US3173860A - Hydrorefining of crude oil and catalyst therefor - Google Patents

Hydrorefining of crude oil and catalyst therefor Download PDF

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US3173860A
US3173860A US160902A US16090261A US3173860A US 3173860 A US3173860 A US 3173860A US 160902 A US160902 A US 160902A US 16090261 A US16090261 A US 16090261A US 3173860 A US3173860 A US 3173860A
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crude oil
catalyst
metallic compound
hydrorefining
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John G Gatsis
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Universal Oil Products Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
    • C10G45/16—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles suspended in the oil, e.g. slurries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/64—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

Definitions

  • the present invention relates to a novel, method for preparing a catalyst particularly adaptable for utilization in the hydro-refining of petroleum crude oils, heavy vacuum gas oils, heavy cycle stocks, etc.
  • the present invention involves a process for the hydrorefining of heavy hydrocarbon charge stocks to effect the removal of nitrogen and sulfur therefrom, and aitords unexpected advantages when employed for the removal of metals and/or to convert the pentane-insoluble fraction thereof into useful pentane-soluble hydrocarbon oils.
  • crude oil and heavier hydrocarbon fractions contain quantities of metallic contaminants which exert detrimental effects upon the catalyst utilized in various processes to which the crude oil or heavy hydrocarbon fraction is ultimately subjected.
  • the most common metallic contaminant are nickel and vanadium, although other metals including iron, copper, etc., are often present. These metals may occur in a variety of forms: they may exist as metal oxides or as sulfides, introduced into the crude oil as metallic scale or particles; in the form of soluble salts of such metals; usually, how ever, they exist in the form of organo-metallic compounds such as metal porphyrins and the derivatives thereof.
  • the metallic contaminants existing as oxide or sulfide scale may be removed, at least in part, by a relatively simple filtering technique, and the water-soluble salts are at least in part removable by washing and subsequent dehydration, a much more severe treatment is generally required to remove the organo-metallic compounds, and to the degree required in order that the resulting crude oil or heavy hydrocarbon fraction is suitable for further processing.
  • organernetallic compounds including metal porphyrins
  • crude oils contain greater quantities of sulfurous and nitrogenous compounds than are found in li hter hydrocarbon fractions such as gasoline, kerosene, light gas oil, etc.
  • a Wyoming sour crude having a gravity of 23.2" API at 60 F., contains about 2.8% by weight of sulfur and about 2700 ppm. of total nitrogen.
  • the nitrogenous and sulfurous compounds are converted, up on being subjected to a treating process, into hydrocarbons, ammonia, and hydrogen sulfide, the latter being readily removed from the system in a gaseous phase. Reduction in the concentration of the metallic contaminants is not as easily achieved, and to the extent that the crude oil or heavy hydrocarbon charge stock becomes suitable for further processing.
  • the composition of the catalytic composite which is closely controlled with respect to the "ice nature of the charge stool; being processed and to the desired product quality and quantity, is changed considerably as the result of the deposition of the metallic contaminants onto the catalyst, the changed composite resulting in changed catalytic characteristics.
  • Such an effect is undesirable with respect to the cracking process, since the deposition of metallic contaminants upon the catalyst tends to result in a lesser quantity of valuable liquid product, and large amounts of hydrogen and coke, the latter producing relatively rapid catalyst deactivation.
  • the presence of organic metal compounds, including metal porphyrins affects deleteriously other processes including catalytic reforming, isomerization, hydrodeallrylation, etc.
  • crude oils and other heavier hydrocarbon fractions generally contain large quantities of pentane-insoluble material.
  • the Wyoming sour crude consists of about 8.37% by weight of pentane-insoluble asphaltenes which are hydrocarbonaceous compounds considered as coke-precursors having the tendency to become immediately deposited within the reaction zone and onto the catalytic composite employed in the form of a gummy hydrocarbonaceous residue. This constitutes a large loss of charge stock; it is economically desirable to convert such asphaltcnes into useful hydrocarbon oil fractions.
  • the object of the present invention is to provide a much more efficient process for hydrorefining heavier hydrocarbonaceous material, and particularly petroleum crude oils, utilizing a catalyst prepared in a particular manner.
  • metals are generally removed from the charge stock by deposition of the same on the catalyst employed. This greatly increases the amount of catalyst in a very short time, and precludes the use of a fixed-bed catalyst system as employed in practicing present-day methods.
  • Slurry processes, employing catalytically active metals deposited upon silica and/or alumina, are extremely erosive, and make plant maintenance ditficult and expensive.
  • the present invention teaches the preparation of a collodially dispersed, unsupported catalyst useful in a slurry process, and which will not effect extensive erosion 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 foregoing contaminants.
  • the process of the present invention is particularly advantageous in eifecting the removal of the organic metal compounds without significant product yield loss, while simultaneously converting pentane-insoluble material into pentane-soluble liquid hydrocarbons.
  • the present invention relates ,to a hydrorefim'ng catalyst which comprises at least one decomposed organza-metallic compound of the metals of Group VI-B, having an atomic number greater than 24, and the Iron-group.
  • Another broad embodiment of the present invention involves a method of preparing a hydrorefining catalyst which comprises forming a hydrocarbon solution of at least one organo-metallic compound of the metals of Group VI-B, having an atomic number greater than 24, and the Iron-group, land decomposing said organo-metallic compound in said hydrocarbon.
  • a more limited embodiment of the present invention affords a process for hydroreiining a hydrocarbon charge stock which comprises admixing said charge stock with at least one organo-metallic compound of the metals of Group VI-B, having an atomic number greater than 24,
  • the method of the present invention involves the preparation of a catalyst utilizing metals selected from Group VI-B and the Iron-group of the Periodic Table.
  • the catalyst prepared in accordance with the method of the present invention, may comprise one or more metals from the group of molybdenum, tungsten, iron, nickel and cob-alt. It is noted that the metal selected from Group VI-B, namely molybdenum and/or tungsten, has an atomic number greater than 24.
  • the catalyst is prepared by initially dissolving an organic complex of the selected metal, or metals, in the hydrocarbon charge stock containing the pentane-insoluble fraction which is to be converted into soluble hydrocarbons.
  • the quantity of the organo-metallic compound employed is such that the colloidal suspension, or dispersion, which results when the organo-metallic compound is decomposed within the hydrocarbon charge stock, comprises from about 1.0% to about 10.0% by weight, calculated as the elemental metal.
  • Suitable oragno-metallic compounds include molybdenum hexacarbonyl, tungsten hexacarbonyl, iron pentacarbonyl,
  • molybdenum hexacarbonyl in combination with nickel formate tungsten hexacarbonyl in combination with iron carbonyl, various cobalt complexes, etc.
  • the process is effected, as hereinabove set forth, by initially dissolving the desired quantity of the organometallic compound, such as molybdenum hexacarbonyl, in the hydrocarbon charge stock.
  • the resulting mixture is then heated, preferably in a non-reducing atmosphere,
  • the presence of free hydrogen during the decomposition of the organometallic compound has a tendency to affect detrimentally the activity of the catalyst with respect to the conversion of the pentane-insoluble fraction as well as the removal of metals.
  • the colloidal dispersion is then passed into a suitable reaction zone at a temperature within the range of from about 225 C. to about 500 C. under a hydrogen pressure within the range of about 500 to about 5000 pounds per square inch gauge.
  • reaction zone In order to maintain the catalyst in its decomposed form, either as the metal or as a lower oxide thereof, it is necessary that the reaction zone be maintained substantially completely free from carbon monoxide. Following the decomposition of the molybdenum hexacarbonyl, some carbon monoxide will be present in the gaseous phase. This is readily removed upon venting prior to passing the mixture into the reaction zone. Where some of the carbon monoxide is dissolved in the liquid phase, it is preferred to remove the same by suitable stripping means.
  • the process may be conducted in a batch-type procedure or in an enclosed vessel through which the colloidal suspension is passed; when efiected in a continuous manner, the process may be conducted in either upward flow or downflow.
  • the normally liquid hydrocarbons are separated from the total reaction zone effiuentby'any suitable means, for example, through the use of a centrifuge, the resulting catalyst sludge being converted back to the oragno-metallic compound by any well-known'chemical means.
  • the ammonia and hydrogen sulfide, resulting from the destructive conversion of sulfurous and nitrogenous compounds contained within the hydrocarbon charge stock, are removed, along with any light paraffinic hydrocarbons including methane, ethane and propane, in a gaseous phase.
  • the decomposition of the organo-metallic compound such as molybdenum hexacarbonyl
  • the decomposition to form the colloidal suspension be conducted in substantial absence of other well-known reducing agents.
  • the dispersed material will be the elemental metal or a lower oxide form thereof. In any event, it is understood that the stated concentrations are computed on the basis of the elemental metal.
  • the decomposiion of the oragno-metallic compound is conducted at a temperature less than about 310 C. in order to avoid initial cracking of the petroleum crude oil prior to effecting complete decomposition.
  • Example 1 The crude oil employed to illustrate the benefits afforded through the utilization of the present invention, was a Wyoming sour crude oil having a gravity of 232 API at 60 F, and containing 2.8% by weight of sulfur, approximately 2700 ppm. of nitrogen, 18 ppm. of nickel and 71 ppm. of vanadium as metal porphyrins, computed as the elemental metal.
  • the sour crude consisted of 8.37% by weight of pentane-insoluble asphaltenes.
  • the process of the present invention efiects the conversion of a significant proportion of such asphaltenes, and to the degree that the same no longer exert a detrimental effect upon further processing.
  • the colloidally dispersed catalysts were prepared by decomposing the indicated organo-metallic compounds within the sour crude oil, thereafter subjecting the mixture to conversion in a rotating autoclave maintained at about 400 C., at an imposed hydrogen pressure of about 200 atmospheres. Each of the colloidal suspensions remained in the autoclave at the foregoing conditions for a period of from about 4 to about 8 hours.
  • Molybdenum hexacarbonyl in an amount of 23.3 grams was admixed with 200 grams of the Wyoming sour crude, the mixture being charged to the rotating autoclave and heated to a temperature of 250 C. for a period of 3 hours. After venting to remove carbon monoxide, the autoclave was pressured to atmospheres with hydrogen, and then heated to a temperature of 400 C. for a period of about 8 hours, the final pressure being about 200 atmospheres.
  • the gravity, API at 60 F., of the resulting normally liquid product effluent was 40.], indicating a substantial degree of conversion to lower-boiling hydrocarbon products.
  • the liquid product indicated only 7.1 ppm. of nitrogen, about 0.02% by weight of sulfur, about 0.10% by weight of pentane-insoluble asphaltenes, less than about 0.02 ppm. of nickel and less than about 0.02 ppm. of vanadium.
  • a process for hydrorefining a hydrocarbon charge stock which comprises admixing said charge stock with at least one organo-metallic compound selected from the group consisting of hexacarbonyls and pentacarbonyls of molybdenum, tungsten, iron, nickel and cobalt, heating the resulting mixture in a non-reducing atmosphere at a temperature less than about 310 C. and for a time sufficient to decompose said organo-metallic compound, thereafter adding hydrogen to the resulting colloidal suspension and reacting the mixture thus formed at a temperature in excess of about 225 C. and at a pressure greater than about 500 pounds per square inch gauge, and recovering a hydrorefined liquid product.
  • organo-metallic compound selected from the group consisting of hexacarbonyls and pentacarbonyls of molybdenum, tungsten, iron, nickel and cobalt
  • organo-metallic compound comprises molybdenum hexacarbonyl.
  • a process for hydrorefining a petroleum crude oil containing pentane-insoluble asphaltenes which comprises admixing said crude oil with at least one organo-metallic compound selected from the group consisting of hexacarbonyls and pentacarbonyls of molybdenum, tungsten, iron, nickel and cobalt, heating the resulting mixture in a non-reducing atmosphere at a temperature less than about 310 C. for a time sufficient to decompose said organometallic compound, thereafter adding hydrogen to the resulting colloidal suspension and reacting the mixture thus formed at a temperature in excess of about 225 C. and at a pressure greater than about 500 pounds per square inch gauge, and recovering said crude oil substantially free from pentane-insoluble asphaltenes.
  • organo-metallic compound selected from the group consisting of hexacarbonyls and pentacarbonyls of molybdenum, tungsten, iron, nickel and cobalt
  • organo-metallic compound comprises molybdenum hexacarbonyl.
  • organo-metallic compound comprises molybdenum hexacarbonyl and nickel formate.
  • a process for hydrorefining a petroleum crude oil containing pentane-insoluble asphaltenes which comprises admixing said crude oil with molybdenum hexacarbonyl, heating the resulting mixture at a temperature less than about 310 C. in a non-reducing atmosphere and for a time suflicient to decompose said molybdenum hexacarbonyl, thereafter adding hydrogen to the resulting colloidal suspension and reacting the mixture thus formed, in the substantial absence of carbon monoxide, at a temperature within the range of from about 225 C. to about 500 C. and at a pressure of from about 500 to about 500 pounds per square inch gauge, and recovering said crude oil substantially free from pentane-insoluble asphaltenes.

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Description

United States Patent 3,173,860 HYDROREFINING 53F CRUDE OIL AND CATALYST T EiEREFQR John G. Gatsis, Chicago, BL, assignor to Universal Gil Products Company, Des Plaines, EL, a corporation of Delaware N0 Brawirw. Filed Dec. 2%, 1961, Ser. No. 10fi2 9 Claims. (Cl. 208-264) The present invention relates to a novel, method for preparing a catalyst particularly adaptable for utilization in the hydro-refining of petroleum crude oils, heavy vacuum gas oils, heavy cycle stocks, etc. More specifically, the present invention involves a process for the hydrorefining of heavy hydrocarbon charge stocks to effect the removal of nitrogen and sulfur therefrom, and aitords unexpected advantages when employed for the removal of metals and/or to convert the pentane-insoluble fraction thereof into useful pentane-soluble hydrocarbon oils.
Crude petroleum oil, and the heavier hydrocarbon fractions and/ or distiliates obtained therefrom, generally contain nitrogenous and sulfurous compounds in large quantities. In addition, crude oil and heavier hydrocarbon fractions contain quantities of metallic contaminants which exert detrimental effects upon the catalyst utilized in various processes to which the crude oil or heavy hydrocarbon fraction is ultimately subjected. The most common metallic contaminant are nickel and vanadium, although other metals including iron, copper, etc., are often present. These metals may occur in a variety of forms: they may exist as metal oxides or as sulfides, introduced into the crude oil as metallic scale or particles; in the form of soluble salts of such metals; usually, how ever, they exist in the form of organo-metallic compounds such as metal porphyrins and the derivatives thereof.
Although the metallic contaminants existing as oxide or sulfide scale may be removed, at least in part, by a relatively simple filtering technique, and the water-soluble salts are at least in part removable by washing and subsequent dehydration, a much more severe treatment is generally required to remove the organo-metallic compounds, and to the degree required in order that the resulting crude oil or heavy hydrocarbon fraction is suitable for further processing. In addition to the organernetallic compounds, including metal porphyrins, crude oils contain greater quantities of sulfurous and nitrogenous compounds than are found in li hter hydrocarbon fractions such as gasoline, kerosene, light gas oil, etc. For example, a Wyoming sour crude, having a gravity of 23.2" API at 60 F., contains about 2.8% by weight of sulfur and about 2700 ppm. of total nitrogen. The nitrogenous and sulfurous compounds are converted, up on being subjected to a treating process, into hydrocarbons, ammonia, and hydrogen sulfide, the latter being readily removed from the system in a gaseous phase. Reduction in the concentration of the metallic contaminants is not as easily achieved, and to the extent that the crude oil or heavy hydrocarbon charge stock becomes suitable for further processing. Notwithstanding that the concentration of these compounds, such as metal porphyrins, is relatively small, for example, less than about 10 p.p.m., calculated as the elemental metal, subsequent processing techniques will be adversely aifccted thereby. For example, when a hydrocarbon charge stock containing metals in excess of about 3.0 p.p.m., is subjected to a cracking process for the purpose of producing lowerboiling components, the metals become deposited upon the catalyst employed, steadily increasing in quantity until such time as the composition of the catalytic composite is changed to the extent that undesirable results are obtained. That is to say, the composition of the catalytic composite, which is closely controlled with respect to the "ice nature of the charge stool; being processed and to the desired product quality and quantity, is changed considerably as the result of the deposition of the metallic contaminants onto the catalyst, the changed composite resulting in changed catalytic characteristics. Such an effect is undesirable with respect to the cracking process, since the deposition of metallic contaminants upon the catalyst tends to result in a lesser quantity of valuable liquid product, and large amounts of hydrogen and coke, the latter producing relatively rapid catalyst deactivation. The presence of organic metal compounds, including metal porphyrins, affects deleteriously other processes including catalytic reforming, isomerization, hydrodeallrylation, etc.
In addition to the foregoing described contaminating influences, crude oils and other heavier hydrocarbon fractions, generally contain large quantities of pentane-insoluble material. For example, the Wyoming sour crude consists of about 8.37% by weight of pentane-insoluble asphaltenes which are hydrocarbonaceous compounds considered as coke-precursors having the tendency to become immediately deposited within the reaction zone and onto the catalytic composite employed in the form of a gummy hydrocarbonaceous residue. This constitutes a large loss of charge stock; it is economically desirable to convert such asphaltcnes into useful hydrocarbon oil fractions.
The object of the present invention is to provide a much more efficient process for hydrorefining heavier hydrocarbonaceous material, and particularly petroleum crude oils, utilizing a catalyst prepared in a particular manner. As above set forth, metals are generally removed from the charge stock by deposition of the same on the catalyst employed. This greatly increases the amount of catalyst in a very short time, and precludes the use of a fixed-bed catalyst system as employed in practicing present-day methods. Slurry processes, employing catalytically active metals deposited upon silica and/or alumina, are extremely erosive, and make plant maintenance ditficult and expensive. The present invention teaches the preparation of a collodially dispersed, unsupported catalyst useful in a slurry process, and which will not effect extensive erosion 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 foregoing contaminants. The process of the present invention is particularly advantageous in eifecting the removal of the organic metal compounds without significant product yield loss, while simultaneously converting pentane-insoluble material into pentane-soluble liquid hydrocarbons.
In a broad embodiment, the present invention relates ,to a hydrorefim'ng catalyst which comprises at least one decomposed organza-metallic compound of the metals of Group VI-B, having an atomic number greater than 24, and the Iron-group.
Another broad embodiment of the present invention involves a method of preparing a hydrorefining catalyst which comprises forming a hydrocarbon solution of at least one organo-metallic compound of the metals of Group VI-B, having an atomic number greater than 24, and the Iron-group, land decomposing said organo-metallic compound in said hydrocarbon.
A more limited embodiment of the present invention affords a process for hydroreiining a hydrocarbon charge stock which comprises admixing said charge stock with at least one organo-metallic compound of the metals of Group VI-B, having an atomic number greater than 24,
and the Iron-group, heating the resulting mixture at a temperature less than about 310 C. and for a time sufiicient to decompose said organo-metallic compound, reacting the resulting colloidal suspension with hydrogen at a temperature in excess of about 225 C. and at a pressure of carbon monoxide, at a temperature within the range of from about 225 C. to about 500 C. and at a pressure of from about 500 to about 5000 pounds per square inch gauge, and recovering said crude oil substantially free from pentane-insoluble asphaltenes.
From the foregoing embodiments, it is readily ascertained that the method of the present invention involves the preparation of a catalyst utilizing metals selected from Group VI-B and the Iron-group of the Periodic Table. The catalyst, prepared in accordance with the method of the present invention, may comprise one or more metals from the group of molybdenum, tungsten, iron, nickel and cob-alt. It is noted that the metal selected from Group VI-B, namely molybdenum and/or tungsten, has an atomic number greater than 24. I have found that organic chromium complexes, upon decomposition, do not yield acceptable results, particularly with respect to the conversion of the pentane-insoluble material, and the destructive removal of the organo-metals such as nickel and/ or vanadium porphyrins. The catalyst is prepared by initially dissolving an organic complex of the selected metal, or metals, in the hydrocarbon charge stock containing the pentane-insoluble fraction which is to be converted into soluble hydrocarbons. The quantity of the organo-metallic compound employed is such that the colloidal suspension, or dispersion, which results when the organo-metallic compound is decomposed within the hydrocarbon charge stock, comprises from about 1.0% to about 10.0% by weight, calculated as the elemental metal. Suitable oragno-metallic compounds include molybdenum hexacarbonyl, tungsten hexacarbonyl, iron pentacarbonyl,
molybdenum hexacarbonyl in combination with nickel formate, tungsten hexacarbonyl in combination with iron carbonyl, various cobalt complexes, etc.
The process is effected, as hereinabove set forth, by initially dissolving the desired quantity of the organometallic compound, such as molybdenum hexacarbonyl, in the hydrocarbon charge stock. The resulting mixture is then heated, preferably in a non-reducing atmosphere,
particularly in the absence of free hydrogen, at a tempera ture less than about 310 C. and for a time sufficient to effect the decomposition of the organo-metallic compound, thereby resulting in a colloidal suspension, or dispersion, of the metallic component Within the hydrocarbon charge stock. As hereinafter set forth, the presence of free hydrogen during the decomposition of the organometallic compound has a tendency to affect detrimentally the activity of the catalyst with respect to the conversion of the pentane-insoluble fraction as well as the removal of metals. The colloidal dispersion is then passed into a suitable reaction zone at a temperature within the range of from about 225 C. to about 500 C. under a hydrogen pressure within the range of about 500 to about 5000 pounds per square inch gauge. In order to maintain the catalyst in its decomposed form, either as the metal or as a lower oxide thereof, it is necessary that the reaction zone be maintained substantially completely free from carbon monoxide. Following the decomposition of the molybdenum hexacarbonyl, some carbon monoxide will be present in the gaseous phase. This is readily removed upon venting prior to passing the mixture into the reaction zone. Where some of the carbon monoxide is dissolved in the liquid phase, it is preferred to remove the same by suitable stripping means. The process may be conducted in a batch-type procedure or in an enclosed vessel through which the colloidal suspension is passed; when efiected in a continuous manner, the process may be conducted in either upward flow or downflow. The normally liquid hydrocarbons are separated from the total reaction zone effiuentby'any suitable means, for example, through the use of a centrifuge, the resulting catalyst sludge being converted back to the oragno-metallic compound by any well-known'chemical means. The ammonia and hydrogen sulfide, resulting from the destructive conversion of sulfurous and nitrogenous compounds contained within the hydrocarbon charge stock, are removed, along with any light paraffinic hydrocarbons including methane, ethane and propane, in a gaseous phase.
Although the process of the present invention is conducted in the presence of hydrogen, the decomposition of the organo-metallic compound, such as molybdenum hexacarbonyl, is effected in the absence thereof. If present, hydrogen will react with the carbon monoxide, resulting in the formation of water, methane and carbon. It is further preferred that the decomposition to form the colloidal suspension be conducted in substantial absence of other well-known reducing agents. Depending upon the particular organo-metallic compound selected at the catalyst source, the dispersed material will be the elemental metal or a lower oxide form thereof. In any event, it is understood that the stated concentrations are computed on the basis of the elemental metal. The decomposiion of the oragno-metallic compound is conducted at a temperature less than about 310 C. in order to avoid initial cracking of the petroleum crude oil prior to effecting complete decomposition.
The following example is given to illustrate the process of the present invention and the effectiveness thereof in removing nickel and vanadium from the petroleum crude oil, and in converting pentane-insoluble asphaltenes while simultaneously effecting the conversion of sulfurous and nitrogenous compounds into sulfur and nitrogen-free hy= drocarbons. It is not intended that the present invention be unduly limited to the catalyst, charge stock, and/or operating conditions employed within the example. Spectrographic emission was employed to analyze the product effluent for the concentration of metals remaining.
Example The crude oil employed to illustrate the benefits afforded through the utilization of the present invention, was a Wyoming sour crude oil having a gravity of 232 API at 60 F, and containing 2.8% by weight of sulfur, approximately 2700 ppm. of nitrogen, 18 ppm. of nickel and 71 ppm. of vanadium as metal porphyrins, computed as the elemental metal. In addition, the sour crude consisted of 8.37% by weight of pentane-insoluble asphaltenes. As hereinafter indicated, the process of the present invention efiects the conversion of a significant proportion of such asphaltenes, and to the degree that the same no longer exert a detrimental effect upon further processing. I
The colloidally dispersed catalysts were prepared by decomposing the indicated organo-metallic compounds within the sour crude oil, thereafter subjecting the mixture to conversion in a rotating autoclave maintained at about 400 C., at an imposed hydrogen pressure of about 200 atmospheres. Each of the colloidal suspensions remained in the autoclave at the foregoing conditions for a period of from about 4 to about 8 hours.
Molybdenum hexacarbonyl, in an amount of 23.3 grams was admixed with 200 grams of the Wyoming sour crude, the mixture being charged to the rotating autoclave and heated to a temperature of 250 C. for a period of 3 hours. After venting to remove carbon monoxide, the autoclave was pressured to atmospheres with hydrogen, and then heated to a temperature of 400 C. for a period of about 8 hours, the final pressure being about 200 atmospheres. The gravity, API at 60 F., of the resulting normally liquid product effluent was 40.], indicating a substantial degree of conversion to lower-boiling hydrocarbon products. The liquid product indicated only 7.1 ppm. of nitrogen, about 0.02% by weight of sulfur, about 0.10% by weight of pentane-insoluble asphaltenes, less than about 0.02 ppm. of nickel and less than about 0.02 ppm. of vanadium.
When utilizing 23.3 grams of molybdenum hexacarbonyl, decomposed in situ, in the presence of hydro gen, the final liquid product was found to contain 347 -p.p.m. of nitrogen compared to 7.1 ppm. of nitrogen as hereinabove set forth.
A mixture of 23.3 grams of molybdenum hexacarbonyl, 2.5 grams of nickel formats and 200 grams of the Wyoming sour crude, initially heated to a temperature of 250 C. for a period of 4 hours, was placed in the rotating autoclave under a pressure of 100 atmospheres of hydrogen; upon being heated to a temperature of 400 C., the pressure increased to a level of about 200 atmospheres. These conditions were maintained for a period of 8 hours, and the resulting normally liquid product etlluent indicated 124 p.p.m. of nitrogen, 0.02% by weight of sulfur, less than 0.1% by weight of pentane-insoluble asphaltenes, less than 0.04 ppm. of nickel and less than 0.04 ppm. of Vanadium.
The foregoing specification and example clearly illustrate the advantages afiorded the hydroreiining of petroleum crude oils through the utilization of the method of the present invention. It is of particular interest to note that the concentration of nickel and vanadium, existing as organo-metallic complexes, as well as pentane-insoluble asphaltenes, was decreased to a level permitting subsequent utilization of the crude oil, either for further processing or distillation, and further that at least a portion of the crude oil was converted into lower-boiling hydrocarbon products.
I claim as my invention:
1. A process for hydrorefining a hydrocarbon charge stock which comprises admixing said charge stock with at least one organo-metallic compound selected from the group consisting of hexacarbonyls and pentacarbonyls of molybdenum, tungsten, iron, nickel and cobalt, heating the resulting mixture in a non-reducing atmosphere at a temperature less than about 310 C. and for a time sufficient to decompose said organo-metallic compound, thereafter adding hydrogen to the resulting colloidal suspension and reacting the mixture thus formed at a temperature in excess of about 225 C. and at a pressure greater than about 500 pounds per square inch gauge, and recovering a hydrorefined liquid product.
2. The process of claim 1 further characterized in that the mixture of said charge stock and decomposed organemetallic compound is reacted with hydrogen at a temperature within the range of from about 225 C. to about 500 C. and under a pressure of from about 500 pounds per square inch gauge.
3. The process of claim 1 further characterized in that said organo-metallic compound comprises molybdenum hexacarbonyl.
4. The process of claim 1 further characterized in that said organo-metallic compound is a hexacarbonyl.
5. A process for hydrorefining a petroleum crude oil containing pentane-insoluble asphaltenes, which comprises admixing said crude oil with at least one organo-metallic compound selected from the group consisting of hexacarbonyls and pentacarbonyls of molybdenum, tungsten, iron, nickel and cobalt, heating the resulting mixture in a non-reducing atmosphere at a temperature less than about 310 C. for a time sufficient to decompose said organometallic compound, thereafter adding hydrogen to the resulting colloidal suspension and reacting the mixture thus formed at a temperature in excess of about 225 C. and at a pressure greater than about 500 pounds per square inch gauge, and recovering said crude oil substantially free from pentane-insoluble asphaltenes.
6. The process of claim 5 further characterized in that the suspension of said crude oil and decomposed organometallic compound is reacted with hydrogen in the sub stantial absence of carbon monoxide.
7. The process of claim 5 further characterized in that said organo-metallic compound comprises molybdenum hexacarbonyl.
8. The process of claim 5 further characterized in that said organo-metallic compound comprises molybdenum hexacarbonyl and nickel formate.
9. A process for hydrorefining a petroleum crude oil containing pentane-insoluble asphaltenes, which comprises admixing said crude oil with molybdenum hexacarbonyl, heating the resulting mixture at a temperature less than about 310 C. in a non-reducing atmosphere and for a time suflicient to decompose said molybdenum hexacarbonyl, thereafter adding hydrogen to the resulting colloidal suspension and reacting the mixture thus formed, in the substantial absence of carbon monoxide, at a temperature within the range of from about 225 C. to about 500 C. and at a pressure of from about 500 to about 500 pounds per square inch gauge, and recovering said crude oil substantially free from pentane-insoluble asphaltenes.
References Cited by the Examiner UNITED STATES PATENTS 2,781,410 2/57 Ziegler et a1. 260-68315 2,999,075 9/61 Pruett 252-472 3,006,844 10/61 Limido 208217 3,050,562 8/62 Klopfer 252-431 3,053,756 9/62 Nottes et al. 252431 5 ALPHONSO D. SULLIVAN, Primary Examiner.
PAUL M. COUGHLAN, 1a., Examiner.

Claims (1)

1. A PROCESS FOR HYDROREFINING A HYDROCARBON CHARGE STOCK WHICH COMPRISES ADMIXING SAID CHARGE STOCK WITH AT LEAST ONE ORGANO-METALLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF HEXACARBONYLS AND PENTACARBONYLS OF MOLYBDENUM, TUNGSTEN, IRON, NICKEL AND COBALT, HEATING THE RESULTING MIXTURE IN A NON-REDUCING ATMOSPHERE AT A TEMPERATURE LESS THAN ABOUT 310*C. AND FOR A TIME SUFFICIENT TO DECOMPOSE SAID ORGANO-METALLIC COMPOUND, THEREAFTER ADDING HYDROGEN TO THE RESULTING COLLOIDAL SUSPENSION AND REACTING THE MIXTURE THUS FORMED AT A TEMPERATURE IN EXCESS OF ABOUT 225*C. AND AT A PRESSURE GREATER THAN ABOUT 500 POUNDS PER SQUARE INCH GAUGE, AND RECOVERING A HYDROREFINED LIQUID PRODUCT.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3240718A (en) * 1963-11-13 1966-03-15 Universal Oil Prod Co Regeneration and recovery of catalyst from sludge
US5171727A (en) * 1991-08-26 1992-12-15 Uop Method of preparing a catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks

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US2781410A (en) * 1953-04-04 1957-02-12 Ziegler Polymerization of ethylene in the presence of an aluminum trialkyl catalyst
US2999075A (en) * 1955-05-26 1961-09-05 Union Carbide Corp Process for producing nickel and cobalt hydrogenation catalysts
US3006844A (en) * 1957-02-15 1961-10-31 Inst Francais Du Petrole Catalytic hydrogenation of hydrocarbons in the liquid phase
US3050562A (en) * 1961-06-01 1962-08-21 Ethyl Corp Oxo synthesis and catalysts therefor
US3053756A (en) * 1958-07-03 1962-09-11 Basf Ag Refining of industrial hydrocarbon mixtures

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Publication number Priority date Publication date Assignee Title
US2781410A (en) * 1953-04-04 1957-02-12 Ziegler Polymerization of ethylene in the presence of an aluminum trialkyl catalyst
US2999075A (en) * 1955-05-26 1961-09-05 Union Carbide Corp Process for producing nickel and cobalt hydrogenation catalysts
US3006844A (en) * 1957-02-15 1961-10-31 Inst Francais Du Petrole Catalytic hydrogenation of hydrocarbons in the liquid phase
US3053756A (en) * 1958-07-03 1962-09-11 Basf Ag Refining of industrial hydrocarbon mixtures
US3050562A (en) * 1961-06-01 1962-08-21 Ethyl Corp Oxo synthesis and catalysts therefor

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3240718A (en) * 1963-11-13 1966-03-15 Universal Oil Prod Co Regeneration and recovery of catalyst from sludge
US5171727A (en) * 1991-08-26 1992-12-15 Uop Method of preparing a catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks
US5288681A (en) * 1991-08-26 1994-02-22 Uop Catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks

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