US3785958A - Desulfurization and conversion of black oils - Google Patents

Desulfurization and conversion of black oils Download PDF

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Publication number
US3785958A
US3785958A US00287308A US3785958DA US3785958A US 3785958 A US3785958 A US 3785958A US 00287308 A US00287308 A US 00287308A US 3785958D A US3785958D A US 3785958DA US 3785958 A US3785958 A US 3785958A
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weight
solvent
hydrogen
ash
sulfide
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W Gleim
J Gatsis
Hara M O
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Honeywell UOP LLC
Universal Oil Products Co
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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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0454—Solvent desasphalting
    • C10G67/0463—The hydrotreatment being a hydrorefining

Definitions

  • the invention herein described is intended to be applied to the hydrogenative conversion and desulfurization of heavy, asphaltene-containing hydrocarbonaceous charge stocks, especially those contaminated by the inclusion of finely-divided particulate ash. More specifically, the present invention is directed towards a combination process for the continuous conversion of atmospheric tower bottoms products, vacuum tower bottoms products (vacuum residuum), crude oil residuum, topped crude oils, shale oils, coal oils, and especially oils extracted from tar sands, etc., all of which are commonly referred to in the art as black oils, and which contain an appreciable quantity of asphaltenic material.
  • the present combination process affords a high degree of asphaltene conversion into hydrocarbonsoluble products, while simultaneously effecting substantial conversion of sulfurous and nitrogenous compounds to reduce sulfur and nitrogen concentrations.
  • Crude petroleum oils particularly vacuum residuum, shale oil and the heavy oils extracted from tar sands, the latter sometimes referred to a syncrude, contain high molecular weight sulfurous compounds in exceedingly large quantities, being in excess of 1.0% by weight, and often exceeding 3.0% by Weight.
  • these black oils contain excessive quantities of nitrogenous compounds, high molecular weight organometallic complexes principally comprising nickel and vanadium, and asphaltenic material.
  • the ash consists principally of aluminosilicates having nominal diameters in the range of about 1.0 to about 10.0 microns. Such iinelydivided particles have extremely sharp edges and are, therefore, excessively abrasive. Since its erosive tendencies cannot be tolerated, the ash must necessarily be removed prior to subsequent processing. Furthermore the ash will plug, in a very short time, any fixed-bed catalyst reactor.
  • black oils illustratiae of those to which the present invention is applicable, are a vacuum tower bottoms product, having a gravity of 7.1 API and containing 4.1% by Weight of sulfur and 23.7% by weight of asphaltenes; a vacuum residuum having a gravity of 8.8 API and containing about 5.0% by weight of asphaltic material; a shale oil having a gravity of 19.6 API, and containing 0.6% ash; a coal oil having a gravity of 10.1 API, and containing 0.5% ash; and, a tar sands oil having a gravity of about 6.9a API, and containing 10.6% by weight of insoluble asphaltics, 5.23% by weight of sulfur and about 1.8% by weight of ash.
  • the present combination process atords the conversion of the greater proportion of such material, heretofore having been thought to be virtually precluded.
  • the principal diiculty resides in the lack of an operating technique which aords fixed-bed catlaytic 4composites the necessary degree of sulfur stability, While simultaneously producing lowerboiling products from the hydrocarbon-insoluble asphaltic material.
  • Asphaltic material consists primarily of high molecular weight, non-distillable coke precursors, insoluble in light hydrocarbons and which, at the conditions required to obtain acceptable desulfurization, agglomerate and polymerize to the extent that the catalytically active surfaces and sites of the catalyst are shielded from the material being processed.
  • ashcontaining black oils create additional diiculties when processing is attempted in accordance with present-day techniques.
  • the present invention involves a slurry-type process utilizing an unsupported catalytic agent of at least one metal com ponent selected from the group consisting of the metals from Groups IV, V, and VI of the Periodic Table.
  • the asphaltic material and catalyst are thus maintained in a dispersed state within a principally liquid phase rich in hydrogen. Intimate contact is thus aforded between the asphaltic ⁇ material and the catalyst, thereby effecting reaction with hydrogen; the liquid phase is itself dispersed in a hydrogen-rich gas phase so that the dissolved hydrogen is continuously replenished.
  • a principal object of the present invention is to provide a more efficient process for the hydrogenative conversion (hydroreining) of heavy hydrocarbonaceous material containing insoluble asphaltenes and particulate ash.
  • Term hydroretining connotes the catalytic treatment, in an atmosphere of hydrogen, of a hydrocarbon fraction and/or distillate for the purpose of eliminating, or reducing, the concentration of the various contaminating inliuences hereinabove set forth, accompanied by hydrogenation and significant conversion into lower-boiling hydrocarbon products.
  • the present process affords greater yields of normally liquid hydrocarbon products which are more suitable for subsequent processing, without experiencing the difiiculties otherwise resulting from the presence of the foregoing contaminating inuences.
  • our invention encompasses a process for the conversion of a sulfurous, ashand asphaltene-containing hydrocarbonaceous charge stock, which process ycomprises the steps of: (a) deashing said charge stock, in contact with a selective solvent, in a solvent deashing zone to provide a solvent-lean, ash-containing phase and a solvent-rich, asphaltene-containing phase; (b) reacting at least a portion of said asphaltenecontaining phase with hydrogen, in a first reaction zone, in contact with an unsupported sulfide of a metal from Groups IV-B, V-B and VI-B; (c) separating the resulting first reaction zone efuent to recover a metal-containing sludge and a hydrocarbon phase; (d) reacting at least a portion of said hydrocarbon phase with hydrogen, in a second reaction zone, in contact with a catalytic composite of a porous carrier material and at least one metal cornponent from the metals of Groups VI-B and VIH;
  • reaction with hydrogen in the first and second reaction zones is effected in the presence of about 2.0% to about 30.0% (on a mole basis) of hydrogen sulfide.
  • the unsupported metallic sulfide is admixed with said charge stock in an amount from about 1.0% to about 30.0% by weight.
  • the present combination process makes use of solvent deashing, in a solvent extraction zone, to precipitate the ash in a solvent-lean bottoms phase.
  • the solvent-rich phase containing virgin asphaltenic compounds, is withdrawn as a solvent-rich phase and reacted in part with hydrogen in contact with an unsupported catalytic component.
  • the remainder is subjected to additional reaction with hydrogen in contact with a fixed-bed catalytic composite of a porous carrier material and at least one metallic component from the metals of Groups VI-B and VIII of the Periodic Table.
  • the ashcontaining, asphaltenic charge stock is introduced into an upper portion of a solvent extraction zone, wherein it countercurrently contacts a suitable selective solvent introduced into a lower portion of the extraction zone.
  • the extraction zone will function at a temperature in the range of about 50 F. to about 500 F., and preferably from about F. to about 300 F.; the pressure will be maintained Within the range of about 100 to about 1,000 p.s.i.g., and preferably from about 200 to about 600 p.s.i.g.
  • the precise operating conditions will generally depend upon the physical characteristics of thel charge stock as well as the selective solvent, in order to recover the greater proportion of the asphaltenes in the solventrich phase.
  • Suitable solvents include those hereinbefore described with respect to prior art deasphalting techniques.
  • the solvent will be selected from the group of light hydrocarbons such as ethane, methane, propane, butane, isobutane, pentane, isopentane, neopentane, hexane, isohexane, heptane, isoheptane, the mono-olefinic counterparts thereof, various mixtures, etc.
  • the solvent may be a normally liquid naphtha fraction containing hydrocarbons having from about 5 to about 14 carbon atoms per molecule, preferably a naphtha fraction having an end boiling point below about 200 F.
  • the asphaltene-containing, solvent-rich normally liquid phase is introduced into a suitable solvent recovery system, the design and techniques of which are thoroughly described in the prior art.
  • the catalytic component is selected from titanium sulfide, vanadium sulfide, chromium sulfide, zirconium sulfide, niobium sulfide, molybdenum sulfide, hafnium sulfide, tantalum sulfide and tungsten sulfide.
  • tungsten sulfide, titanium sulfide and vanadium sulfide are preferred, with non-stoichiometric vanadium sulfide apparently producing the most advantageous result.
  • Non-stoichiometric vanadium sulfide, the method of its preparation and its use in the conversion of asphaltenic material is detailed in U.S. Pat. No. 3,558,474 (Class 208-108).
  • the process may be elected as a batch-type operation, or in a continuous manner in either upward flow, or downward iiow.
  • a preferred technique utilizes an elongated reaction chamber through which the reactants are passed in upward flow.
  • the normally liquid hydrocarbons are separated from the total reaction zone product efiiuent by any suitable means, the remaining metal-containing sludge being treated as hereinafter set forth.
  • the sludge is a viscous fluid containing the catalytic component and substantially all the metallic components originally present in the black oil feed stock-Le.
  • the hydrocarbon product contains less than 10.0 p.p.m. by weight of metallic contaminants.
  • the sludge contains some soluble hydrocarbons, other heavy carbonaceous material and the catalytically active agent.
  • the metal-containing sludge is combined with fresh hydrocarbon charge stock. :In order to prevent a build-up of coke, unconverted -asphaltenic material and other carbonaceous residue, a controlled portion of the sludge will be withdrawn from the process and sent to a suitable metal recovery system.
  • the withdrawn sludge may be subjected to the regeneration technique described in U.S. Pat. No. 3,645,912 (Class 252-411).
  • Suitable metallic components are those selected from the group consisting of metals of Groups VI-B and VIII of the Periodic Table, and include one or more metallic components from the group of molybdenum, tungsten, chromium, iron, cobalt, nickel, platinum, palladium, iridium, osmium, rhodium, ruthenium, and mixtures thereof.
  • concentration of the active metallic component, or components is primarily dependent upon the particular metal as well as the characteristics of the charge stocks.
  • the metallic components of Groups VI-B are preferably present in an amount within the range of about 4.0% to about 35.0% by weight, the iron-group metals in an amount within the range of about 0.2% to about 10.0% by weight, Whereas the platinum-group metals are preferably present in an amount of about 0.1% to about 5.0% by weight, all of which are calculated as if the components existed within the finished catalytic composite as the elemental metal.
  • the operating conditions imposed upon the fixed-bed reaction zone are primarily dependent upon the physical and chemical properties of the charge as Well as the desired end result. However, these conditions will generally include a maximum catalyst bed temperature in the range of about 600 F. to about 900 F.
  • Other operating variables include a pressure from about 500 to about 5,000 p.s.i.g., a liquid hourly space velocity (defined as volumes of fresh feed charge stock per hour, per volume of catalyst disclosed within the reaction zone) of about 0.1 to about 5.0 and a hydrogen concentration of about 1,000 to about 50,000 s.c.f./bbl.
  • a liquid hourly space velocity defined as volumes of fresh feed charge stock per hour, per volume of catalyst disclosed within the reaction zone
  • Judicious operating techniques generally dictate that the temperature gradient be limited to a maximum of about F., and, in order to insure that the temperature does not exceed the maximum allowed, conventional quench streams, either normally liquid or normally gaseous may be introduced into one or more intermediate loci of the catalyst bed. A portion of the normally liquid product eliiuent from the fixed-bed catalytic reaction zone may be recycled as a diluent to combine with the fresh feed charge stock. In this situation, the combined liquid feed ratio to the catalytic reaction zone will generally be in the range of about 1.1 to about 6.0.
  • reactor 8 In order to prevent a build-up of metallic components resulting from the hydrogenative destruction of the metal porphyrins in the charge stock, from about 5.0% to about 20.0% by weight of the metal-containing sludge will continue through line 11 to a metals recovery system.
  • the asphaltene-free product from the catalyst recovery zone 10 passes by Way of line 12, in admixture with a hydrogen-rich recycle gas from line 13 into fixedbed reactor 14.
  • Reactor 14 contains a catalytic composite of 2.0% by weight of nickel, 16.0% by weight of molybdenum, 8.8% by weight of silica and 73.2% by weight of alumina.
  • Reactor 14 is maintained at a pressure of 2,000 p.s.i.g. and a maximum catalyst bed temperature of about 750 F., the reactants traverse the catalyst bed at a liquid hourly space velocity of about 1.0.
  • the product effluent in line 15, following utilization as a heat-exchange medium and further cooling to a temperature of about 80 F., is introduced into cold separator 16.
  • the deasphalted oil was processed over a fixed-bed of a catalytic composite of 64.7% by weight alumina, 8.8% by weight of silica, 16.0% by weight of molybdenum and 2.0% by weight of nickel.
  • the operating conditions ineluded a liquid hourly space Velocity of about 1.0, a maximum catalyst bed temperature of 800 F., a pressure of about 2,500 p.s.i.g., and a hydrogen concentration of about 10,000 s.c.f./bbl.
  • Product analyses indicated a gravity of about 22.9 API, a sulfur concentration of about 0.25% by Weight and an asphaltene concentration of about 0.4% by weight.
  • Example II The tar sands oil charge stock was subjected to deashing utilizing n-heptane at a pressure of about 250i p.s.i.g. and a temperature of about 350 F.
  • the solvent to charge volumetric ratio was about 3.0 to 1.0.
  • the resulting deashed product had a gravity of about 8.5 API, contained 4.94% by weight of sulfur and about 9.0% by Weight of insoluble asphaltenes.
  • the normally liquid product efiiuent from the slurry operation was admixed with about 10,000 s.c.f./bbl. of hydrogen and introduced into a fixed-bed reaction zone maintained at a pressure of about 2,000 p.s.i.g. and a maximum catalyst bed temperature of about 750 F.
  • the catalyst was a composite of 6.97% by weight of silica, 8.18% by weight of boron phosphate, 1.89% by weight of nickel, 16.0% by weight of molybdenum and 66.96% by weight of alumina, the reactants traversing the catalyst bed at a liquid hourly space velocity of about 1.0.
  • the pentane and heavier, normally liquid portion of the product effluent indicated a gravity of 24.9 API, an asphaltene concentration of nil and a sulfur concentration of only 0.03% by weight, a degree of desulfurization of asphaltic stocks, never achieved before at such economical liquid hourly space velocities.
  • a process for the conversion of a sulfurous, ashand asphaltene-containing hydrocarbonaceous charge stock which comprises the steps of:
  • catalytic composite comprises an alumina-silica carrier material and at least one metallic component from the metals of Groups VI-B and the iron-group.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
US00287308A 1972-09-08 1972-09-08 Desulfurization and conversion of black oils Expired - Lifetime US3785958A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920538A (en) * 1973-11-30 1975-11-18 Shell Oil Co Demetallation with nickel-vanadium on silica in a hydrocarbon conversion process
US4557823A (en) * 1984-06-22 1985-12-10 Phillips Petroleum Company Hydrofining process for hydrocarbon containing feed streams
US4582594A (en) * 1984-09-04 1986-04-15 Phillips Petroleum Company Hydrofining process for hydrocarbon containing feed streams
US4659453A (en) * 1986-02-05 1987-04-21 Phillips Petroleum Company Hydrovisbreaking of oils
US6511937B1 (en) 1999-10-12 2003-01-28 Exxonmobil Research And Engineering Company Combination slurry hydroconversion plus solvent deasphalting process for heavy oil upgrading wherein slurry catalyst is derived from solvent deasphalted rock

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58108084U (ja) * 1982-01-20 1983-07-22 トステム株式会社 サツシ開閉装置
US4564439A (en) * 1984-06-29 1986-01-14 Chevron Research Company Two-stage, close-coupled thermal catalytic hydroconversion process
CN1400997A (zh) * 2000-02-15 2003-03-05 埃克森美孚研究工程公司 重质原料通过溶剂脱沥青及其后的将得自溶剂脱沥青的沥青浆液加氢处理而改质的方法
RU2405026C1 (ru) * 2009-07-07 2010-11-27 Илья Александрович Данилов Способ обработки угля с высоким содержанием серы

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3558474A (en) * 1968-09-30 1971-01-26 Universal Oil Prod Co Slurry process for hydrorefining petroleum crude oil
US3525684A (en) * 1968-11-13 1970-08-25 Universal Oil Prod Co Catalyst and process for hydrorefining petroleum crude and residual oils

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920538A (en) * 1973-11-30 1975-11-18 Shell Oil Co Demetallation with nickel-vanadium on silica in a hydrocarbon conversion process
US4557823A (en) * 1984-06-22 1985-12-10 Phillips Petroleum Company Hydrofining process for hydrocarbon containing feed streams
US4582594A (en) * 1984-09-04 1986-04-15 Phillips Petroleum Company Hydrofining process for hydrocarbon containing feed streams
US4659453A (en) * 1986-02-05 1987-04-21 Phillips Petroleum Company Hydrovisbreaking of oils
US6511937B1 (en) 1999-10-12 2003-01-28 Exxonmobil Research And Engineering Company Combination slurry hydroconversion plus solvent deasphalting process for heavy oil upgrading wherein slurry catalyst is derived from solvent deasphalted rock

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DE2344251A1 (de) 1974-04-04
DE2344251C3 (de) 1980-01-31
FR2198990B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1976-10-01
CA997698A (en) 1976-09-28
DE2344251B2 (de) 1979-06-07
FR2198990A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1974-04-05
JPS5336843B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1978-10-05
GB1435350A (en) 1976-05-12
ZA736099B (en) 1974-09-25
JPS49108104A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1974-10-15
IT996146B (it) 1975-12-10
SU476752A3 (ru) 1975-07-05

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