US3598724A

US3598724A - Production of propane and butanes

Info

Publication number: US3598724A
Application number: US858128A
Authority: US
Inventors: Bernard F Mulaskey
Original assignee: Chevron Research and Technology Co
Current assignee: Chevron USA Inc
Priority date: 1969-09-15
Filing date: 1969-09-15
Publication date: 1971-08-10
Anticipated expiration: 1988-08-10

Abstract

A HYDROCARBON FEED BOILING ABOVE 100* F. IS CONVERTED O HIGH YIELDS OF C3-C4 HYDROCARBONS BY CONTACT WITH A CATALYST COMPRISING MORDENITE, THOROUGHLY ADMIXED WITH AN AMORPHOUS POROUS INORGANIC OXIDE CONTAINING NICKEL, OR COMPOUNDS THEREOF, AND TIN, OR COMPOUNDS THEREOF , AT HYDROCRACKING CONDITIONS SUFFICIENTLY SEVERE TO CONVERT AT LEAST 30 PERCENT OF THE FEED TO PRODUCTS BOILING BELOW 100*F.

Description

United States Patent O U.S. Cl. 208-111 9 Claims ABSTRACT OF THE DISCLOSURE A hydrocarbon feed boiling above 100 F. is converted to high yields of C -C hydrocarbons by contact with a catalyst comprising mordenite, thoroughly admixed with an amorphous porous inorganic oxide containing nickel, or compounds thereof, and tin, or compounds thereof, at hydrocracking conditions sufficiently severe to convert at least 30 percent of the feed to products boiling below 100" F.

CROSS-REFERENCES This application is a continuation-in-part of application Ser. No. 742,321, filed July 3, 1968, now US. Pat. 3,487,007, which is in turn a continuation-in-part of application Ser. No. 645,855, filed June 8, 1967, now US. Pat. No. 3,399,132, which is in turn a continuation-in-part of application Ser. No. 568,536, filed July 28, 1966, now abandoned.

BACKGROUND OF THE INVENTION Field The present invention relates to a hydrocracking process for producing C -C components from naphtha boiling range materials.

Prior art The lightest materials produced in refining are gases at atmospheric pressure, for example, hydrogen, methane, ethane, propane, and butane. Butane and propane are particularly important for use as liquified petroleum gas (LPG). The light hydrocarbon gases have generally been synthesized as a byproduct from the catalytic cracking and hydrocracking of hydrocarbon oils to obtain gasolines and higher boiling products. Although the light gases produced are only a few weight percent of the hydrocarbon feed cracked, they are very valuable, especially the gases containing three or four carbon atoms which are sold as LPG for use as chemical raw materials and household fuels. The use of LPG has rapidly expanded during the last decade. Thus, processes for increasing the production of LPG efliciently have been and are being examined. Processes which primarily produce propane and butane without excessive production of lighter hydrocarbons are especially desired.

SUMMARY OF THE INVENTION It has now been discovered that a catalyst comprising a mixture of mordenite and an amorphous porous inorganic oxide associated with nickel and tin, or their compounds, is surprisingly active in converting 100 F.+ boiling range materials to C -C hydrocarbons during hydrocracking.

Thus, the process of the present invention comprises producing high yields of C -C hydrocarbons by contacting 100 F.+ boiling range feed in the presence of hydrogen at hydrocracking conditions with a catalyst com- 3,598,724 Patented Aug. 10, 1971 at least 30 volume percent of the feed to products boiling below F.

DESCRIPTION OF THE INVENTION The catalyst finding use in the present process is a mixture of two components: (1) mordenite and (2) an amorphous porous inorganic oxide, e.g., silica, containing nickel, or compounds thereof, and tin, or compounds thereof, in an amount of from 2 to 50 combined weight percent metals with a nickel to tin weight ratio of 0.25 to 20. The weight percents of the nickel and tin, or their compounds, are determined on the basis of the amorphous porous inorganic oxide component of the catalyst. Preferably the mordenite component of the catalyst is present in an amount from 10 to 85 weight percent and more preferably from 20 to 80 weight percent, based on the finished catalyst composition.

Of the various natural and synthetic zeolites now available in the industry, only mordenite is satisfactory for purposes of the present invention. Other crystalline zeolites such as zeolite A, zeolite X, zeolite Y and faujasite are unsatisfactory. This is attributed to the combination of pore size and unusual catalytic activity of the mordenite. Mordenite has an ordered crystallite structure having a ratio of silicon atoms to aluminum atoms of about 5 to 10. The sodium form can be represented by the following formula:

Nag (A1203 8 4024H2O Mordenite can exist or be prepared having cations other than sodium, for example, mordenite can be prepared having a cation of lithium, potassium, calcium and the like.

' Mordenites ordered crystallite structure is believed to be made up of chains of five-membered rings of tetrahedra and its adbsorbency suggests a parallel system of channels having a free diameter on the order of 4 A. to 6.6 A., interconnected by smaller channels, parallel to another axis, on the order of 2.8 A. free diameter.

Although mordenite is generally prepared in the sodium form, it is preferred for purposes of the present invention that the sodium ions be replaced with other ions lower in the electromotive series than sodium. The sodium ion concentration on the mordenite should preferably be less than about 5 weight percent and more preferably less than about 1 weight percent. Thus, the mordenite may contain, in place of sodium, an ion such as, for example, calcium, magnesium, strontium, barium, rare earth metal ions, Group IV-VIII metal ions, etc. It is particularly preferred that the mordenite exist substantially in the ammonium or hydrogen form and that it be maintained substantially free of any catalytic loading metal or metals. The hydrogen form of mordenite can be prepared by conventional techniques which include the exchange of mordenite with acid solution, or more commonly and preferably, conversion of the mordenite to the ammonium form via base exchange with an ammonium salt and calcination of the resultant ammonium-form mordenite to cause thermal degradation of the ammonium ions and formation of the desired hydrogen cation sites.

The other component of the catalyst mixture used in the present invention comprises an amorphous porous inorganic oxide having associated therewith nickel and tin or their compounds. The amorphous porous inorganic oxide preferably has a surface area of 50-750 m. /gm., preferably -750 m. /gm. The carrier can be natural or synthetically-produced inorganic oxides or' a combination of inorganic oxides. Typical inorganic oxide supports which can be used are silica, alumina, magnesia, and zirconia. Combinations of amorphous porous inorgan c oxides can be used, e.g., silica-alumina, silica-magnesia,

silica-zirconia, silica-magnesia-titania, and silica-aluminazirconia.

A particularly preferred amorphous porous inorganic oxide carrier is silica. A variety of methods are available for producing suitable silica supports. Silica can be produced by hydrolyzing tetraethyl orthosilicate with aqueous 'HCl solution. Likewise, silica can be prepared by contacting silicon tetrachloride with a cold methanol and water solution or with 95 percent ethyl alcohol, or with cold water or ice. Also silica can be prepared by contacting sodium silicate with an ion-exchange resin to remove the sodium or by contacting with an acid at a pH of about 2.5 or less. Further, silica can be prepared by adding preferably under pressure, to sodium silicate.

The amorphous porous inorganic oxide will have in association therewith nickel and tin or their compounds. Preferably the nickel and tin will be present in an amount of from 2 to 50 combined weight percent metals based on the amorphous porous inorganic oxide component of the catalyst mixture. Regardless of the form in which the nickel and tin exist on the catalyst, whether as metallic nickel and metallic tin, or compounds of nickel and compounds of tin, such as the oxides or sulfides, the total combined weight percent of the nickel and tin associated with the amorphous porous inorganic oxide, calculated as the metal, should be from 2 to 50. Preferably the nickel and tin, or compounds thereof, are present in an amount of from 5 to 30 combined weight percent and more preferably from 7 to 25.

The nickel and tin, or their compounds, should be present in association with the amorphous porous inorganic oxide in a weight ratio of nickel to tin of from 0.25 to 20 determined as the metals. Preferably the nickel to tin weight ratio is from 0.5 to 20 and more preferably from 0.5 to 10. In general, when employing high combined weights of nickel and tin, it is preferred to use high nickel to tin weight ratios.

The presence of tin in association with nickel and an amorphous porous inorganic oxide imparts increased hydrogenation activity and cracking activity to the catalytic composition as compared to a catalyst comprising nickel but without tin. Furthermore, the presence of tin decreases the fouling rate of the catalyst during hydrocracking as compared to a catalyst comprising nickel without tin. Still further, as an additional advantage of using nickel and tin together in association with an amorphous porous inorganic oxide, the tin helps prevent the rapid formation of nickel crystallites during hydrocracking, particularly when high concentrations of mordenite are present (the presence of mordenite leads to nickel crystallite growth during hydrocracking which leads to early deactivation of the catalyst).

The portion of the catalyst comprising the amorphous porous inorganic oxide in association with nickel and tin can be prepared by any of the conventional methods for associating catalytically active amounts of hydrogenating metal components with the carrier. Thus, the nickel and tin components can be associated with an amorphous porous inorganic oxide by impregnation or by ion-exchange. Impregnation is generally accomplished using an aqueous solution of a suitable nickel compound and/or tin compound. Either simultaneous or sequential impregnation of the metal components is suitable. Ion-exchange is generally accomplished by using an aqueous solution of a suitable nickel and/or tin salt wherein the nickel and/or tin is present in the cationic state. As examples, in the preparation of a catalyst wherein the carrier is an amorphous silica-alumina, the nickel and tin are normally associated with the silica-alumina by impregnation. Typical nickel and tin compounds which can be used for impregnation or ion-exchange are the chlorides, nitrates,

alumina can be prepared by sulfates, acetates and amine complexes. The tin can be in the stannous or stannic oxidation state.

The nickel and tin, or theircompounds, can be associated with the amorphous porous inorganic oxide by c0- precipitation or cogelation of a mixture of compounds of the hydrogenating metals and compounds of the metals and/or nonmetals whose oxides form the amorphous porous inorganic oxide carrier. Both hydrogenating metal components can be coprecipitated or cogelled with the compounds of the metals and/ or nonmetals whose oxides form the inorganic oxide carrier; or, one of the hydrogenating metal components can be associated with the amorphous porous inorganic oxide carrier by coprecipitation or cogelation, and the other hydrogenating metal component then intimately associated with the coprecipitated composite by impregnation or other suitable means. For example, a coprecipitated composite of tin, or compound thereof, and silica-alumina can be prepared by coprecipitating a mixture of stannous chloride, aluminum chloride, and sodium silicate. Nickel, e.g., as nickel chloride, can then be initimately associated with the coprecipitated composite by impregnation.

A preferred method of preparation of the novel catalytic composition of the present invention is by simultaneous coprecipitation or cogelation of a mixture of nickel and tin compounds, and compounds of the metals and/ or nonmetals whose oxides form the amorphous porous inorganic oxide carrier. The method of preparation of a coprecipitated composite of only one of the hydrogenating metals and an amorphous porous inorganic oxide is, in general, the same as that for a coprecipitated composite of both metals and an amorphous porous inorganic oxide. For the same of brevity, the preparation of a coprecipitated composite will be described only in terms of using both hydrogenating metals in the coprecipitated composite. In general, preparation of the coprecipitated composite can be accomplished by forming a solution and/ or a sol of the compounds, subsequently precipitating the mixture, preferably at a pH from about 5.5 to 8, by the addition of a precipitating agent as, for example, a base, and then washing the coprecipitated composite to remove extraneous materials. Finally, the coprecipitated composite can be dried and then calcined at an elevated temperature. Thus, for example, a coprecipitated composite comprising nickel and tin intimately associated with silicaforming an aqueous solution of aluminum chloride, sodium silicate, nickel chloride and stannous chloride. The solution can then be coprecipitated by the addition of ammonium hydroxide; thereafter the coprecipitated composite can be washed, dried and calcined.

In order to prepare a coprecipitated composite comprising an amorphous porous inorganic oxide and nickel and tin components, it is desirable that the starting components be such that when admixed togetherthe resulting mixture will form a solution and/or sol so as to obtain uniform dispersion throughout the mixture.

The compounds in the initial mixture can advantageously be salts such as the nitrates, citrates, formates, alcoxides, and sulfates. Preferably chlorides and acetates are employed. In view of the process advantages of using chloride salts due to their readiness to form solutions with other compounds, their commercial availability and relatively low price, it is often desirable to employ them. The anion content, e.g., chloride, in the final coprecipitate is preferably reduced to below about 0.25 percent of the total weight of the final coprecipitate. Washing with water can often effectively lower the anion content to the desirable limit. If anions are present in the coprecipitate which are diflicult to remove by washing, such anions can be ion-exchanged with anions more easily removed by washing. Preferred anions for use in ion-exchange are the bicarbonates, carbonates, acetates, and formates.

After formation of the initial mixture, it is coprecipitated by conventional techniques. Precipitation is preferably conducted at a pH between about 5.5 and about 8. Thus, the initial mixture, if acidic, can be precipitated by the addition of a base. If the mixture is basic, it can be precipitated with an acid. The precipitation can be stepwise, as by a form of titration, or simultaneous, as by mixing of acidic or basic solutions, as the case may be, in the proper ratios. It is preferable that the precipitating agent should not introduce any components in the mixture that are deleterious.

Following precipitation of the mixture of compounds, the excess liquid is usually removed by filtration. Thereafter the precipitate is washed and ion-exchanged to remove impurities. Washing is generally conducted in more than one step, using water or dilute aqueous solutions of ammonium salts, e.g., ammonium acetate. The coprecipitated composite is then dried in air or inert gases at a temperature less than 400 F., preferably from about 150 F.-300 F. The coprecipitate is then calcined, generally at a temperature of from about 750 to 1400 F. in the presence of an oxygen-containing gas.

The mordenite and the amorphous porous inorganic oxide carrier associated with nickel and tin, or their compounds, can be admixed with each other in any of a number of different ways. For example, the mordenite can be suspended and distributed throughout an amorphous porous inorganic oxide. Thus, the mordenite can be dispersed in a sol of the amorphous porous inorganic oxide, e.g., a siliceous sol or aluminous sol, prior to gelation of the sol. Alternately the mordenite can be dispersed in a hydrogel of the amorphous porous inorganic oxide.

It is particularly preferred that the catalyst mixture consist of a physical particle-form mixture of the mordenite and the nickel-tin-amorphous porous inorganic oxide. A physical particle-form catalyst mixture can be prepared by mixing the mordenite and the nickel-tinamorphous porous inorganic oxide in the form of discrete particles, or the components can be admixed, pelleted, cast, molded or otherwise formed into pieces of desired size and shape such as rods, spheres, pellets or other configuration. The particle size of the individual components of the physical mixture may be very small, e.g., less than about 50 microns. Alternately, the particles may be sufficiently large and distinct as to permit ready separation thereof by mechanical means which in turn makes possible separate regeneration, reactivation, and replacement of the two components. Accordingly, the particle size of the two components making up the particle-form physical mixture may fall within the approximate range of 2 to 50 mesh (Tyler).

The catalyst of the present invention can be promoted for hydrocracking activity by the addition of halides, e.g., chloride or fluoride; preferably fluoride is employed. The total halide content is preferably from 0.01 to weight percent based on the finished catalyst. The halide can be incorporated onto the catalyst at any suitable stage of catalyst manufactureas, for example, prior to or follow ing incorporation of nickel and tin, or compounds thereof, with the amorphous porous inorganic oxide. In general, the halide is combined with the catalyst by contacting suitable compounds such as ammonium halide or hydrogen halide, either in a water soluble form or a gaseous form with the catalyst. Preferably the halide is incorporated onto the catalyst with an aqueous solution containing the halide.

It is encompassed as part of the present invention that a layered crystalline clay-type aluminosilicate may also be present with the catalyst composition. The layered crystalline clay-type aluminosilicate can generally be present in a small amount, for example, less than weight percent, based on the finished catalyst. The layered crystalline clay-type aluminosilicate may be any catalytically active layered aluminosilicate, although the synthetic hydrated layered crystalline clay-type aluminosilicate of Granquist (U.S. Pat. 3,252,757) and the dehydrated form of Capell and Granquist (U.S. Pat. 3,252,889) are preferred. Said layered crystalline claytype aluminosilicates are referred to hereinafter for the sake of brevity as layered aluminosilicate. The preferred hydrated layered aluminosilicate referred to in U.S. Pat. 3,252,575, incorporated herein by reference thereto, has the empirical formula nSiO A1 0 mAB xH O where the layer lattices comprise said silica, said alumina, and said B, and where n is from 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence not greater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F1 OH", /20"* and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a d spacing at said humidity within the range which extends from a lower limit of about 10.4 A. to an upper limit of about 12.0 A. when A is monovalent, to about 14.7 A. when A is divalent, and to a value intermediate between 12.0 A. and 14.7 A. when A includes both monovalent and divalent cations. The equivalent of an exchangeable cation, A, in said mineral may be chosen from the group consisting of H+, NH Li+, K+, /2 Ca++, /2 Mg++, /2 Sr++, and /2 Ba++, and mixtures thereof.

The preferred dehydrated layered aluminosilicate referred to in U.S. Pat. 3,252,889, incorporated herein by reference thereto, has the empirical formula:

2.4 to 3.0 SiO :Al O :0.2 to 0.6AB

wherein the layer lattices comprise silica (SiO alumina (A1 0 and B; and

wherein A is one equivalent of an exchangeable cation selected from the group consisting of hydrogen, alkali metal, and alkaline earth metal ions, and mixtures thereof; and

wherein B is one equivalent of an anion selected from the group consisting of fluoride, hydroxyl, and oxygen ions, and mixtures thereof;

said crystalline material being further characterized by a d spacing ranging from 9.6 to 10.2 angstrom units determined at 50% relative humidity and being predominantly ordered in two dimensions.

The dehydrated layered aluminosilicate of 3,252,889 is obtained from the hydrated layered aluminosilicate of U.S. Pat. 3,252,757 by calcination at a temperature within the range of 600 to 1450 F., preferably 600 to 1200 F. Upon calcination of the hydrated form, and removal of water, the d spacing of the aluminosilicate collapses somewhat, resulting in a layered aluminosilicate of a smaller d spacing. According to the teachings of U.S. Pat. 3,252,889, the collapse is irreversible and the dehydrated layered aluminosilicate is no longer capable of swellingapparently the removal of water from the hydrated form results in a new and different chemical and indeed mineralogical species from the starting material.

The hydrocarbon feed used in producing high yields of C C hydrocarbons will generally boil within the range from about F. to 550 F. Generally, naphtha feedstocks are particularly advantageous for use in the present process. The naphtha can be either a straight-run naphtha or a thermally cracked or a catalytically cracked naphtha or blends thereof. While such feedstocks are generally used in reforming processes to produce high octane gasoline, the increase in demand for LPG has resulted in the use of such feeds in LPG production. While feeds boiling above 550 F. could be utilized in the process of the present invention, it is particularly desired that the feed 7 boil below 550 F. and preferably below 450 F. High boiling feeds are generally more diflicult to handle, for example, requiring a longer contact time with the catalyst. The feeds may contain sulfur and/ or nitrogen components but generally it is preferred that the feeds be low in sulfur and nitrogen, i.e., contain less than 50 p.p.n1. sulfur and less than ppm. nitrogen.

In general, the conditions used in the present process will include a temperature of from 450 to 900 F. and

' a pressure between about 500 to 10,000 p.s.i.g. Lower pressures could be used, e.g., as low as 200 p.s.i.g. Higher temperatures and pressures are generally used with the higher boiling feedstocks. Preferably pressures between 1000 and 6000 p.s.i.g. are used. The hydrogen flow rate into the reactor is generally maintained between 1000 to 20,000 s.c.f./bbl. of feed, preferably in the range of 4000 to 10,000 s.c.f./bbl. The hydrogen consumption will vary depending on the properties of feed and on the other hydrocracking conditions used. In general the hydrogen consumption will range from 500 to 5000 s.c.f./

bbl. The excess hydrogen not consumed in the reaction is separated from the treated feed and preferably purified and recycled. The liquid hourly space velocity (LHSV) will generally be in the range from 0.1 to 10 and preferably 0.3 to 5. It is recognized that the severity of hydrocracking can be varied over a wide range within the limits of the process conditions above specified. Thus, in order to produce high yields of light hydrocarbon gases, that is, propanes and butanes, it is preferred that the process conditions be controlled to permit conversion of at least volume percent of the feed to products boiling below about 100 F. Preferably, the severity of the reaction is controlled so that at least percent and preferably percent of the feed is converted to products boiling below about F.

As indicated, an advantage of the process of the present invention is the significant conversion of hydrocarbons to light gases, particularly propanes and butanes. It is particularly significant that paraffins are converted in high yields to propanes and butanes. Any hydrocarbons, including paraffins, not converted can be recovered from the product and recycled to the reaction zone for further treatment.

The process of the present invention will be better understood and further explained by reference to the following example.

Example A series of catalysts were prepared and tested for naphtha cracking. A catalyst of the present invention, that is a catalyst comprising a mixture of (1) mordenite and r (2) silica in association with nickel and tin or their compounds, was prepared, the mixture containing 50 weight percent mordenite and 50 weight percent of the nickel-tinsilica component. The nickel-tin-silica component of the catalyst contained 14.3 weight percent nickel and 7.7 weight percent tin, calculated as the metals. The nickel to tin weight ratio was 1186.

The nickel-tin-silica component of the catalyst was prepared by mixing sodium silicate in water, SnCl -2H O, acetic acid and nickel chloride. The resulting mixture was neutralized by the addition of ammonium hydroxide. The resulting slurry was aged for about 1 hour at 200 F. and filtered and then washed with ammonium acetate. In preparing the nickel-tin-silica catalyst, the following amounts of the components were used (or multiples thereof): 87.8 grams of sodium silicate in 4 liters of water, 53.2 grams of SnCl -2H O, 180 grams of acetic acid, 447 grams of nickel chloride solution containing 181 grams per liter of nickel, and 8.3 liters of water.

To the wet nickel-tin-silica hydrogel, dry mordenite powder in substantially the hydrogen form was blended therewith. The resulting mixture was then extruded several times and dried at 200 F. overnight and then calcined at an elevated temperature around 900 F. for approximately 2 hours.

For comparison purposes a nickel-tin-silica-alumina catalyst was prepared and tested for naphtha cracking. The nickel-tin-silica-alumina catalyst was prepared substantially as described in the specification above. A solution was prepared by adding SnCl -2H O, an AlCl solution and an NiCl solution to a vessel containing water and glacial acetic acid. Thereafter commercial sodium silicate dissolved in water was added. The resulting mixture was rapidly stirred to form a clear solution and/or sol. The components were then coprecipitated to a final pH of about 7.5 by slowly adding, accompanied by stirring, a solution composed of ammonium hydroxide in water. The resulting slurry was then aged at a temperature around F. and then cooled and filtered to remove excess water and the precipitate recovered. The precipitate was then washed with ammonium acetate and finally dried around 150 F. and then calcined at a temperature range from 400 to 1000 F. The resulting composite contained 11.2 weight percent nickel oxide, 4.9 weight percent tin oxide, and 83.9 weight percent silicaalumina, the silica to alumina weight ratio being 1.9. Prior to naphtha cracking the coprecipitated composite of nickel-tin-silica-alumina was contacted with a flowing hydrogen atmosphere for a short period of time.

For further comparison purposes a palladium on mordenite catalyst was prepared by impregnating the hydrogen form of mordenite with a palladium chloride- HCl solution in suflicient concentration to provide 1 weight percent palladium on the finished catalyst. The thus-impregnated mordenite catalyst was dried around 200 F. for 8 to 12 hours and then calcined at approximately 900 F. for about 2 hours.

The catalysts were tested for the hydrocracking of a naphtha boiling within the range from 216 F. to 365 F. and containing 12.6 weight percent aromatics, 28.9 weight percent naphthenes, and 58.6 weight percent paraffins. Reaction conditions included a pressure of 1000 p.s.i.g., a hydrogen input rate of 5000 s.c.f./bb1. and a liquid hourly space velocity of 1.0. The temperature in the reaction zone was varied over a suitable range in order to vary the weight percent conversion of the feed to lower boiling products. The three catalysts had different activities. For example, the temperatures required to convert 60 percent of the feed to products below C for the catalyst of the present invention, the nickel-tin-silica-alumina catalyst, and the palladium-mordenite catalyst were 734 F., 805 F., and 560 F., respectively.

The catalyst of the present invention, that is, the catalyst mixture comprising mordenite and nickel-tin-silica, was far more effective in converting the feed to lower boiling products and in producing more nearly the same amounts of C and C hydrocarbons than the other catalysts tested. This fact is an advantage of the process of the present invention. It is highly desirable for many operatrons to produce substantially equivalent amounts of butanes and propane for use as LPG. The process of the present invention using the mordenite and nickel-tinsilica catalyst resulted in high selectivity in the production of butanes and propanes. Thus, when reaction conditions were such to convert approximately 60 weight percent of the feed to products boiling below C s, the following product distribution with the three catalysts were obtained and are tabulated in the following table. (The yield weight percent is determined as the weight percent of the product divided by the weight percent conversion below C The foregoing description of this invention is not to be considered as limiting since many variations can be made by those skilled in the art without departing from the spirit or scope of the appended claims.

I claim:

1. A process which comprises contacting a hydrocarbon feed boiling above about 100 F. in the presence of hydrogen with a catalyst comprising mordenite, thoroughly admixed with an amorphous porous inorganic oxide containing nickel, or compounds thereof, and tin, or compounds thereof, in an amount from 2 to 50 combined Weight percent metals With a nickel to tin weight ratio of 0.25 to 20, at hydrocracking conditions sufficiently severe to convert at least 30 weight percent of the feed to products boiling below about 100 F. I

2. The process of claim 1 wherein said mordenite is in the hydrogen form.

3. The process of claim 1 wherein said mordenite is present in an amount of from 10 to 85 weight percent.

4. The process of claim 1 wherein the hydrocracking conditions are sufiiciently severe to produce at least 40' Weight percent of the feed to products boiling below about 5. The process of claim 1 wherein said hydrocracking conditions are sufficiently severe to produce at least 50 weight percent of the feed to products boiling below about 100 F.

6. The process of claim 1 wherein said amorphous porous inorganic oxide is silica.

7. The process of claim 1 wherein said nickel, or compounds thereof, and said tin, or compounds thereof, are present in an amount of from 5 to 30 combined weight percent metals.

8. A process for producing high yields of light hydrocarbon gases of primarily propane and butane which comprises contacting a feed boiling within the range from about 100 to 450 F. and in the presence of hydrogen with a catalyst comprising mordenite, thoroughly admixed in a matrix of an amorphous porous inorganic oxide containing nickel and tin, or their compounds, in an amount of from 2 to combined weight percent metals with a nickel to tin combined weight ratio of from 0.25 to 20, at hydrocracking conditions sufliciently severe to convert at least 30 weight percent of the feed to products boiling below about F.

9. A process in accordance with claim 1 wherein the amorphous porous inorganic oxide comprises silicaalumina.

References Cited UNITED STATES PATENTS 3,140,253 7/1964 Plank et al. 208- 3,236,761 2/1966 Rabo et al 208-111 3,385,782 5/1968 Buss 208-111 2,708,180 5/1955 Fuener et a1. 208l11 3,304,254 2/1967 Eastwood et al 2081 11 3,399,132 8/1968 Mulas'key 2081 11 DELBERT E. GANTZ, Primary Examiner G. E. SCHMITKONS, Assistant Examiner US. Cl. X.R.