US2892774A - Catalytic desulfurization of crude petroleum hydrocarbons - Google Patents

Catalytic desulfurization of crude petroleum hydrocarbons Download PDF

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US2892774A
US2892774A US332661A US33266153A US2892774A US 2892774 A US2892774 A US 2892774A US 332661 A US332661 A US 332661A US 33266153 A US33266153 A US 33266153A US 2892774 A US2892774 A US 2892774A
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hydrofining
fraction
liquid
sulfur
gaseous
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Porter Frederick Willi Bertram
Northcott Roy Purdy
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BP PLC
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BP PLC
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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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only

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  • This invention relates to the catalytic desulfurization of petroleum hydrocarbons by passing the hydrocarbons in admixture with hydrogen over a sulfur-resistant hydrogenation catalyst at elevated temperature and pressure such that organically-combined sulfur contained in the hydrocarbons is converted into hydrogen sulfide which may readily be removed from the treated hydrocarbons.
  • a sulfur-resistant hydrogenation catalyst at elevated temperature and pressure such that organically-combined sulfur contained in the hydrocarbons is converted into hydrogen sulfide which may readily be removed from the treated hydrocarbons.
  • Such a process may conveniently be called hydrofining.
  • a typical temperature for the practice of the hydrofining process is 780 F. and a typical pressure 1000 lb./sq. in.
  • Any sulfur-resistant hydrogenation catalyst may be used but particularly effective is a catalyst comprising the oxides of cobalt and molybdenum either as such or combined as cobalt molybdate, and preferably deposited on or incorporated with a support such, for example, as alumina.
  • the present invention is concerned with the application of the hydrofining process to petroleum feedstocks which under the normal conditions of the process are present in the reaction zone as a mixed gas/liquid phase. This condition applies particularly to the hydrofining of crude oil and crude oil residue.
  • the gas oil is mainly in the liquid phase with a space velocity of 1.3 v./v./hr., whereas at the high recycle rate, it is wholly in the vapor phase, with a space velocity of 7.3 v./v./hr. resulting in less sulfur removal for the gas oil fraction.
  • the kerosene is wholly in the vapor phase in both cases but at the low recycle rate, the sulfur content of the vaporized feed is 0.187% weight compared with 0.78% weight for the stocks which under the conditions necessary to bring 2,892,774 Patented June 30, 1959 about the reaction exist as a mixed gas/liquid phase, which results in greater overall desulfurization than is f at present possible.
  • a petroleum feedstock which under hydrofining conditions exists as a mixed gas/liquid phase is continuously separated into a gaseous fraction and a liquid fraction and the fractions passed continuously to separate hydrofining zones.
  • This method of operation enables the reaction conditions in the separate hydrofining zones to be adjusted to the optimum for both the gaseous and liquid fractions.
  • the space velocity may be varied by adjusting the size of the effective catalyst volume.
  • the process may advantageously be operated with the recycle gas flowing in series through the two reactors.
  • the latent heat required to convert part of the feedstock into vapor may be supplied by the heat of reaction in the liquid phase reactor by flowing the recycle gas through a vapor disengaging zone intermediate the two reaction zones and into which the feedstock is fed.
  • the preheated feedstock may be passed to a disengaging zone wherein it is contacted with the hot recycle gases from the liquid phase reaction zone, whereby it is separated into a gaseous fraction and a liquid fraction, the gaseous fraction being passed with the recycle gases to a hydrofining zone, the products from which, after cooling, are separated into a desulfurized liquid product and a hydrogen-rich gaseous product, while the liquid fraction is passed through the liquid phase reactor in counter-current to the recycle gases and is then let down to atmospheric pressure and passed to a distillation zone, or, after cooling, to storage.
  • the liquid fraction may be passed through the liquid phase reactor concurrently with the recycle gases, in which case the products leaving the reactor are passed to a hot separator operating at elevated pressure for the separation of the gases and vapors whereupon the liquid product is let down to atmospheric pressure as before.
  • the liquid fraction will contain any sodium and/ or vanadium contained in the crude petroleum or residue and although the quantities involved are small, they are sufiicient to cause a hydrofining catalyst of the cobalt molybdate type to lose activity, which loss in activity is not entirely regained on regeneration.
  • the liquid phase reaction zone may therefore advantageously be formed in two parts, one of which contains a substance, such, as bauxite, capable of removing vanadium and/or sodium from the liquid fraction, while the other contains the hydrofining catalyst.
  • bauxite in this way for avoiding deactivation of a hydrofining catalyst forms the subject of copending application No. 276,256, filed March 13, 1952, now U.S. Patent No. 2,769,758.
  • the crude petroleum or residue passes via line 10 to furnace 11 wherein it is heated so that its temperature on leaving the furnace is 780 F. for example. From the furnace, the oil passes to a disengaging chamber 12 wherein it is contacted at a pressure of 1000 lb./sq. in.,
  • the gaseous fraction from the chamber 12 passes overhead via line 14 into a vapor phase reactor 15 maintained, for example, at 750 F. and 1000 p.s.i. wherein it is contacted with a sulfur-resistant hydrogenation catalyst, for example of the mixed cobalt and molybdenum oxide type.
  • the products from the reactor 15 pass through a cooler 16 to a separator 17 from which a hydrogen-rich gas is taken overhead and passed to a vessel 18 for the removal of hydrogen sulfide after which the hydrogen-rich gasis recycled via line 19, make-up hydrogen.beingaddedvia line 20.
  • .Desulfurizedliquid product is removed via line 21 and is passed todistillation unit. or otherwise disposed. of.
  • the liquid fractionfrom the chamber .12 is passed ,to a two-stage reactor system comprising the reactors 22 and 23 in series, one of Which is filled with bauxite and the other with hydrofining catalyst, for example of the mixed cobalt and molybdenum oxide type, and .both maintained at an elevated pressure of, for example 1000 lb./sq. in.
  • Theliquid product may be .caused to flow downwardly through the reactors 22 and 23, asindicated by thefullline .24, in which case the reactor.22 contains bauxite and thereactor 23 hydrofining catalyst.
  • the liquid product passes from reactor 23 via line 25 to a hot separator 26 wherein it is letdownto atmospheric pressure, the gaseous products passing via line 27 to a hydrogen recovery unit and the liquid product passing via line 28 to a vacuum distillation unit, or after cooling, to storage.
  • the liquid product may be passed upwardly through the reactors 23 and 22 as indicated by broken line 29in which case thereactor 23 contains bauxite and the reactor 22 hydrofining catalyst.
  • the liquid product leaves reactor 22 via line 30 and passes to a hot separator31 maintained under reactor pressure from which gaseous products are removed via line 32, and the'liquid product via line 33, the liquid product passing to hot separator 34 wherein it is let down -to atmospheric pressure, gaseous products passing via line 35 to a hydrogen recovery unit and liquid products via line 36 to a vacuum distillation unit or, after cooling, to storage.
  • the recycle gases from line 19 are passed through heater 37 from which they pass via line 38 at a temperature of, :forexample, 780 F. into the reactor 23.
  • the recycle gases pass out of the reactor 22 via lines 39 and 13 into the chamber 12 whilein the case of the up-flow reaction system the recycle gases flow intoline 13 from line 32.
  • Example I A Kuwait crude oil was split into a liquid fraction comprising 50% weight on the crude and a gaseous fraction comprising a gasoline fraction to 150 C., a kerosene fraction 150-230 C. and a gas oil fraction 230-350 C.
  • the liquid fraction was passed to the liquid phase reaction zone under the following conditions.
  • the gaseous fraction was passed to the vapor phase I reaction zone under the following conditions.
  • Example 11 A Kuwaitresidue (53 percent volume on crude) was split into a liquid fraction comprising 80 percent weight on the residue and a gaseous fraction comprising 20 percent weight on the residue.
  • the liquid fraction was passed to the liquid phase reaction .zone under the following conditions:
  • the gaseous fraction was passed to the vapor phase reaction zone under the following conditions:
  • a process for the hydrofining of crude oils and residues thereof containing at least about 20% vaporizable constituents which comprises heating the feedstock to ,an elevated temperature at which-the feedstock is in the mixed gas/liquid phase, separating the heated feedstock into a gaseous fraction and a liquid fraction, passing the gaseous fraction toafirst hydrofining zone wherein it is contacted with a sulfur-resistant hydrogenation catalyst at elevated temperature and pressure such that the fraction is maintained substantially in the gaseous phase, passing the liquid fraction to a second hydrofining zone wherein it is contacted with a sulfur-resistant hydrogenationcatalyst' at elevated temperature and pressure such that the fraction is maintained substantially in the liquid phase, and recovering desulfurized liquid products from said hydrofining zones.
  • a process for the hydrofining of crude oils and residues thereof containing at least about 20% vaporizable constituents which comprises heating the feedstock to an elevated temperature at which the feedstock is in the mixed gas/liquid phase, passing the heated feedstock to a vapor disengaging zone, passing the liquid product from said vapor disengaging zone to a first hydrofining zone wherein it is contacted with a sulfur-resistant hydrogenation catalyst at elevated temperature and pressure such that it is maintained substantially in the liquid phase, passing the vaporous product from said vapor disengaging zone to a second hydrofining zone wherein it is contacted with a sulfur-resistant hydrogenation catalyst at elevated temperature and pressure such that it is maintained substantially in the vapor phase, passing a hydrogen-containing recycle gas first through said first hydrofining zone, then through said vapor disengaging zone, and

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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)
US332661A 1952-01-28 1953-01-22 Catalytic desulfurization of crude petroleum hydrocarbons Expired - Lifetime US2892774A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3179586A (en) * 1959-11-24 1965-04-20 Sinclair Research Inc Process for preparing heavy fuel oils
US3658681A (en) * 1970-02-24 1972-04-25 Texaco Inc Production of low sulfur fuel oil
US3893909A (en) * 1971-12-27 1975-07-08 Universal Oil Prod Co Fuel oil production by blending hydrodesulfurized vacuum gas oil and hydrodesulfurized deasphalted residuum
US4990242A (en) * 1989-06-14 1991-02-05 Exxon Research And Engineering Company Enhanced sulfur removal from fuels
US5389235A (en) * 1992-12-02 1995-02-14 Uop Catalytic reaction zone for sulfur contaminant sensitive catalyst

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2910433A (en) * 1954-09-23 1959-10-27 Hydrocarbon Research Inc Oil refining with hydrogen
US2951807A (en) * 1955-09-19 1960-09-06 Gulf Oil Corp Hydro-treating a blend of straight-run fuel oil and thermally cracked gasoline

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1827537A (en) * 1926-06-28 1931-10-13 Universal Oil Prod Co Desulphurization and purification of hydrocarbon oil
US1881534A (en) * 1929-08-31 1932-10-11 Standard Ig Co Process of refining hydrocarbon oils
US2025255A (en) * 1934-02-07 1935-12-24 Shell Dev Method of treating cracked oil distillates
US2042298A (en) * 1929-08-31 1936-05-26 Standard Ig Co Process for the purification and desulphurization of low boiling distillates
US2070295A (en) * 1933-09-15 1937-02-09 Universal Oil Prod Co Treatment of hydrocarbon oils
US2090007A (en) * 1928-09-26 1937-08-17 Texas Co Manufacture of motor fuel
US2371298A (en) * 1945-03-13 Treatment of hydrocarbon oils
US2516877A (en) * 1946-09-27 1950-08-01 Gulf Research Development Co Desulfurization of heavy petroleum hydrocarbons
US2516876A (en) * 1946-09-27 1950-08-01 Gulf Research Development Co Desulfurization of light petroleum hydrocarbons
US2574446A (en) * 1947-12-16 1951-11-06 Anglo Iranian Oil Co Ltd Catalytic desulfurization of gas oilkerosene mixtures
US2587987A (en) * 1949-05-10 1952-03-04 Gulf Oil Corp Selective hydrodesulfurization process
US2694671A (en) * 1950-09-01 1954-11-16 Standard Oil Dev Co Selective hydrogenation process
US2758060A (en) * 1951-01-15 1956-08-07 British Petroleum Co Removal of vanadium and/or sodium from petroleum by hydrogenation in the presence of bauxite

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2371298A (en) * 1945-03-13 Treatment of hydrocarbon oils
US1827537A (en) * 1926-06-28 1931-10-13 Universal Oil Prod Co Desulphurization and purification of hydrocarbon oil
US2090007A (en) * 1928-09-26 1937-08-17 Texas Co Manufacture of motor fuel
US2042298A (en) * 1929-08-31 1936-05-26 Standard Ig Co Process for the purification and desulphurization of low boiling distillates
US1881534A (en) * 1929-08-31 1932-10-11 Standard Ig Co Process of refining hydrocarbon oils
US2070295A (en) * 1933-09-15 1937-02-09 Universal Oil Prod Co Treatment of hydrocarbon oils
US2025255A (en) * 1934-02-07 1935-12-24 Shell Dev Method of treating cracked oil distillates
US2516877A (en) * 1946-09-27 1950-08-01 Gulf Research Development Co Desulfurization of heavy petroleum hydrocarbons
US2516876A (en) * 1946-09-27 1950-08-01 Gulf Research Development Co Desulfurization of light petroleum hydrocarbons
US2574446A (en) * 1947-12-16 1951-11-06 Anglo Iranian Oil Co Ltd Catalytic desulfurization of gas oilkerosene mixtures
US2587987A (en) * 1949-05-10 1952-03-04 Gulf Oil Corp Selective hydrodesulfurization process
US2694671A (en) * 1950-09-01 1954-11-16 Standard Oil Dev Co Selective hydrogenation process
US2758060A (en) * 1951-01-15 1956-08-07 British Petroleum Co Removal of vanadium and/or sodium from petroleum by hydrogenation in the presence of bauxite

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3179586A (en) * 1959-11-24 1965-04-20 Sinclair Research Inc Process for preparing heavy fuel oils
US3658681A (en) * 1970-02-24 1972-04-25 Texaco Inc Production of low sulfur fuel oil
US3893909A (en) * 1971-12-27 1975-07-08 Universal Oil Prod Co Fuel oil production by blending hydrodesulfurized vacuum gas oil and hydrodesulfurized deasphalted residuum
US4990242A (en) * 1989-06-14 1991-02-05 Exxon Research And Engineering Company Enhanced sulfur removal from fuels
US5389235A (en) * 1992-12-02 1995-02-14 Uop Catalytic reaction zone for sulfur contaminant sensitive catalyst

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