenation condi¬ tions include a temperature of about 700° to about 1250°F (370⁰ - 680°C), a presure of about 0 to 1000 psig (0 - 6,900 kPa - gage), an LHSV of about 1 to about 40 hr."¹

OMPI and higher, and a hydrogen to hydrocarbon mole ratio of about 1:1 to about 20:1.

For hydrocracking and isomerizing operations the preferred catalyst composition of this invention comprises, on an elemental basis, about 0.01 to about 5 wt.% platinum group component, about 0.01 to about 5 wt.% phosphorus, and about 0.01 to about 15 wt. % chlorine on alumina, with about 10 wt. % chlorine being especially preferred. Additionally for hydrocracking and isomerizing operations, the catalyst composition of this invention may also include a Friedel-Crafts metal halide component. Suitable metal halides of the Friedel-Crafts type include aluminum chloride, aluminum bromide, ferric chloride, ferric bromide, zinc chloride, and the like compounds with aluminum chloride being preferred. The Friedel-Crafts component may be utilized in any catalytically effective amount and may be incorporated with the catalyst composite in any conventional method either before, while or after other catalyst compon¬ ents are incorporated. In hydrocracking operations high boiling paraffins, for example, are split and hydrogenated to lower boiling paraffins. In isomerizing operations normal paraffins, for example, are isomerized to the corresponding isoparaffins. Hydrocracking conditions include a temperature of about 400° to about 900°F (200° - 480°C), a pressure of about 500 psig to about 3000 psig (3,450 - 20,700 kPa - gage), an LHSV of about 0.1 to about 10 hr.^_1 and hydrogen circulation rates of about 1000 to about 20,000 standard cubic feet per barrel (17,800 - 356,000 Std w /wβ) of charge. Isomerization conditions include a temperature of about 32° to about 1000°F (0 - 540°C), a pressure of about 0 to about 1500 psig, (0 - 10,350 kPa - gage), an LHSV of about 0.2 to about 10 hr.-l and a hydrogen to hydrocarbon mole ration of about 0.5:1 to about 20:1.

OMPI (b) MANUFACTURE

An alumina support material comprising 1/16 inch spheres was prepared by: forming an alumina hydrosol by dissolving substantially pure aluminum pellets in a hydro¬ chloric acid solution, adding hexamethylenetetramine to the alumina sol, gelling the resulting solution by dropping it into an oil bath to form spherical particles of an alumina hydrogel, aging and washing the resulting particles, and finally drying and calcining the aged and washed spheres to form spherical gamma-alumina particles containing about 0.3 wt. % combined chloride. Additional details as to this method of preparing the alumina support material are given in the teachings of U.S. Patent No. 2,620,314.

An a umina support material containing 0.5 wt..% phosphorus was similarly prepared except hypophosphorous acid was also added to the alumina sol prior to gelling the support material.

Five different platinum-containing reforming catalysts were then prepared by contacting these support materials with different impregnat-ion solutions. One of the impregnation solutions contained chloroplatinic acid and hydrochloric acid. Another contained chloroplatinic acid, hydrochloric acid and hypophosphorous acid. Still another impregnation solution contained hypophosphorous acid.

Catalyst "A" contained 0.275 wt. % platinum and 0.98 wt. % chlorine. It was prepared by contacting the alumina support material with the chloroplatinic acid and hydrochloric acid impregnation solution with constant agitation. The amount of the platinum component contained in this impregnation solution was calculated to result in a final composite containing, on an elemental basis, about 0.275 wt. % platinum. In order to ensure uniform distri¬ bution of the platinum component throughout the support

OMPI material, the amount of hydrochloric acid used was about 2 wt. % of the alumina particles. Additionally, the volume of the impregnation solution was approximately the same as the bulk volume of the support material particles so that all the particles were immersed in the impregnation solution. The impregnation solution was maintained in contact with the support material particles for about 1/2 to about 3 hours at a temperature of about 70°F (21°C). Thereafter, the temperature of the impregnation solution was raised to about 225°F (107°C) and the excess solution was evaporated in about- 2 to 3 hours. The resulting dried impregnated particles were then subjected to an- oxidation step in a dry air stream at a temperature of about 975°F (5240C) and a GHSV of about 500 hr."¹ for about 1/2 hour. This oxidation step was intended to convert substantially all of the platinum to the oxide form. The resulting oxidized particles were subsequently contacted in a halogen-treating step with a sulfur-free air stream containing water and HC1 in a mole ratio of about 30:1 for about 2 hours at 975°F (524°C), and a GHSV of about 500 hr.-l in order to adjust the halogen content of the catalyst composite to a value of about 1.0 wt. %. The halogen-treated particles were, thereafter, subjected to a second oxidation step with a dry air stream at 975°F and a GHSV of 500 hr.-l for an additional period of about 1/2 hour. The oxidized and halogen-treated catalyst particles were then subjected to a dry reduction step, designed to reduce the platinum to the elemental state, by contacting them for about 1 hour with a dry hydrogen stream contain¬ ing less than 5 vol. ppm water at a temperature of about 1050°F (566°C), a pressure slightly about atmospheric and a flow rate of hydrogen of about 400 hr.^_1 GHSV.

Catalyst "B" contained 0.275 wt. % platinum, 0.91 wt. % chlorine and 0.5 wt. % phosphorus. This catalyst was prepared in the same manner as Catalyst "A" above except the alumina support material was contacted with the impregnation solution containing chloroplatinic acid, hydrochloric acid and hypophosphorous acid so the platinum group component and the phosphorous component were compo¬ sited together with the porous support material. After the impregnation step the catalyst particles were dried, oxidized and reduced in the same manner as Catalyst "A".

Catalyst "C" contained 0.275 wt. % platinum, 0.92 wt. % chlorine and 0.5 wt. % phosphorus. This catalyst was prepared in the same manner as Catalyst "A" above except the alumina support material was first contacted with the impregnation solution containing hypophosphorous acid. The amount of the phosphorous component contained in this impregnation solution was calculated to result in a final catalyst composite containing, on an elemental basis, about 0.5 wt. % phosphorus. This impregnation step was performed by adding the alumina support material particles to the impregnation solution in a nitrogen ^' atmosphere with constant agitation. The impregnation solution was maintained in contact with the particles for about 1 hour at a temperature of about 70°F (21°C). Thereafter, the temperature of the impregnation solution was raised to about 225°F (107°C) and the excess solution was evaporated in about 1 hour. The resulting dried catalyst particles were then subjected to a reduction step in a substantially dry an pure hydrogen stream at a temperature of about 975°F (524°C) for about 1 hour. Then the catalyst particles were contacted with the impregnation solution containing chloroplatinic acid and hydrochloric acid to incorporate the platinum component in the manner discussed above. So for this catalyst, the phosphorous component was composited first and then the platinum group component was composited with the phosphorus-containing porous support material.

OMPI Catalyst "D", representing an embodiment of our invention, contained 0.275 wt. % platinum, 0.91 wt. % chlorine, and 0.5 wt. % phosphorus. This catalyst was prepared by first impregnating the platinum component in the manner discussed above for Catalyst "A", drying, oxidizing, and reducing the catalyst composite and then impregnating the phosphorous component in the manner discussed above for Catalyst "C", and then drying and re- reducing the final catalyst composite. For the catalyst of our invention, then, the platinum group component was composited first and then the phosphorous component was composited with the porous support material and platinum group composite.

Catalyst "E" contained 0.275 wt. % platinum, 1.04 wt. % chlorine and.0.5 wt. % phosphorus. This catalyst was prepared by contacting the alumina support containing about 0.5 wt. % phosphorus with the chloroplatinic acid and hydrochloric acid impregnation solution, drying,- oxidizing, and then reducing the final catalyst composite in the manner discussed above for Catalyst "A." So for this catalyst, the phosphorous component was composited first while the porous support material was being prepared and then the platinum group component was composited with the phosphorus-containing support material.

We studied Catalysts "A", "B", "C", "D", and "E" for physical characteristics by hydrogen temperature- programmed-desorption (H2-TPD) experiments. These experi¬ ments comprised the following steps: (1) catalyst pretreatment/reduction, (2) hydrogen preadsorption, (3) removal of physically adsorbed hydrogen with a purge gas, (4) programmed desorption of chemisorbed hydrogen into a stream of a carrier gas, and (5) detection and analysis of the desorbed hydrogen. The experimental reactor is surrounded by a furnace connected to a programming controller which maintains the catalyst sample temperature constant or which raises or lowers the temperature linearly with time at controlled rates. As the catalyst temperature increases, for example, the hydrogen adsorbed on the catalyst desorbs and joins the carrier gas stream flowing to the detector where a signal proportional to the hydrogen concentration in the carrier gas is obtained. Conventional thermal conductivity cells, like those used in gas chromatography, including thermistor sensors, can be employed as detectors. The detector forms part of a bridge circuit which is connected to a recorder like those used in gas chromatography. Curves obtained from the recorder representing hydrogen concentration in the carrier gas as a function of temperature (or time) will be referred to in this application as desorption chromatograms. Generally, if there are different active sites on the catalyst, peaks in the hydrogen concentration signal of the chromatogranrwill appear at different temperatures (or times), largely determined by the differences in the activation energy of hydrogen desorption for that type of catalytic site, desorption at lower temperatures requiring less activation energy than desorption at higher temperatures. (See for example, R. J. Cvetanovic and Y. Amenomiya, "Application of a Temperature - Programmed Desorption Technique to Catalyst Studies," 17, Advances in Catalysis, pp. 103 - 149 (1967), the disclosure of which article is hereby expressly incorporated by reference.)

In our experiments about 0.5 g samples of the catalysts were placed in the reactor and heated at 10°C per minute from room temperature to about 500°C in about 50 ml. per minute of flowing hydrogen at about atmospheric pressure. After several hours at 500°C, the samples were then cooled in flowing hydrogen back to about room temperature. After about 30 minutes at room temperature, ^• the flowing hydrogen stream was replaced by about 50 ml

OMPI per. minute of flowing purge helium for about 30 minutes to remove physically adsorbed hydrogen. Then the samples were heated at a constant rate of 10°C per minute to about 500°C in flowing helium and the amount of hydrogen desorbed from the samples during the heating step was measured by a Carle Instruments, Inc. (Anaheim, California), Model 111H thermistor detector with a hydrogen separator.

The results of these H2-TPD experiments are presented in FIGURE 1. In the Figure desorption chromato- grams for the five catalyts tested are superimposed for comparison. From FIGURE 1, it is apparent that the con¬ figuration or general shape of the chromatograms for Catalysts "A", "B", "C", and "E" are quite similar. These catalysts are characterized by chromatogram configurations which are substantially flat. There may be shoulders and plateaus in the curves of the chromatograms for these ^"catalysts, but there are no pronounced peaks characterized by steeply rising and falling portions of the curve on either side of the peak. Especially, there are no pronounced peaks in the curves for these catalysts above about 300°C. The chromatogram for Catalyst "D" of our invention, on the other hand, is remarkably different in configuration or general shape from the chromatograms for the other catalysts. The catalyst of our invention is characterized by a chromatogram curve with a substantial peak above about 300°C. This curve corresponds to a catalyst composition with a particular high hydrogen bonding strength characterized by a high hydrogen desorption activation energy.

Also, we studied Catalysts "A", "B", "C", "D", and "E" by hydrogen chemisorption (H /Pt) experiments. These experiments comprised the following steps; (1) catalyst pretreatment/reduction, (2) hydrogen preadsorption, (3) removal of physically adsorbed hydrogen with a purge gas.

OMPI _ (4) titration of adsorbed hydrogen with oxygen, and (5) titration of adsorbed oxygen with hydrogen. During the titration with oxygen, it reacts with adsorbed hydrogen to form water. Also, the oxygen chemisorbs on the platinum. During the titration with hydrogen, it reacts with the adsorbed oxygen to form water and chemisorbs on the platinum also. Results of these experiments can be interpreted using the following stoichiometries:

(1) H2 chemisorption

Pt + 1/2 H₂ —*• Pt - H

(2) O2 titration

Pt - H + 1/20₂ —» 1/2 Pt₂0 + 1/2 H2O ^'

(3) O2 chemisorption

Pt + 1/40₂ — 1/2 Pt₂0

^' (4) H2 titration

1/2 Pt₂0 + H₂ —> Pt - H + 1/2 H₂0

The H2/Pt ratio, considered a measure of the degree of dispersion or availability for chemisorption of the platinum metal, is equal to the amount of diatomic hydrogen, in moles required to titrate the adsorbed oxygen and to saturate the available platinum metal divided by the amount of platinum, in moles, in the sample.

In our experiments about 2.0 g samples of the catalysts were placed in a reactor and heated at about 10°C per minute from room temperature to about 500°C in about 100 ml. per minute of flowing hydrogen at about atmospheric pressure. After several hours at 500°C in hydrogen, the catalyst samples were purged in about 100 ml. per minute of flowing helium for about 45 minutes and cooled to about room temperature in the helium. Then the catalysts were contacted with about 100 ml. per minute of flowing air for about 45 seconds and then purged again with flowing helium. Then seven successive 1 ml. aliquots of hydrogen were injected in 60 second intervals into the flowing helium upstream of the catalyst samples. The injected hydrogen which is not adsorbed on the sample flows with the helium carrier gas to a chromatographic detector where a signal proportional to the amount of unadsorbed hydrogen is obtained. The amount of adsorbed hydrogen is determined by difference from the measured injected amount and the measured unadsorbed amount. (See for example, H. L. Gruber, "An Adsorption Flow Method for Specific Metal Surface Area Determination," 34, Analytical Chemistry (13), pp. 1828-1831 (1962), the disclosure of which article is hereby expressly incorporated by reference.)

The results of these H2/Pt experiments are presented in TABLE I.

TABLE I

H2/Pt RATIOS

Catalyst A B C D E

H₂/Pt 0.94 0.94 1.06 0.60 1.02

From TABLE I, it is apparent that the H2/Pt ratios for Catalysts "A", "B", "C", and "E" are quite similar. These Catalysts are characterized by ratios of about 1.0. The ratios for the platinum- and phosphorus-containing Catalysts "B", "C", and "E" are equal to or greater than the ratio for the platinum only containing Catalyst "A." The ratio for Catalyst "D" of our invention, on the other hand, is much lower than all the other ratios, even the platinum only Catalyst "A." This ratio corresponds to a catalyst composition with a particular platinum-phosphorus interaction characterized by a low availability of platinum for chemisorption of hydrogen.

BRIEF DESCRIPTION OF DRAWINGS

FIGURE 1 represents temperature programmed desorp¬ tion chromatograms for the platinum and phosphorus catalyst of our invention, catalyst "D", compared to chromatograms for a platinum catalyst "A" and other platinum and phosphorus catalysts "B", "C" and "D". The chromatogram for the cata¬ lyst of our invention is charcterized by a pronounced peak above about 300°C. This peak corresponds to a platinum and phosphorus hydrocarbon conversion catalyst characterized by a high hydrogen desorption activation energy.

BEST MODE

EXAMPLE I

These Catalysts "A", "B", "C", "D" and "E" were then separately tested to determine their relative activity, selectivity and stability characteristics in a process for reforming a light Arabian naphtha charge stock, an analysis of which is presented in Table II.

OMPI Table II

Analysis of Charge Stock

Gravity, ^OAPI at 60^OF (16°C) 59.0

Specific Gravity at 60°F (16°C) 0.743

Distillation Profile, °F (°C)

Initial Boiling Point 225 (107)

10% Boiling Point 239 (115)

30% 256 (130)

50% 275 (135)

70% 300 (149)

90% 326 (163)

End Boiling Point 353 (179)

Chloride Content, wt. ppm 0.10

Nitrogen ^' " 0.2

Sulfur ^■ " 0.3

Water 6.0

Research Octane Number 31.0

Paraffins, wt. % 67.0

Naphtenes, " 26.0

Aromatics, " 7.0

These tests were each performed at identical conditions which included a reactor heater temperature which was adjusted to achieve and maintain a target C5+ reformate product research octane number of 101.5, a pressure of 300 psig (2,070 kPa-gage) and LHSV of 23.5 hr.-l and a 4:1 hydrogen to hydrocarbon mole ratio. All tests were performed in a pilot-plant-scale reforming unit comprising a reactor containing a fixed catalyst bed, a hydrogen separation zone, a debutanizer column, suitable heating and condensing means, suitable pumping and compressing means and the like conventional pilot plant equipment. In this plant a hydrogen recycle stream is commingled with the charge stock and the resulting mixture is heated to the desired conversion temperature. The heated mixture is passed downflow through the reactor containing the catalyst undergoing evalution. An effluent stream is withdrawn from the bottom of the reactor, cooled to about 55°F (13°C) and passed to a hydrogen separation zone wherein hydrogen-rich gaseous phase is separated from a liquid hydrocarbon phase. A porition of the gaseous phase is continuously passed through a high- surface-area sodium scrubber and the resulting substantially sulfur-free and water-free hydrogen stream is returned to the reactor as the hydrogen recyle stream. Excess gaseous phase from the hydrogen separation zone is recovered as hydrogen-rich product stream. The liquid phase from the separation zone is withdrawn therefrom and passed to a debutanizer column wherein light gaseous products including Ci to C4 hydrocarbons are taken overhead as debutanizer gas and C5+ hydrocarbons are receovered from the debutanizer bottoms as the high aromatics content reformate product.

The results of the separate tests performed on the cata¬ lyst of our invention, Catalyst "D", and the four control catalysts, Catalysts "A",. "B", "C", and "E", are presented in TABLE III.

TABLE III

Reformi ng Test Results

Catalyst A B C D

Conversion 981 995 986 1005 981 Temperature (528) (535) (530) (540) (528) OF (oc)*

C5 + Yield, LV%* 69.8 69.1 68.6 71.3 68.7

Hydrogen Produced, SCFB (Std m3/m3)* 978 1020 997 1184 983 (17,408) (18,156) (17,747) (21,075) (17,497)

*at 0.3 barrels of charge stock per pound of catalyst life

From TABLE III it is apparent that Catalyst "D" of our invention exhibits substantially higher selectivity, represented by the higher C5+ yield for the test, than the control catalysts. Also, the Catalyst "D" of our invention produced more hydrogen, in standard_cubic feet of hydrogen per barrel of charge stock, than the control catalysts.

EXAMPLE II

We studied the effect of the amount of phosphorous component relative to the amount of platinum group component on catalysts of our invention. Four catalysts were prepared. Catalyst "F" contained 0.275 wt. % platinum, about 1.1 wt. % chlorine and 0.060 wt. % sulfur. This catalyst was prepared in the same manner as Catalyst "A" above except the platinum component impregnation solution was contacted with the alumina support material under vacuum. Then the catalyst composite was dried, oxidized, halogen-treated and reduced like Catalyst "A" and the additional sulfur component was incorporated by contacting the reduced cata¬ lyst with hydrogen sulfide in dry nitrogen at ambient temperature. Catalysts "G", "H", and "I"., representing different embodiments of our invention, were then prepared from portions of Catalyst "F" by adding different amounts of phosphorous component from aqueous impregnation solutions of hypophosphorous acid. Catalyst "G" contained 0.275 wt. % platinum, about 1.1 wt. % chlorine, 0.060 wt. % sulfur and 0.05 wt. % phosphorus. The phosphorus to platinum atomic ratio for this catalyst was 1.1. Catalyst "H" con¬ tained the same amounts of components except it contained 0.28 wt. %, instead of 0.05 wt. %., phosphorus The phos¬ phorus to platinum atomic for this catalyst was 6.4. Cata¬ lyst "I" also contained the same amounts of components except it contained 0.45 wt. % phosphorus. The phosphorus to platinum atomic ratio for this catalyst was 10.3.

These catalysts were then separately tested in the same manner as the catalysts in Example I. The results of the reforming tests are presented in TABLE IV.

TABLE IV

Reforming Test Results

Catalyst I

Conversion Temperature, 964 963 970 980 OF (oc)* (518) (517) (521) (527)

C₅ + Yield, LV%* 70.7 73.3 73.4 72.5

Hydrogen Produced SCFB (Std m3/_m3)* 941 1030 1052 1057 (16,750) (18,334) (18,726) (18,815)

*at 0.3 barrels of charge stock per pound of catalyst life

From TABLE IV it is apparent that Catalysts "G", "H" and "I" of our invention exhibit substantially higher

OMPI selectivity, as represented by the higher C5+ yields for the test than Catalyst "F" without the phosphorous component. Also, these catalysts of our invention produced more hydro¬ gen, ..in standard cubic feet per barrel of charge stock, than the other catalyst. Furthermore, at the phosphorous levels tested, the advantages of our catalysts do not appear to be a strong function of the phosphorus to platinumm group component atomic ratio.

EXAMPLE III

Also, we studied the effects on several platinum- and phosphorus-containing catalysts of our invention of oxidation and reduction steps after the phosphorus incor¬ poration step. Three catalysts were prepared. Catalysts "J" contained 0.3 wt. % platinum and about 1.0 wt. % chlorine. This catalyst was prepared in- the same manner as Catalyst "A" above. Catalyst "K" contained 0.3 wt. % platinum, about 1.0 wt. % chlorine, and 0.04 wt. % phosphorus. This catalyst was prepared in the same manner as Catalyst "J" except phosphorus was added to the oxidized and reduced platinum-containing composite from an impregna¬ tion solution of triphenylphosphine and benzene. Then, that composite was dried, oxidized in 1728 GHSV of air at about IOOO^OF (538⁰C) for about 2 1/1 hours and reduced in 1440 GHSV of dry hydrogen at about 1050OF (566°C) for about 1 hour. Catalyst "L" also contained 0.3 wt. % platinum, about 1.0 wt. % chlorine and 0.04 wt. % phosphorus. This catalyst was prepared in the same manner as Catalyst "K" except after the phosphorus was added the composite was dried and then reduced, without an intermediate oxidation step, in 1440 GHSV of dry hydrogen at about 1050OF (%660C) for about 1 hour.

These catalysts were then separately tested in the same manner as the catalysts in Example I. The results of the reforming test are presented in TABLE V. TABLE V

Reforming Test Results

Catalyst J K L

Conversion Temperature 958 968 971 OF (oc)* (514) (520) (522)

C₅+ Yield, LV%* 69.9 69.1 71.1

Hydrogen Produced, SCFB (Std m3/_m3)* 830 791 955

(14,744) (14,080) (16,999)

* at 0.4 barrels of charge stock per pound of catalyst life.

For TABLE V it is apparent that Catalyst "L" exhibits substantially higher selectivity as represented by the higher C5+ yield for the test. Also, the Catalyst "L" produced more hydrogen, in standard cubic feet per baπrel of charge stock, than the other catalysts.

For reforming hydrocarbons boiling in the gasoline range, we have obtained best results with a catalyst accord¬ ing to our invention which comprises, on an elemental basis, about 0.37 wt. % platinum, 1.00 wt. % cobalt, 0.30 wt. %^• tin, 0.20 wt. % phosphorus and about 1.00 wt. % chlorine on gamma alumina of about 0.56 ABD. This catalyst is best prepared by impregnating the alumina containing the tin, which has been added as stannic chloride to the alumina hydrogel before oil dropping, with an aqueous solution of chloroplatinic acid and hydrochloric acid, and drying, oxidizing and reducing the composite. Then, the platinum- and tin-containing composite is impregnated with an aqueous solution of cobalt nitrate hexahydrate and hypophosphorous acid, and dried and reduced without an intermediate oxidation step.

Summarily, it is clear from the data presented in TABLES III, IV, and V that a catalyst composite according to our invention comprising a platinum group component, a phosphorous component and a porous support material provides a reforming catalyst with improved selectivity and hydrogen production characteristics.

INDUSTRIAL APPLICABILITY

The catalysts of this invention are useful for the conversion of hydrocarbons on an industrial scale, especially reforming of hydrocarbons boiling in the gasoline range to produce high octane reformate for gasoline blending or high aromatics content reformate for petrochemical feedstocks.

Claims

WHAT WE CLAIM IS:

1. A catalyst comprising a platinum group component and a phosphorous component with a porous support material characterized by a hydrogen temperature-programmed-desorption chromatogram having the same general configuration as that of Catalyst "D" in Figure 1.

2. A catalyst comprising a platinum group component and a phosphorous component with a porous support material characterized by a hydrogen temperature-programmed-desorption chromatogram with a substantial peak above about 300°C.

3. A catalyst composition comprising a platinum group component and a phosphorous component with a porous support material characterized by a high hydrogen desorption activa¬ tion energy indicated by a hydrogen .temperature-programmed-de- sorption chromatogram with a substantial peak above about 300°C.

4. A catalyst composition comprising a platinum group component and a phosphorous component with a porous sup¬ port material characterized by an H^/Pt ratio less than the H-/Pt ratio for the same catalyst comprising a platinum group component but without the phosphorous component.

5. A catalyst composition comprising a platinum group component and a phosphorous component with a porous sup¬ port material characterized by a low availability of platinum for chemisorption of hydrogen compared to the same catalyst comprising a platinum group component but without the phos¬ phorous component.

6. A catalyst comprising a platinum group component, a phosphorous component and a porous support material , said catalyst being made by the method of

(a) compositing a platinum group component with a porous support material^",

(b) contacting the composite from step (a) with phosphorus or a compound of phosphorus at a temperature less than 700°F so that the phosphorus to platinum group component atomic ratio is greater than 0.5, and

(c) then reducing the composite from step (b) without an intermediate oxidation step.

7. A process for converting hydrocarbons which com¬ prises contacting the hydrocarbons at reforming conditions with a catalyst made by the method of ^'

(a) compositing a platinum group component with a porous support material ,

(b) contacting the composite from step (a) with phos¬ phorus or a compound of phosphorus at a temperature less than 700°F so that the phosphorus to platinum group component atomic ratio is greater than 0.5, and

8. A method for making a catalyst which comprises the steps of

(a) compositing a platinum group component with a porous support material ,

(b) contacting the composite from step (a) with phos¬ phorus or a compound of phosphorus at a temperature less than 700°F so that the phosphorus to platinum group component atomic ratio is greater than 0.5, and (c) then reducing the composite from step (b) without an intermediate oxidation step.

9. A method for making a catalyst which comprises the steps of

(a) compositing a platinum group component with a porous support material ,

(b) drying, oxidizing and reducing the composite from step (a),

(c) contacting the composite from step (b) with phos¬ phorus or a compound of phosphorus at a temperature less than 700°F so that the phosphorus to platinum group component atomic ratio is greater than 0.5, and

(d) drying, and then reducing the composite from step (c) without an intermediate oxidizing step.

10. A process for reforming hydrocarbons which com¬ prises contacting the hydrocarbons at reforming conditions with a catalyst made by contacting a composite comprising a platinum group component and a porous support material with phosphorus or a compound of phosphorus to incorporate the phosphorous com¬ ponent.

11. A catalyst composition comprising a platinum group component, a gallium component and a phosphorous component with a porous support material.

12. A catalyst composition comprising a platinum group component, a rhenium component and a phosphorous component with a porous support material .

13. A catalyst composition comprising a platinum group component, a cobalt component and a phosphorous component with a porous support material .

14. A catalyst composition comprising a platinum group component, a nickel component and a phosphorous compo¬ nent with a porous support material .

15. A catalyst composition comprising a platinum group component, an iridium component and a phosphorous compo¬ nent with a porous support material.

16. A catalyst composition comprising a platinum group component, a rhenium component, a cobalt component and a phosphorous component with a porous support material.

17. A catalyst composition comprising a platinum group component, a rhenium component, a nickel component and a phosphorous component.

18. .A catalyst composition comprising a platinum group component, a rhenium,component, an iridium component and a phosphorous component with a porous support material.

19. A catalyst composition comprising a platinum group component, a rhenium component, a tin component and a phosphorous component with a porous support material.

20. A catalyst composition comprising a platinum group component, a cobalt component, a tin component and a phosphorous component with a porous support material.

21. A catalyst composition comprising a platinum group component, a cobalt component, an indium component and a phosphorous component with a porous support material.

22. A catalyst composition comprising a platinum group component, a cobalt component, a uranium component and a phosphorous component with a porous support material.

23. A catalyst composition comprising a platinum group component, a rhodium component, a gallium component and a phosphorous component with a porous support material.

24. A catalyst composition comprising a platinum group component, a tin component and a phosphorous component with a porous support material.

25. A catalyst composition comprising a platinum group component, a germanium component and a phosphorous com¬ ponent with a porous support material.

OMPI >.