US3196104A

US3196104A - Hydrorefining of crude oils

Info

Publication number: US3196104A
Application number: US207069A
Authority: US
Inventors: William K T Gleim; Joseph T Arrigo
Original assignee: Universal Oil Products Co
Current assignee: Universal Oil Products Co
Priority date: 1962-07-02
Filing date: 1962-07-02
Publication date: 1965-07-20
Anticipated expiration: 1982-07-20

Description

United States Patent 3,196,104 HYBROREFINHQG GE (IRUDE GILS William K. 'i. Eleim, Island Lake, and Joseph T. Ari-ago, Mount lrospect, Ill assignors to Universal Eli! Products Company, Des ilaines, ill.., a corporation of Delaware No Drawing. Filed .luly 2, 1962, Ser. No. 207,069 16 Claims. Ci. fits-464) This invention relates to a novel process for hydrorefining petroleum crude oils, heavy vacuum gas oils, heavy cycle stocks, etc, and to a novel catalyst especially adapted thereto. More specifically, the present invention involves a process for hydrorefining heavy hydrocarbon charge stocks to effect the removal of nitrogen and sulfur therefrom, and affords unexpected advantages when employed for the removal of metal contaminants and/ or the conversion of pentane-insoluble asphaltenes into pantane solu ble hydrocarbon oils.

Crude petroleum oils, and also the heavier hydrocarbon fractions and/or distillates derived therefrom, generally contain considerable quantities of sulfurous and nitrogenous compounds. in addition, the crude oils, and the heavy hydrocarbon fractions thereof, contain certain metallic contaminants which have an adverse effect on the activity of catalysts utilized in various processes to which crude oils, or heavy hydrocarbon fractions thereof, are ultimately subjected. The most common metallic contaminants are nickel and vanadium, although other metals includin iron, copper, etc., are often present. These metals occur in a varity of forms. They may exist as metal oxides or sulfides introduced into the crude oil as metallic scale or similar particles, or they may exist in the form of Water-soluble salts of such metals. Usually, however, they exist in the form of thermally stable organo-metallic compounds, such as metal porphyrins and the various derivatives thereof.

Although the metallic contaminants existing in the form of an oxide or sulfide scale may be separated, at least in part, by relatively simple filtering techniques, and the water-soluble salts are at least in part removable by Washing and subsequent dehydration, more extensive treatment is required to remove the thermally stable organometallic compounds before the crude oil or heavy hydrocarbon charge is suitable for further processing.

In addition to the thermally stable organometallic compounds, crude oils contain greater quantities of sulfurous and nitrogenous compounds than are found in lighter hydrocarbon fractions such as gasoline, kerosene, light gas oil, etc. For example, a Wyoming sour crude, having a gravity of 232 API at 60 F., contains about 2.8 Wt. percent sulfur and about 2700 p.p.m. of total nitrogen. Reduction in the concentration of the sulfurous and mitrogenous compounds to the extent that the crude oil or heavy hydrocarbon charge is suitable for further processing, is accomplished with little difficulty by conversion thereof to hydrogen sulfide and ammonia which are readily removed from the system in a gaseous phase. However, reduction in the concentration of the thermally stable organometallic compounds to the extent that the crude oil or heavy hydrocarbon charge is suitable for further processing, is not as readily achieved. Although the concentration of the thermally stable organometallic compounds is relatively small, for example, often less than about p.p.rn. calculated as the elemental metal, subsequent processing techniques are adversely affected thereby. For example, when a hydrocarbon charge stock containing metallic contaminants in excess of about 3 ppm. is subjected to catalytic cracking, the metals become deposited on the catalyst, altering the composition thereof to the extent that undesirable by-products are formed. That is to say, the composition of the catalyst, which is closely 3,l%,ld Patented July 20, 1963 controlled with respect to the nature of the charge stock being processed and the quality and quantity of the product desired, is considerably changed as a result of the metal deposition theron during the course of the cracking process. As a consequence the liquid product recovery is reduced, and coke and hydrogen are formed in excessive amounts, the former producing relatively rapid catalyst deactivation. The presence of thermally stable organometallic compounds, including metal porphyrines, has an adverse effect on other processes including catalytic reforming, isomerization, hydrodc-alkylation, etc.

in addition, crude oils and other heavy hydrocarbon fractions generally contain large quantities of pentaneinsoluble materials present in the form of a colloidal suspension or dispersion difiicult of effective contact with conventional hydrorefining catalysts. These pentane-insoluble materials, described as asphaltenes, are carbonaceous materials considered as coke precursors having a tendency to become immediately deposited Within the reaction zone and on the catalytic composite as a gummy hydrocarbonaceous residue. It is further considered that said asphaltenes contain the bulk of the difiiculty removable metal contaminants as well as a considerable portion of the nitrogenous and sulfurous compounds.

The object of the present invention is to provide a process for hydrorefining heavier hydrocarbonaceous materials, particularly petroleum crude oils, utilizing a catalyst formed in a particular manner. In other hydrorefiniug processes, the metals contained Within the crude oil charge stock are removed therefrom by deposition of the same on the hydrorefining catalyst employed. This practice greatly increases the amount of catalyst in a very short time, precluding the use of a fixed-bed catalyst system commonly employed in the present-day refining operations. Slurry processes, employing catalytioal ly active metals deposited upon silica and/or alumina, are Very errosive, and make plant upkeep diflicult and expensive. The present invention teaches the preparation of a colloidally dispersed unsupported catalyst useful in a slurry type process, and which catalyst will not effect extensive errosion of the reaction system. The present process yields a liquid hydrocarbon product Which is more suitable for further processing Without experiencing the difiiculties otherwise resulting from the presence of the above-described contaminants. The process of the present invention is particularly advantageous in effecting the removal of thermally stable organometallic compounds Without significant product yield loss, while simultaneously converting the pentane-insoluble materials into pentant-soluble liquid hydrocarbons.

In a broad embodiment, the present invention relates to a hydrorefining catalyst comprising the thermal decomposition product of an organometallic complex obtained by the reaction of a halide of a metal of Groups 53, 6B, and the Iron Group with an oxygen-containing organic compound.

in another broad embodiment, the present invention relates to a method of preparing a hydrorefining catalyst which comprises admixing a hydrocarbon charge stock and an organometallic complex obtained by the reaction of a covalent halide of a metal of Groups 5B, 6B, and the Iron Group with an oxygen-containing organic compound, and heating said mixture at a temperature of less than about 310 C. for a time sufiicient to decompose said organometallic complex.

In still another broad embodiment the present invention relates to a process for hydrorefining a petroleum crude oil which comprises admixing said crude oil and an organometallic complex obtained by the reaction of a covalent halide of a metal Iron Group, with an oxygen-containing organic compound, and heating said mixture at a temperature of of Groups 5B, 6B, and the.

less than about 310 C. for a time sufiicient to decompose said organometallic complex, reacting the resulting colloidal suspension with hydrogen at a temperature in excess of about 225 C. and at a pressure in excess or about 500 p.-s.i.g., and recovering the resulting hydrorefined petroleum crude oil.

From the foregoing embodiments it is readily ascertained that the process of this invention involves the utilization of a novel hydrorefining catalyst comprising the thermal decomposition product of an organometallic complex. The organometallic complex of the present invention' is the reaction product of a halide of a metal of Groups 53, 6B, and the Iron Group of the Periodic Table (Handbook of Chemistry and Physics, 43rd ed.), preferably a covalent halide of said metals, and an oxygen-containing organic compound including, for example, an organic acid, anhydride, ester, ether, alcohol, ketone, aldehyde, and the like. The aforementioned oxygen-containing organic compound can be aliphatic or cyclic, containing up to about 20 carbon atoms, and with carbon to carbon saturation or unsaturation. Suitable oxygen-containing organic compounds thus include the various structural isomers of methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, etc., and higher homologs thereof, as well as Z-propenoic acid, Z-butenoic acid, 3-butenoic acid, 2pentenoic acid, etc., and also including cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, and the like. Suitable oxygencontaining organic compounds also include the various anhydrides of the aforementioned acids, for example, ethanoic anhydride, propanoic anhydride, butanoic anhydride, etc. Said oxygen-containing organic compound may be an aldehyde such as, for example, the various structural isomers of methanal, ethanal, propanal, butanal, pentanal, etc., and higher homologs thereof, and also 2-propenal, Z-butenal, etc., or a ketone including Z-propanone, Z-butanone, Z-pentanone, 3-pentanone, 3-penten- 2-one, cyclopentanone, cyclohexanone, etc. Ethers, such as methyl ether, ethyl ether, methyl ethyl ether, propyl ether, butyl ether, pentyl ether, hexyl ether, and the like, as well as furan, pyran, etc., are suitable oxygen-containing organic compounds. Alcohols, including the various structural isomers of methanol, ethanol, propanol, butanol, pentanol, hexanol, 4-penten-1-ol, cyclopentanol, cyclohexanol, etc., and also esters of the aforementioned acids, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc., are also suitable oxygen-containing organic compounds.

The aforementiioned halide of a metal of Groups 513, 6B and the Iron Group can be a halide of vanadium, niobium, tantalum, molybdenum, tungsten, chromium, iron, nickel, or cobalt, and preferably a covalent halide of said metals. Suitable metal halides thus include vanadium trichloride, vanadium tetrachloride, vanadium pentachloride, vanadium oxychloride, vanadium oxydichloride, vanadium oxytrichloride, niobium trichloride, niobium pent-achlonde, niobium oxytrichloride, tantalum pentachloride, molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum oxytrichloride, molybdenum oxytetrachloride, molybdenum dioxydichloride, molybdenum trioxypentachloride, tungsten dichloride, tungsten tetrachloride, tungsten pentachloride, tungsten hexachloride, tungsten. oxytetrachloride, tungsten dioxydichloride, chromium dichloride, chromium trichloride, chromium dioxydichloride, ferrous chloride, ferric chloride, nickel chloride, cobaltous chloride, cobaltic chloride, etc., as Well as the corresponding fluorides, bromides, and iodides of the aforementioned metals.

The halides of the metals of Groups 5B, 6B, and the Iron Group, of which the above enumerated halide are illustrative, react vigorously with oxygen-containing organic compounds of the class hereinabove described. During thecourse' of the reaction, which involves the abstraction of the halogen atom of the metal halide and the cleavage of an oxygen-carbon bond, or an oxygen-hydrogen bond as the case may be, of the oxygen-containing organic compound, said compound combines with the metal portion of the aforesaid metal halide by means of the residual valences created, to form the desired organometallic complex. The organometallic complex thus formed contains at least one metal from the group of vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, nickel, and cobalt.

One preferred embodiment of this invention relates to a hydrorefining catalyst comprising the thermal decomposition product of an organometallic complex obtained by reacting molybdenum pentachloride and ethyl ether.

Another preferred embodiment relates to a hydrorefining catalyst comprising the thermal decomposition product or" an organometallic complex obtained by reacting vanadium trichloride and ethyl ether.

Still another preferred embodiment relates to a hydrorefining catalyst comprising the thermal decomposition product of an organornetallic complex obtained by reacting molybdenum pentachloride and acetic acid.

Yet another preferred embodiment of this invention relates to a hydrorefining catalyst comprising the thermal decomposition product of an organometallic complex obtained by reacting molybdenum pentachloride and propanone.

The organometallic complex of this invention may be prepared simply by mixing the selected metal halide with at least a slight excess of the selected oxygen-containing organic compound. The reaction can be effected at from about room temperature to about the boiling point of the particular oxygen-containing organic compound employed. Or the reaction may be effected in the presence of an inert solvent, such as a chlorinated hydrocarbon, in which case the reaction mixture can be heated at about the boiling point of said solvent. On completion of the reaction, indicated by complete solution of the metal halide, the excess oxygen-containing organic compound and solvent is evaporated or distilled from the desired organometallic complex.

The catalyst is formed by initially dissolving the organometallic complex in the hydrocarbon charge stock containing contaminating influences, including pentane-insoluble asphaltenes which are to be converted into pentane solublehydrocarbons. The quantity of the organometallic complex employed is such that the colloidal suspension or dispersion, resulting when the complex is thermally decomposed in the hydrocarbon charge stock, comprises from about 1.0 wt. percent to about 10.0 wt. percent calculated as the elemental metal. The resulting mixture is heated at a temperature less than about 310 C. for a time sufficient to effect decomposition of the organometallic complex, thereby forming the catalyst as a colloidal suspension or dispersion within the hydrocarbon charge stock. It is preferred that the aforesaid mixture be thus heated in an atmosphere substantially free of hydrogen. The presence of free hydrogen during the decomposition of the organometallic complex tends to have an adverse effect on catalyst activity with respect to the conversion of the pentaneinsoluble fraction and removal of the thermally stable organometallic compounds such as porphyrins. The colloidal suspension or dispersion is then charged into a suitable reaction zone maintained at a temperature of from about 225 C. to about 500 C., and at a hydrogen pressure of from about 500 to about 5000 pounds per square inch gauge.

The process of this invention may be efected in any suitable manner and may comprise either a batch or a continuous type of operation. For example, when a batch type of operation is employed, hydrogen and the petroleum hydrocarbon containing a decomposed organometallic complex are charged to an enclosed vessel and maintained therein at the desired temperature and pressure and with stirring. On completion of the hydrorefining process the normally liquid hydrocarbons are separated from the reaction mixture by any suitable means, for example, through the use of a settling tank or by means of a centrifuge, the resulting catalyst sludge being recovered for reuse as such, or converted back to the organometallic complex by any of the well-known chemical means. The ammonia and the hydrogen sulfide, resulting from the destructive conversion of sulfurous and nitrogenous compounds contained within the petroleum crude oil, are removed in a gaseous phase along with any light paratfinic hydrocarbons such as methane, ethane, propane, etc. In a continuous type of operation, the starting material comprising hydrogen and the colloidal suspension, are continuously charged to a reactor maintained at the proper conditions of temperature and pressure. The reaction product is continuously withdrawn from the reactor at a rate which will insure an adequate residence time therein. The normally liquid hydro carbons may be separated from the reactor efiluent in the above described manner and the catalyst sludge recycled as a portion of the charge to the aforesaid reactor.

Although the hydrorefining process of the present invention is conducted in the presence of hydrogen, it is preferred that the decomposition of the organometallic complex be efiected in the absence thereof. The decomposition of the organometallic complex is conducted at a temperature less than about 310 C. in order to avoid ini tial cracking of the petroleum crude oil prior to effecting complete decomposition of the organometallic complex.

The following example are presented to illustrate the process of the present invention and the efiectiveness there of with relation to the conversion of sulfurous and nitrogenous compounds into sulfur-free and nitrogen-free hydrocarbons, the conversion of pentane-insoluble asphaltenes into pentane-soluble hydrocarbons, and the removal of nickel and vanadium from a petroleum crude oil. It is not intended that the present invention be unduly limit ted to the catalyst, charge stock, and/ or operating conditions employed within the example.

Example I The crude oil employed to illustrate the benefits afforded through utilization of the present invention, was

21 Wyoming sour crude oil having a gravity of 232 API at 60 F. The crude oil contained 2.8 wt. percent sulfur, approximately 2700 ppm. of nitrogen, 18 ppm. of nickel and 81 ppm. of vanadium as metal porphyrins computed as the elemental metal. In addition, the sour crude consisted of 8.3 wt. percent pentane-in soluble asphaltenes. As hereinafter indicated, the process of the present invention effects the conversion of a significant proportion of such asphaltenes to the degree that the same no longer exert a detrimental effect upon further processmg.

An organometallic complex was prepared by slowly adding 180 g. of molybdenum pentachloride to about 1 liter of ethyl ether, and dissolving said molybdenum pentachloride therein. Thereafter, the excess ether was evaporated over a steam bath to yield a brown oil reaction product which was heated an additional two hours over the aforesaid steam bath. This brown oil reaction product of molybdenum pentachloride and ethyl ether was mixed with about 3000 g. of crude oil and the resulting mixture was stirred at a temperature of about 275 C. for a 1 hour period. Thereafter, the mixture was cooled and passed through a colloidal mill.

The resulting colloidal suspension was charged to a reactor consisting of a high pressure vibromixer at the rate of about 125 cc. per hour for a liquid hourly space velocity of about 0.2, and in admixture with about 35,000 c.f./bbl. recycle hydrogen. The reactor was maintained at about 2000 p.s.i.g. and 430 C. The reactor effluent was centrifuged and the normally liquid hydrocarbons recovered. The hydrorefined product, consisting of normally liquid hydrocarbons, contained about 347 ppm. of nitrogen, 0.69 wt. percent sulfur, 0.134 wt. percent asphaltenes and less than 0.03 ppm. of nickel, 0.03 ppm. of vanadium, and 0.1 ppm. of molybdenum.

Example 11 800 g. of molybdenum naphthenate, comprising about 5 wt. percent molybdenum, which can be described as a reaction product of naphthenic acids and molybdenum pentachloride, was mixed with about 4,000 g. of Wyoming sour crude oil and said mixture was diluted with about 4,000 g. of a vacuum gas oil having a gravity of 22.1 API and a boiling range of 600-950" F. at an absolute pressure of 0.20 mm. Hg. The resulting mixture contained 2.40 wt. percent sulfur, 2,096 p.p.m. of nitrogen, 4.45 wt. percent asphaltenes, 36.8 ppm. of vanadium, 10.9 ppm. of nickel, and 1800 p.p.m. of molybdenum. This mixture was stirred at a temperature of about 275 C. for a one hour period. The resulting colloidal suspension was charged at the rate of about 110 g./hour to a reactor consisting of a high pressure vibromixer for a liquid hourly space velocity of approximately 0.21, and in admixture with about 35,000 c.f./bbl. recycle hydrogen. The reactor was maintained at a pressure of about 2,000 p.s.i.g. and at a temperature of about 430 C. The reactor eflluent was centrifuged and the normally liquid hydrocarbons separated therefrom. The hydrorefined product, consisting of said normally liquid hydrocarbons, contained about 555 p.p.m. of nitrogen, 0.38 wt. percent sulfur, 0.079 wt. percent asphaltenes, and less than 0.04 ppm. of nickel, 0.01 ppm. of vanadium, and 0.1 ppm. of molybdenum.

Example Ill An organometallic complex was prepared by slowly adding 6 g. of molybdenum pentachloride to about 20 g. of acetone (propanone) and dissolving said molybdenum pentachloride therein. Upon completion of the reaction the excess acetone was evaporated from the reaction product, which was a brown oil. This last mentioned reaction product of molybdenum pentachloride and acetone, comprising about 2.1 g. of molybdenum, was added to g. of Wyoming sour crude and the mixture heated at about 220 C. to decompose the organometallic complex. The resulting colloidal suspension was charged to an autoclave, pressured to 200 atmospheres with hy drogen, and heated at 400 C. The autoclave was continuously rotated at these conditions for a period of 4 hours. The reaction mixture was recovered from the autoclave and centrifuged to separate the normally liquid hydrocarbons from the catalyst sludge. The hydrorefined product, comprising the aforesaid normally liquid hydrocarbons, contained 234 ppm. of nitrogen and 0.48 wt. percent sulfur. A sour crude oil, hydrorefined in this manner, will contain less than about 0.5 wt. percent asphaltenes, and less than about 0.05 ppm. of nickel, 0.01 ppm. of vanadium and 0.1 ppm. of molybdenum.

Example IV An organometallic complex was prepared by slowly adding 7 g. of vanadium oxytrichloride to about 50 milliliters of ethyl ether and dissolving said molybdenum pentachloride therein. On completion of the reaction the excess ether was evaporated from the reaction product which was a brown oil. This last mentioned reaction product of vanadium oxytrichloride and ethyl ether, comprising about 2 g. of vanadium, was added to 100 g. of Wyoming sour crude and the mixture was heated at about 220 C. to decompose the organometallic complex. The resulting colloidal suspension was charged to an autoclave, pressured to 200 atmospheres with hydrogen, and heated at 400 C. The autoclave was continuously rotated at these conditions for a period of 4 hours. The reaction mixture was recovered from the autoclave and centrifuged to separate the normally liquid hydrocarbons from the catalyst sludge. The hydrorefined product, com prising the aforesaid normally liquid hydrocarbons, contained 879 ppm. of nitrogen and 1.3 wt. percent sulfur.

Z A sour crude oil, hydrorefined in this manner, will contain less than about 0.5 wt. percent asphaltenes, and less than about 0.05 ppm. of nickel, 0.01 p.p.m. of vanadium and 0.1 ppm. of molybdenum.

Example V An organometallic complex was prepared by slowly adding 7 g. of vanadium tetrachloride to about 50 milliliters of ethyl ether and dissolving said vanadium tetrachloride therein. On completion of the reaction the excess ether was evaporated from the reaction product, which was a brown oil. This last mentioned reaction product of vanadium tetrachloride and ethyl ether, comprising about 1.6 g. of vanadium, was added to 100 g. of Wyoming sour crude and the mixture heated at about 220 C. to decompose the organometallic complex. The resulting colloidal suspension was charged to an autoclave, pressured to 200 atmospheres of hydrogen, and heated at 400 C. The autoclave was continuously rotated at'these conditions for a period of 4 hours. The reaction mixture was recovered from the autoclave and centrifuged to separate the normally liquid hydrocarbons from the catalyst sludge. The hydrorefined product, comprising the aforesaid liquid hydrocarbons, contained 865 ppm. of nitrogen and 0.97 wt. percent sulfur. A sour crude oil, hydrorefined in this manner, will contain less than about 0.5'wt. percent asphaltenes, and less than about 0.05 ppm. of nickel, 0.01 ppm. of vanadium and 0.1 p.p.m. of molybdenum We claim as our invention:

1. A catalyst comprising the thermal decomposition product of an organometallic complex obtained by the reaction of a halide of a metal selected from the group consisting of vanadium, niobium, tantalum, molybdenum, tungsten, chromium, iron, nickel and cobalt with an alkyl ether having from 1 to about 6 carbon atoms in each of its alkyl groups.

2,. A catalyst comprising the thermal decomposition product of an organometallic complex obtained by the reaction of a covalent halide of a metal selected from the group consisting of vanadium, niobium, tantalum, molybdenum, tungsten, chromium, iron, nickel and cobalt with an alkyl ether having from 1 to about 6 carbon atoms in each of its alkyl groups.

3. A method of preparing a catalyst which comprises admixing a hydrocarbon charge stock and an organometallic complex obtained by the reaction of a covalent halide of a metal selected from the group consisting of vanadium, niobium, tantalum, molybdenum, tungsten, chromium, iron, nickel and cobalt with an alkyl ether having from 1 to about 6 carbon atoms in each of its alkyl groups, and heating the resultant mixture at a temperature less than about 310 C. for a time sufficient to decompose said organometallic complex.

4. The method of claim 3 further characterized in that said organometallic complex is obtained by the reaction of a covalent molybdenum halide with said ether.

5. The method of claim 3 further characterized in that said organometallic complex is obtained by the reaction of a covalent molybdenum halide with ethyl ether.

6. The method of claim 3 further characterized in that said organometallic complex is obtained by the reaction of a covalent vanadium halide with said ether.

7. The method of claim 3 further characterized in that said organometallic complex is obtained by the reaction of a covalent vanadium halide with ethyl ether.

8. A process for hydrorefining a petroleum oil which comprises admixing said oil and an organometallic complex obtained by the reaction of a covalent halide of a metal selected from the group consisting of vanadium, niobium, tantalum, molybdenum, tungsten, chromium,

'8 iron, nickel and cobalt with an alkyl ether having from 1 to about 6 carbon atoms in each of its alkyl groups heating the resultant mixture at a temperature less than about 310 C. for a time suiiicient to decompose said organometallic complex, reacting the resulting colloidal suspension with hydrogen at a temperature in excess of about 225 C. and at a pressure in excess of about 500 p.s.i.g., and recovering the resulting hydrorefined petroleum oil.

9. The process of claim 8 further characterized in that said organometallic complex is obtained by the reaction of a covalent molybdenum halide with said ether.

10. The process of claim 8 further characterized in that said organometallic complex is obtained by the reaction of a covalent molybdenum halide with ethyl ether.

11. The process of claim 8 further characterized in that said organometallic complex is obtained by the reaction of a covalent vanadium halide with said ether.

12. The process of claim 8 further characterized in that said organometallic complex is obtained by the reaction of a covalent vanadium halide with ethyl ether.

13. A process for hydrorefining a petroleum crude oil which comprises admixing said crude oil with an organometallic complex obtained by reacting molybdenum pentachloride and ethyl ether, heating the resulting mixture at a temperature less than about 310 C. for a time sufficient to decompose said organometallic complex, reacting the resulting colloidal suspension with hydrogen at a temperature of from about 225 C. to about 500 C. and at a pressure of from about 500 to about 5000 p.s.i.g., and recovering a hydrorefined petroleum crude oil.

lid. A process for hydroreiining a petroleum crude oil which comprises admixing said crude oil with an organometallic complex obtained by reacting vanadium oxytrichloride and ethyl ether, heating the resulting mixture at a temperature less than about 310 C. for a time sufficient to decompose said organometallic complex, reacting the resulting colloidal suspension with hydrogen at a temperature of from about 225 C. to about 500 C. and at a pressure of from about 500 to about 5000 p.s.i.g., and recovering a hydrorefined petroleum crude oil.

15. A process for hydrorefining a petroleum crude oil which comprises admixing said crude oil with an organometallic complex obtained by reacting molybdenum pentachloride and naphthenic acid, heating the resulting mixture at a temperature less than about 310 C. for a time suiticient to decompose said organometallic complex, reacting the resulting colloidal suspension with hydrogen at a temperature of from about 225 C. to about 500 C. and at a pressure of from about 500 to about 5000 p.s.i.g., and recovering a hydrorefined petroleum crude oil.

16. A process for hydrorefining a petroleum crude oil which comprises admixing said crude oil with an organometallic complex obtained by reacting molybdenum pentachloride and acetone, heating the resulting mixture at a temperature less than about 310 C. for a time sufficient to decompose said organometallic complex, reacting the resulting colloidal suspension with hydrogen at a temperature of from about 225 C. to about 500 C. and at a pressure of from about 500 to about 5000 p.s.i.g., and recovering a hydrorefined petroleum crude oil.

References Cited by the Examiner UNlTED STATES PATENTS 2,636,841 4/53 Mason 208-217 2,999,075 9/61 Pruett 252472 3,006,844 10/61 Limido 2082l7 3,053,756 9/62 Nottes et a1. 208-189 ALPHONSO D. SULLIVAN, Primary Examiner.

Claims

1. A CATALYST COMPRISING THE THERMAL DECOMPOSITION PRODUCT OF AN ORGANOMETALLIC COMPLEX OBTAINED BY THE REACTION OF HALIDE OF A METAL SELECTED FROM THE GROUP CONSISTING OF VANADIUM, NIOBIUM, TANTALUM, MOLYBDENUM, TUNGSTEN, CHROMIUM, IRON, NICKEL AND COBALT WITH AN ALKYL ETHER HAVING FROM 1 TO ABOUT 6 CARBON ATOMS IN EACH OF ITS ALKYL GROUPS.

8. A PROCESS FOR HYDROREFINING A PETROLEUM OIL WHICH COMPRISES ADMIXING SAID OIL AND AN ORGANOMETALLIC COMPLEX OBTAINED BY THE REACTION OF A COVALENT HALIDE OF A METAL SELECTED FROM THE GROUP CONSISTING OF VANADIUM, NIOBIUM, TANTALUM, MOLYBDENUM, TUNGSTEN, CHROMIUM, IRON, NICKEL AND COBALT WITH AN ALKYL ETHER HAVING FROM 1 TO ABOUT 6 CARBON ATOMS IN EACH OF ITS ALKYL GROUPS HEATING THE RESULTANT MIXTURE AT A TEMPERATURE LESS THAN ABOUT 310*C. FOR A TIME SUFFICIENT TO DECOMPOSE SAID ORGANOMETALLIC COMPLEX, REACTING THE RESULTING COLLOIDAL SUSPENSION WITH HYDROGEN AT A TEMPERATURE IN EXCESS OF ABOUT 225*C. AND AT A PRESSURE IN EXCESS OF ABOUT 500 P.S.I.G., AND RECOVERING THE RESULTING HYDROREFINED PETROLEUM OIL.