US2908633A

US2908633A - Catalyst and hydrocarbon conversion therewith

Info

Publication number: US2908633A
Application number: US505046A
Authority: US
Inventors: Henry E Reif; Herbert L Johnson
Original assignee: Sun Oil Co
Current assignee: Sunoco Inc
Priority date: 1955-04-29
Filing date: 1955-04-29
Publication date: 1959-10-13
Anticipated expiration: 1976-10-13

Description

United States Patent O.

CATALYST AND HYDROCARBON CONVERSION THEREWITH Henry E. Reif, Drexel Hill, and Herbert L. Johnson,

Media, Pa., assignors to Sun Oil Company, Philadelphia, Pa., a corporation of New Jersey No Drawing. Application April-29, 1955 Serial No. 505,046

20 Claims. (Cl. 208-110) This invention relates to catalytic compositions elfective in catalytic processes for converting hydrocarbons. More particularly, the invention relates to new and improved inexpensive catalytic compositions, their preparation, and to processes for using the new catalysts such as processes for removing non-hydrocarbons from mixtures thereof with hydrocarbons and for converting heavy hydrocarbons to relatively low, boiling hydrocarbons.

Heavy hydrocarbon materials such as residues from petroleum cracking operations, reduced heavy crude oil, still tars, and the like, are of little Value. Processes for converting such materials to more valuable lower boiling products have been described. Such processes generally involve contacting the hydrocarbon material with hydrogen and a cracking or hydrogenation catalyst at high temperature and high pressure, the pressure usually being of a magnitude of about 3000 p.s.i.g. or higher. These processes generally require special, expensive catalysts, and suffer from one or more other drawbacks, such as poor yields of the desired distillate liquid products, excessive coke formation resulting in plugged equipment and other ditliculties, and high yields of dry gas. v

An especially serious drawback of processes heretofore used is the degradation of the relatively high boiling products of the process so that they are unsuitable, or at least less suitable, for use in recycling to the process. By degradation is meant the conversion of a portion of the relatively high boiling materials of the charge stock to other relatively high boiling materials which, when again used in the process such as by recycling, are converted to coke. Degradation also includes concentrating such high boiling materials, which are converted to coke on reuse, in the recycle fraction. The Ramsbottom carbon residue method (ASTM D524-42) of evaluating the coke forming tendencies of both the charge stock and recycle stock of the process provides a measure of the degradation of the relatively high boiling materials. Thus, when the Ramsbottom carbon residue of the recycle stock from the process is greater than the Ramsbottorn carbon residue of the charge stock, the recycle stock has been degraded and its reuse in the process results in the formation of relatively large quantities of coke. Conversely, when the Ramsbottom carbon residue of the recycle stock is less than the Ramsbottom carbon residue of the charge stock, the materials of the recycle stock have been upgraded and their reuse in the process results in a decrease in coke formation. Upgrading the recycle stock permits recycling to substantial extinction to form relatively low boiling hydrocarbons as the sole products of the process.

An object of the present invention is to provide new and improved inexpensive catalytic compositions effective for converting hydrocarbons. A further object is to provide a process for preparing the new catalytic compositions of the invention. Another object is to provide a process for converting heavy hydrocarbon materials to relatively low boiling hydrocarbon products. A particular object is to provide a hydrocracking process for converting residual oils to distillate products in good yields, using GENERAL New catalytic compositions have been discovered which give improved results in converting hydrocarbons. The

new catalytic compositions comprises regenerated spent clay having deposited thereon as an essential ingredient a minor quantity of molybdic oxide. Preferably one other oxide of a metal from group VI(B) or group VIII of the periodic table is also deposited on the regenerated spent clay. The new catalyst can thus advantageously comprise molybdic oxide and tungstic oxide deposited on regenerated spent clay. If desired, still another metal oxide, conveniently designated as a promoting oxide, is combined therewith with good results, this latter oxide also preferably being from group VI(B) or VIII of the periodic table. A preferred catalytic composition may thus consist of regenerated spent clay having deposited thereon molybdic oxide, another oxide of a metal of group VI(B) or VIII such as tungstic oxide, and prefer ably an oxide of still another metal, also preferably from group VI( B) or VIII, such as an oxide of chromium, iron, cobalt or nickel, but oxides of other metals may be substituted therefor with good results, such as the oxides of zinc, manganese, zirconium or vanadium. When three metal oxides are deposited on regenerated spent clay toform a preferred catalytic composition in accordance with the invention, the promoting oxide must be an oxide other than the required molybdic oxide and must be an oxide different from the oxide selected from the oxides of the metals of groups VI(B) and VIII, although it may be i also selected from the same groups.

It is essential that the metal oxide constitutents of the composition be present within narrowly defined ranges as hereinafter described.

The reactions involved in the preferred process employing the novel catalysts of the invention are primarily the cracking of the relatively high boiling hydrocarbon materials to lower boiling hydrocarbon materials and the hydrogenation of unsaturated hydrocarbons to saturated hydrocarbons. The overall process, therefore, can conveniently be designated as hydrocracking. Reaction variables used in the hydrocracking process are described hereinafter.

The new catalytic compositions of the invention may be prepared by a variety of means, the general techniques of which are known in the art. It is of primary importance that the limits on the ranges of components present in the catalytic composition be observed as hereinafter discussed.

THE CATALYST combinations thereof, which have been employed for the treating of hydrocarbons by contact therewith, such as in processes for decolorization of mineral oils, until their adsorbent capacity has been substantially consumed, and which have thereafter been separated from the body of oil and-oil adhered thereto has been removed by burning.

' Patented Oct. 13, 1959 aeoaess 3 I a The resulting regenerated spent clay should contain from 0.5% to 4%, and preferably from 1% to 2% by weight carbon. Such spent clay has heretofore provided a disposal problem in petroleum refineries, and the use of this inexpensive material for preparing inexpensive but highly effective catalysts is a substantial advantage of the invention.

Regenerated spent clay is an essential constituent of the catalytic compositions of the invention and other materials, such as silica, alumina, mixtures of silica and alumina such as synthetic mixtures, carbon, bauxite, and the like, cannot be substituted therefor. Natural adsorbent clays that give good results include, for example, kaolin, fullers earth, attapulgite and the montmorrilonite clays including bentonite. The natural adsorbent clay may have been activated, such as by treatment with a mineral acid such as hydrochloric acid or sulfuric acid, prior to its use in the hydrocarbon treatment process, and good results obtained therewith in the present invention. It is not known why regenerated spent clay is remarkably effective, when combined with certain metal oxides, in converting hydrocarbons. It is believed that the prior use of the adsorbent clay in a hydrocarbon treating process, followed by burning adhered oil therefrom leaving deposited on the clay from about 0.5 to 4% by weight carbon, and usually from about 1 to 2% by weight carbon, adjusts the surface characteristics, such as the surface area including pore diameter, of the clay so that it is an especially effective component of the present catalytic compositions.

The quantity of molybdic oxide deposited on the regenerated spent clay must be within the range of from 0.2 to 5% by weight. At quantities below 0.2% sub stantial conversion of heavy hydrocarbon materials to lighter boiling materials requires relatively high temperatures and results in excessive coke formation, and in the degradation of the recycle stock of the process. At concentrations above 5% by weight, prohibitively high yields of dry gas, an undesired product, are obtained from the process. When used, the other oxide of a metal selected from the group consisting of groups VI(B) and VIII of the periodic table, which is preferably tungstic oxide, may be present in a concentration up to 5% by weight. With a concentration of such other oxide above 5% by weight, substantially the same difficulties are observed as when the quantity of molybdic oxide is above the stated range therefor. Remarkably good results are obtained when substantially equal quantities, within the stated range, of molybdic oxide and the other metal oxide, preferably tungstic oxide, are deposited on regenerated spent clay. When at promoting oxide is employed, a quantity sufficient to enhance the activity of the catalyst should be used, such quantity being a promoting quantity. This quantity will generally be substantially equivalent to the quantities of molybdic oxide and tungstic oxide used, i.e., a quantity sufiicient for the metal of the promoting oxide to react stoichiometrically with both the tungsten and molybdenum oxides. For example with C0 0 as the promoting oxide, the quantity of the water soluble compound of cobalt used to impregnate the regenerated spent clay, as hereinafter described, should be such that the quantity of the cobalt is just sulficient to react with the molybdenum compound to form cobalt molybdate and with the tungsten compound to form cobalt tungstate. It appears immaterial whether such reaction, in whole or in part, actually occurs, and hence the promoting material is conveniently described as the metal oxide although it is realized that the metal thereof may at least in part be combined in complex compounds with the tungsten and molybdenum oxides. The promoting oxide is preferably an oxide of chromium, iron, cobalt, nickel, manganese or me.

To illustrate specific catalytic compositions in accordance with the invention, regenerated spent clay having deposited thereon 0.5% by weight M00 and 0.5% by weight W0 gives good results. Deposition of a promoting quantity of an oxide of cobalt, nickel, manganese or zinc on this catalytic composition is advantageous. An oxide of chromium can be substituted for tungsten oxide in the above compositions and good results obtained therewith.

PREPARATION OF CATALYST Although the catalytic compositions of the present invention may be prepared by various means, it is preferred to employ aqueous solutions of water soluble compounds of the metals whose oxides are desired. Such aqueous solutions are used to impregnate the regenerated spent clay, the concentration of the water soluble compound and quantity used to impregnate the clay being such that the resulting concentration of metal oxide will be within the stated ranges. Separate solutions of water soluble compounds of the metals whose oxides are desired in the final catalytic composition may be used, or in a single solution containing two or more water soluble compounds, such as water soluble compounds of molybdenum, tungsten and cobalt, may be used. When separate solutions are employed, impregnation may be done in any succession desired, but it is preferred to impregnate the regenerated spent clay with solutions of all the metals whose oxides are desired prior to calcining the impregnated composition. Calcining of the impregnated regenerated spent clay is conveniently accomplished by heating the impregnated regenerated spent clay to a temperature of from about 800 F. to 1000 F. in contact with an oxygen containing gas such as air to convert the metal compounds to the corresponding metal oxides.

HYDROCRACKING The reactions involved in the present process for converting hydrocarbons to lower boiling hydrocarbons are primarily the cracking of the relatively heavy hydrocarbons and the hydrogenation of unsaturated materials such as olefins, which may be present in the charge stock or formed in the process, to saturated materials. The relatively low boiling products can be separated into desired fractions, such as a gasoline fraction containing hydrocarbons having 4 carbon atoms up to those boiling at 400 F. (C4400 F.), a middle oil containing hydrocarbons boiling from 400 F. to 650 F., a heavy oil containing hydrocarbons boiling from 650 F. to 840 F., and recycle oil consisting of hydrocarbons boiling above 840 F. Other desired fractions can be separated if desired.

A wide variety of heavy hydrocarbon materials having initial boiling points above about 840 F. can be converted in the process of the invention, residues from petroleum cracking operations, reduced heavy crude oil, still tars, and the like, giving good results. It is preferred to use heavy hydrocarbons having a hydrogen to carbon atomic ratio of at least 1.2 and preferably above about 1.4. Good results are obtained when the A.P.I. gravity of the heavy hydrocarbons is below 25, but the process has its greatest utility when the A.P.I. gravity is below about 17. Generally the Ramsbottom carbon residue will be from about 9 to 30, but may be as low as about 4. It is preferred to use tower bottoms from petroleum opera/- tions, including for example the residues from thermal or catalytic cracking operations, or reduced heavy crude oils including crude oils having a high content of sulfur compounds, but other heavy hydrocarbon materials such as Athabasca tar can be used. For convenience, the hydrocracking process of the invention is herein described using residual oil as illustrative of the heavy hydrocarbon materials that can be employed.

In the hydrocracking process, the residual oil is contacted with a catalyst of the invention for from about 15 minutes to 8 hours at a temperature of from 700 F. to 925 F., and a pressure of from 400 p.s.i.g. to 5000 p.s.i.g. Hydrogen must be present and preferably a substantial excess is used, such as a mole ratio of hydrogen to 011 of from 2 to 20. The process may be operated batchwise 'o'r continuously. .lnbatch operation a catalyst to oil weight ratio of from 0.05 to 1 gives good results.

In continuous operation, such as a fixed bed operation, a space rate of oil through the reactor of from 0.2 to 6 volumes of oil per volume of catalyst per hour gives good results. Slurry type operation can also be employed using reaction conditions essentiallyequivalent to those above stated.

It is of primary importance, in operating the process, to relate the reaction conditions so that conversion of the hydrocarbon charge stock to material boiling below the boiling range of the, charge stock is maintained below about 80% by weight for each contacting with the catalyst. At higher conversions the production of coke and dry gas become excessive and deleteriously afiect the process. For an operable process, however, the conversion of the charge stock should be above 30% by weight for each contacting with catalyst.

After contacting the residual oil and catalyst under the conditions as stated above, the oil is separated into desired fractions by distillation. A gasoline fraction can be separated and used as motor fuel, as a component of motor fuel by blending'with hydrocarbons from other sources, or used in subsequent refinery operations such as reforming. Distillate oil products can be used without further treatment such as for fuel oil, or can be used in subsequent refinery operations such as thermal or catalytic cracking. The higher boiling materials, generally the;hydrocarbons boiling above 840 F. provide excellent recycle stock for the process since, as shown hereinafter, such materials are upgraded in the process to contain a smaller quantity of materials that are convertable to coke than is contained by the initial charge material.

EXAMPLES In the following examples the regenerated spent clay was prepared from an acid activated bentonite which had been used in a process for decolorizing a petroleum lubricating oil. When the adsorptive capacity of the clay for the non-hydrocarbon constituents of the lubricating oil. had been substantially depleted, the clay was separated "from the oil and the adherent oil removed by burni ng in contact with air. The resulting regeneratedspent clay contained from about 1% to 2% by weight carbon and impurities fromthe oil treatment which were not removed in the burning step.

Example 1 A "catalytic composition was prepared in accordance with the invention by impregnating the regenerated spent clay with an'aqueous solution of 1.8 parts ofiammonium tungstate and 1.9 parts of ammonium molybdate, in 250 parts of water. The concentration of the water soluble compounds and the quantity .of solution used were calculated to give desired quantities of the metal oxides in the final composition. The impregnated composition was dried and heated to about 1000 F. in contact with air. The resulting composition was screened to pass 100 mesh (U.S. series). The final catalytic composition contained 0.5% by Weight M00 and 0.5% by weight W0 This composition is designated as catalyst A in following Table I.

The process used for the preparation of catalyst A was substantially repeated except that, after impregnation with the aqueous solution of the molybdenum and tungsten compounds, a subsequent impregnation was made using an aqueous solution of nickelous nitrate. The solution contained 6 parts of Ni(NO -6H O in 50 parts of water. The concentration of the nickelous nitrate and quantity of solution used'were calculated-to give an equivalent quantity of nickel, i.e.,' a quantity of nickel just sufficient to react with the molybdenum and tungsten compounds. The resulting composition contained 0.5 by weight M00 0.5 by weight W0 and an equivalent quantity of nickel oxide. This composition is designated as catalyst B in'followingTable I.

In a similar manner other catalytic compositions were prepared in which other promoting oxides were substituted for nickel oxide. {These other promoting oxides were of the following metals, shown together with the designation of the final catalytic composition in Table I:

Catalyst designation It will be understood that each of the above catalytic compositions consisted essentially of regenerated spent clay, 0.5% by weight molybdic oxide, 0.5% by weight tungsten oxide, and an equivalent quantity of the oxide of the indicated metal which, for example, in catalyst C amounted to about 0.3% by Weight cobaltoxide (calculated as cobalt).

Each of the catalytic compositions were used to hydrocrack the same residual oil. The residual oil charge stock was from thevacuum distillation of crude oil, and had an initial boiling point of about 840 R, an A.P.I. gravity of 15.3, a Ramsbottom carbon residue of 9.3 by weight, a hydrogen to carbon atomic ratio of 1.60, and contained 0.77% by weight sulfur compounds (calculated as sulfur).

In carrying out the process, the indicated catalyst and residual oil were introduced into a reactor, the catalyst to oil weight ratio being 0.1. The reactor was flushed with hydrogen and hydrogen introduced to a pressure of 2100 p.s.i.g., the hydrogen to oil mole ratio being about 6. The reactor was then heated and maintained at a temperature of 800 F. for 2 hours. After cooling, the catalyst was separated and the hydrocarbon reaction mixture distilled to separate desired fractions. The results obtained with the several catalysts are shown in following Table I. In Table I, results obtained using regenerated spent clay, prepared aszabove described, as the catalyst are included for comparison, the regenerated spent clay being designated as catalyst H.

TABLE I Catalyst desi nation Product distribution (wt. percent)" Dry gas (C1-C3) Gasoline {O -400 F.)

Heavy oil (650840 F.)

Recycle oil (above 840 F.) Ramsbottom Carbon Residue of Recycle oil (wt. percent) Coke (wt. percent) Charge converted (wt. percen Hydrogen consumed (ft. /bbl.)

V Regenerated spent clay alone.

The data of Table I show good operation of the process of the invention using the catalysts of the invention. The good conversion of the residual oil to distillate products, with only minor quantities of dry gas and coke being formed, shows the effectiveness of the catalytic compositions of the invention. It should be noted that with catalytic compositions A through G, the Ramsbottom carbon residue of the recycle oil is less than the value for the charge stock. Hence the value of the recycle oil for reuse in the process is substantially enhanced in that even better results are obtained therewith, and in that the oil can be recycled to substantial extinction, i.e., can be converted substantially completely to lower boiling more valuable products.

The data obtained with catalyst H, which is not within the scope of the catalytic compositions of the invention, show a degradation of the recycle oil as compared with the charge stock, and hence operation therewith is unsatisfactory.

Example 2 To further illustrate catalytic compositions of the invention and the necessity for using regenerated spent clay as a component of the catalyst, a catalyst was prepared consisting essentially of 2% by weight M on regenerated spent clay (catalyst I). For comparison, a composition consisting essentially of 2% by weight M00 on coke was prepared (catalyst J). The coke was prepared by coking a petroleum residuum and had an apparent density of 0.493, and was ground to pass 100 mesh. Also, a catalyst consisting essentially of M00 on bauxite (catalyst K) and a composition consisting essentially of 5% M00 on a synthetic silica-alumina cracking catalyst whose activity toward cracking hydrocarbons had been decreased about 30% by use in a hydrocarbon cracking process (catalyst L) were prepared. To show the necessity of using molybdic oxide as a component of the catalytic compositions of the invention, a composition consisting essentially of 1% by weight W0 on regenerated spent clay was prepared (catalyst M). The technique of preparation in each instance was substantially as described in Example 1.

The residual oil charge stock, which had a Ramsbottom carbon residue of 9.3% by Weight, and reaction conditions of temperature, pressure, time, hydrogen to oil mol ratio, and catalyst to oil weight ratio were as described for Example 1. Results obtained are shown in following Table II:

TABLE II Catalytic Composition I J K L Product distribution (wt. percent):

Dry gas (Ci-Ca) Gasoline (Ct-400 F.) Middle Oil (400-650" F.) 11 Heavy oil (650840 F.) 24 Recycle oil (above 840 F.) 47

Ramsbottorn Carbon Residue of Recycle oil (wt. percent) Coke (wt. percent) Charge converted (wt. percent) 51 Hydrogen consumed (ft. /bbl.)

These data show that with catalytic composition I, within the scope of the invention, gave good results and upgraded the recycle oil, whereas the remaining compositions, all of which are outside of the compositions of the invention, caused degradation of the recycle oil.

Example 3 8 clay, coke fines obtained from the coking of coal. The coke was screened to pass mesh (U.S. series). The compositions contained the following indicated quantities, in percent by weight, of metal oxides:

Catalyst N2% MoO +1% Cr O Catalyst O2% MoO +1% Mn O Catalyst PO.5% MoO +0.5% W0 Catalyst Q-2% MoO +1% Fe 0 Each of these compositions were used to hydrocrack the residual oil charge stock of Example 1, which had a Ramsbottom carbon residue of 9.3%. The reaction conditions of temperature, pressure, time, hydrogen to oil mol ratio, and catalyst to oil mol ratio were as described for Example 1. Results obtained are shown in following Table III:

TABLE III Catalytic Composition N Product distribution (wt. percent)- Dry gas (C1-C3) Gasoline (C4-400 F.) Middle oil (400-650 F.) Heavy oil (em-840 F.) Recycle oil (above 840 F.)

Ramsbottom Carbon Residue of Recycle oil (wt. percent) oke Charge converted (wt. percent) Hydrogen consumed (itfi/bbl.)

In like manner, an addition series of compositions were prepared using, in place of regenerated spent clay, coke obtained from the coking of a petroleum residuum at an elevated temperature. The coke was comminuted to pass 100 mesh. The compositions contained the following indicated quantities, in percent by weight, of M00 and W0 and equivalent quantities of the indicated promoting oxides (calculated as the appropriate metal as above described):

Each of these compositions were used to hydrocrack the residual oil charge stock of Example 1, which had a Ramsbottom carbon residue of 9.3%. The reaction conditions of temperature, pressure, time, hydrogen to oil mol ratio, and catalyst to oil mol ratio were as described for Example 1. Results obtained are shown in following Table IV: V

TABLE IV Catalytic Composition R S T U V W Product distribution (wt. percent):

Dry gas (Ci-C3) 4 4 3 6 4 4 Gasoline (CA-400 F.) 8 12 11 19 16 12 Middle oil (400650 F.) 14 14 26 19 19 17 Heavy oil (650-840" F.) 20 19 14 21 19 21 Recycle oil (above 840 F.) 52 50 46 83 40 44 Ramsbottom Carbon Residue of Recycle oil (wt. percent).-- 11.1 10. 8 13.1 16. 2 15.0 11. 9 Coke 0.5 0.8 0.3 1.2 1.7 0.6 Charge converted (wt. percent). 48 49 54 65 58 54 Hydrogen consumed (tt. /bb1.).. 478 537 626 Still another series of compositions were prepared using bauxite in place of regenerated spent clay. The bauxite was comminuted to pass 100 mesh. The compositions contained the following indicated quantities, in percent by weight; of metal oxides: "Catalys't X+1% MoO +Co (equivalent quantity cal- -culated as Co) t Catalyst .Y,-2% MoO +1% Cr 0 Catalyst Z-0.5% M0O +0.5% W0 An additional compositionwasprepared by depositing 0.5% by' weight M00 0.5% by weight W0 and an equivalent quantity (calculated as Co) of C0 0 on fresh Attapulgite, i.e. on a natural adsorbent clay which had not previously been used in a process involving contacting hydrocarbons therewith. This is designated as catalyst AA.

Each of these compositions was used to hydrocrack the residual oil charge stock of Example 1, which had a Ramsbottom carbon residue of 9.3%. The reaction conditions of temperature, pressure, time, hydrogen to oil moi. ratio, and catalyst to oil mol. ratio were as described for Example 1. Results obtained are shown in following Table V:

TABLE V Catalytic Composition None of the compositions used in Example 3 were within the scope of the invention, which requires regenerated spent clay as a catalytic component. Substituting other materials therefor, as shown by the data of the examples, defeats the objects of the invention by causing degradation of the recycle fraction of the hydrocarbon product.

The catalytic compositions of the invention can be employed in processes other than hydrocracking, such as in desulfurization of crude oils, distillate oils, or residual oils. To obtain desulfurization it is advantageous to contact the catalyst and oil, in the presence of hydrogen, at relatively low temperatures, say from about 625 F. to 775 F. and pressures of from about 400 p.s.i.g. to 5000 p.s.i.g. with a time of contact sufiicient to achieve the desired degree of sulfur removal.

The foregoing examples illustrate embodiments of the invention. When other catalytic compositions within the scope of the invention are employed, results substantially equivalent to those herein shown are obtained.

The invention claimed is:

'1. A new catalytic composition comprising regenerated spent clay and molybdic oxide.

2. A new catalytic composition comprising regenerated spent clay having deposited thereon from 0.2% to 5% by weight molybdic oxide.

3. A new catalytic composition comprising regenerated spent clay, from 0.2% to 5% by weight molybdic oxide and not above 5% by weight of another oxide of a metal selected from the group consisting of the metals of group VI(B) and of group VIII of the periodic table.

4. A new catalytic composition comprising regenerated spent clay, from 0.2% to 5% by weight molybdic oxide and from 0.2% to 5% by weight tungsten oxide.

5. A new catalytic composition comprising regenerated spent clay, from 0.2% to 5% by weight molybdic oxide and from 0.2% to 5% by weight chromium oxide.

6. A new catalytic composition comprising regenerated spent clay, from 0.2% to 5% by weight molybdic oxide and from 0.2% to 5% by weight iron oxide.-

7. A new catalytic composition comprising regenerated ".10 spent clay, from 0.2% to"5%' by weight molybdic oxide and from 0.2% to 5% by weight cobalt oxid -8. A' newcatalytic composition comprising regenerated spent clayQfr'om' 0.2% to 5% 'by weightlm'olybdic oxide and from 0.2% to 5% by weight nickel oxide.

9. A new catalytic composition consisting essentially of regenerated spent clay,from 0.2% to 5% by weight molybdic oxide, aquantity of not above 5% by weight of another oxide of a metal selected from the group consisting of the metals of group VI-(B) and group VIII of the periodic table, and a promoting quantity of a promoting oxide.

10. A new catalytic composition according to claim 9 wherein said promoting oxide is an oxide of a metal selected from the group consisting of the metals of group VI(B) and group VIII of the periodic table, manganese and zinc.

11. A new catalytic composition consisting essentially of regenerated spent clay, from 0.2% to 5% by weight molybdic oxide, from 0.2 to 5% by weight tungsten oxide, and an equivalent quantity of an oxide of a metal selected from the group consisting of chromium, iron, cobalt, nickel, manganese and zinc.

12. A new catalytic composition comprising regenerated spent clay having deposited thereon about 0.5% molybdic oxide, about 0.5% tungstic oxide, and an equivalent quantity of cobalt oxide.

13. A new catalytic composition comprising regenerated spent clay having deposited thereon about 0.5 molybdic oxide, about 0.5% tungstic oxide, and an equivalent quantity of iron oxide.

14. A new catalytic composition comprising regenerated spent clay having deposited thereon about 0.5% molybdic oxide, about 0.5% tungstic oxide, and an equivalent quantity of chromium oxide.

15. A new catalytic composition comprising regenerated spent clay having deposited thereon about 0.5% molybdic oxide, about 0.5% tungstic oxide, and an equivalent quantity of nickel oxide.

16. A new catalytic composition comprising regenerated spent clay having deposited thereon about 0.5% molybdic oxide, about 0.5% tungstic oxide, and an equivalent quantity of manganese oxide.

17. Process for converting hydrocarbons to lower boiling hydrocarbons which comprises contacting, in the presence of hydrogen, a mixture of hydrocarbons boiling above about 840 F. with a catalytic composition comprising regenerated spent clay having deposited thereon from 0.2% to 5% by weight molybdic oxide under reaction conditions including a temperature of from 700 F. to 925 F. and a presure of from 400 p.s.i.g. to 5000 p.s.i.g. to convert from 30% to by weight of the hydrocarbons to lower boiling hydrocarbons.

18. Process for converting hydrocarbons to lower boiling hydrocarbons which comprises contacting, in the presence of hydrogen, a mixture of hydrocarbons boiling above about 840 F. with a catalytic composition comprising regenerated spent clay having deposited thereon from 0.2% to 5% by weight molybdic oxide and a quantity of not above 5% by weight of an oxide of a metal selected from the group consisting of the metals of group VI(B) and group VIII of the periodic table under reaction conditions including a temperature of from 700 F. to 925 F. and a pressure of from 400 p.s.i.g. to 5000 p.s.i.g. to convert from 20% to 80% by weight of the hydrocarbons to lower boiling hydrocarbons.

19. Process according to claim 18 wherein said catalytic composition contains an equivalent quantity of an oxide of a metal selected from the group consisting of chromium, iron, cobalt(, nickel, manganese and zinc.

20. Process for the preparation of a novel catalytic composition which comprises contacting a natural adsorbent clay with hydrocarbons, separating the clay from the body of hydrocarbons, burning oil adhering to the clay to produce a regenerated spent clay containing from 1,1 12 01. .to 4% by wei ht arbon im n t re- 2 Z 9 58 Sim on etal- -1- +1- O 20 942 generated spent clay with 331 aqueqigs sghifion 01f awater 2,375,402 Cbrson et a1. f. May '8, 1945 soluble pompound io f molybdenum, a 1 1 d heating the im-' 2,417,359 Guyer Mar. 11, '1947 pregnaied spent clay to a terflpenafcfite of frgm about 800 2,423,833 :Hirsh l "July 15, 1947= F. to 1000 F. in cpntaet with an oxygen containing gas. 5 2,457,566 Krieger et a1 .-Dec; 28, 1948 0 2,687,370 Hendricks' Aug. 24, 1954 References Cited in the file of this patent 2,700,014 Anhorn et a1. Jan. 18, '1955 2,703,308 ,Oblad et a1 Mar. 1, 1955 UNITED STATES PATENTS 21,77 ,247 Anhqni et a1. Jen. 1;, 1951 1,550,805 H a t er Aug. 25, 1925 10

Claims

17. PROCESS FORM CONVERTING HYDROCARBONS TO LOWER BOILING HYDROCARBONS WHICH COMPRISES CONTACTIG, IN THE PRESENCE OF HYDROGEN, A MIXTURE OF HYDROCARBONS BOILING ABOVE ABOUT 840*F. WITH A CATALTIC COMPOSITION COMPRISING REGENERATED SPENT CLAY HAING DEPOSITED THEREON FROM 0.2% TO 5% BY WEIGHT MLYBDIC OXIDE UNDER REACTION CONDITIONS INCLUDING A TEMPERATURE OF FROM 700* F. TO 925*F. AND A PRESSURE OF FROM 400 P.S.I.G. TO 5000 P.S.I.G. TO CONVERT FROM 30% TO 80% BY WEIGHT OF THE HYDROCARBONS TO LOWER BOILING HYDROCRBONS.