US2719108A - Catalytic desulphurisation of petroleum hydrocarbons - Google Patents

Catalytic desulphurisation of petroleum hydrocarbons Download PDF

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Publication number
US2719108A
US2719108A US326704A US32670452A US2719108A US 2719108 A US2719108 A US 2719108A US 326704 A US326704 A US 326704A US 32670452 A US32670452 A US 32670452A US 2719108 A US2719108 A US 2719108A
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feedstock
hydrogen
reaction zone
sulphur
desulphurisation
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US326704A
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Porter Frederick Willi Bertram
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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
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps

Definitions

  • This invention relates to the catalytic desulphurisation of petroleum hydrocarbons.
  • Both the hydrofining and the autofining processes involve the recycling of large amounts of hydrogen-containing gases to the desulphurisation zone, since it has been shown that high hydrogen partial pressures are necessary in order to secure an economic degree of desulphurisation at reasonable space velocities.
  • the plant must therefore include pumps and boosting equipment for maintaining the recycle rate.
  • a hydrogen-rich gas may be separated from the products obtained when carrying out the liquid phase process as above described, and that this gas can with advantage be employed to effect further desulphurisation of the treated product and/or to improve its colour.
  • a process for the catalytic desulphurisation of a petroleum feedstock comprises passing the feedstock to a first reaction zone wherein it is contacted with a sulphur-resistant dehydrogenationhydrogenation catalyst under controlled conditions of temperature and pressure such that the feedstock is maintained substantially in the liquid phase and an amount of hydrogen is produced by dehydrogenation of naphthenes contained in the feedstock in excess of that required to convert organically combined sulphur in the feedstock into hydrogen sulphide but without effecting any appreciable change in the boiling range of the feedstock, continuously passing the products from said first reaction zone to a second reaction zone wherein they are contacted at elevated temperature and pressure with a sulphur-resistant hydrogenation catalyst, separating the products from said second reaction zone into a liquid product and a gaseous Q product rich in hydrogen, and recycling said hydrogenrich gaseous product to said second reaction zone.
  • the degree of further desulphurisation that may be effected in the second reaction zone depends upon the amount of hydrogen produced in the first reaction zone, and at the same space velocity of liquid feedstock in both zones, it may not be possible to effect complete desulphurisation in the second zone.
  • Complete desulphurisation in the second zone can, however, be effected by reducing the space velocity in the second zone by increasing the size of the catalyst volume, or by similarly reducing the space velocity in the first zone or by increasing the temperature in the first zone if equilibrium for dehydrogenation has not already been reached.
  • cobalt molybdate type catalysts containing fluorine are particularly preferred.
  • a cobalt molybdate type catalyst is meant a catalyst essentially comprising the oxides of cobalt and molybdenum, either in the form of mixtures of said oxides or in the form of chemical compounds of cobalt, molybdenum and oxygen, either alone or incorporated with a support, such as alumina.
  • the feedstock to be desulphurised is passed via line 10 and heater 11 into reactor A wherein it is contacted with a sulphur-resistant dehydrogenation-hydrogenation catalyst at elevated temperature and pressure.
  • the term perature should be kept as low as possible to avoid substantial vapourisation of the feedstock and is preferably within the range 700800 F., while the pressure may be 500-1000 lb./sq. in., or more depending upon the boiling range of the feedstock.
  • the products leaving the reactor A are passed at substantially the same pressure into the reactor B wherein they are contacted with a sulphurresistant hydrogenation-catalyst at elevated temperature and pressure which are governed by those established in reactor A.
  • the products leaving reactor B are passed through heat exchanger 13 into a separator 14 operating under plant pressure.
  • a gas mixture containing a high proportion of hydrogen is removed from the separator 14 via line 15 and is recycled by means of blower 16 through heater 17 in the reactor B.
  • Liquid product containing hydrogen sulphide dissolved therein is removed from the separator 14 via line 18 and is treated in known manner for the separation of the hydrogen sulphide therefrom.
  • the space velocity in the reactor B is adjusted by adjusting the catalyst volume so that the hydrogen produced in the reactor A is completely consumed in the reactor B.
  • the feedstock was passed to reactor A at a temperature of 780 F., a pressure of 500 p. s. i. ga., and a space velocity of 3.0 v./v./hr.
  • a catalyst in the reactor A of the cobalt molybdate type containing both fluorine and phosphorus as ingredients the sulphur content of the product leaving reactor A was 0.23% weight, i. e., a reduction of 50%.
  • the gas make amounted to 50 cubic feet per barrel and contained 70% by volume of hydrogen. l t was therefore possible to arrange for a consumption of 35 cubic feet per barrel of hydrogen in the reactor B which is more than sufiicient to remove the sulphur remaining in the product passing to reactor B.
  • a gas oil of 1.16 per cent by weight sulphur content was passed to reactor A at a temperature of 750 F., a pressure of 500 p. s. i. ga.,
  • a process for the catalytic desulphurisation of a petroleum feedstock which comprises passing the feedstock to a first reaction zone wherein it is contacted with a sulphur-resistant dehydrogenation-hydrogenation catalyst under controlled conditions of temperature and pressure of about 700-800 F. and about 500-1000 lb./sq. in.

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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)
US326704A 1951-12-21 1952-12-18 Catalytic desulphurisation of petroleum hydrocarbons Expired - Lifetime US2719108A (en)

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GB2719108X 1951-12-21

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US2719108A true US2719108A (en) 1955-09-27

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US (1) US2719108A (en, 2012)
BE (1) BE516424A (en, 2012)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2779713A (en) * 1955-10-10 1957-01-29 Texas Co Process for improving lubricating oils by hydro-refining in a first stage and then hydrofinishing under milder conditions
US2880166A (en) * 1955-10-19 1959-03-31 Phillips Petroleum Co Improving color and color stability of kerosene by combined autofining and hydrofining
US2889274A (en) * 1955-03-22 1959-06-02 British Petroleum Co Catalytic desulphurization of petroleum hydrocarbons and production of hydrogen therefrom
DE1094904B (de) * 1957-04-20 1960-12-15 Metallgesellschaft Ag Verfahren zur katalytischen hydrierenden Raffination von Schmieroelen oder Schmieroelfraktionen
US3028331A (en) * 1959-04-07 1962-04-03 Socony Mobil Oil Co Inc Hydrogen production in a tcc process
DE1174007B (de) * 1959-05-16 1964-07-16 Universal Oil Prod Co Verfahren zur Herstellung von Schmieroel

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2253308A (en) * 1937-05-05 1941-08-19 Standard Catalytic Co Desulphurization of hydrocarbons
US2417308A (en) * 1943-04-12 1947-03-11 Union Oil Co Desulphurization and hydroforming
US2574448A (en) * 1948-06-24 1951-11-06 Anglo Iranian Oil Co Ltd Catalytic desulfurization of gas oil

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2253308A (en) * 1937-05-05 1941-08-19 Standard Catalytic Co Desulphurization of hydrocarbons
US2417308A (en) * 1943-04-12 1947-03-11 Union Oil Co Desulphurization and hydroforming
US2574448A (en) * 1948-06-24 1951-11-06 Anglo Iranian Oil Co Ltd Catalytic desulfurization of gas oil

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2889274A (en) * 1955-03-22 1959-06-02 British Petroleum Co Catalytic desulphurization of petroleum hydrocarbons and production of hydrogen therefrom
US2779713A (en) * 1955-10-10 1957-01-29 Texas Co Process for improving lubricating oils by hydro-refining in a first stage and then hydrofinishing under milder conditions
US2880166A (en) * 1955-10-19 1959-03-31 Phillips Petroleum Co Improving color and color stability of kerosene by combined autofining and hydrofining
DE1094904B (de) * 1957-04-20 1960-12-15 Metallgesellschaft Ag Verfahren zur katalytischen hydrierenden Raffination von Schmieroelen oder Schmieroelfraktionen
US3028331A (en) * 1959-04-07 1962-04-03 Socony Mobil Oil Co Inc Hydrogen production in a tcc process
DE1174007B (de) * 1959-05-16 1964-07-16 Universal Oil Prod Co Verfahren zur Herstellung von Schmieroel

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Publication number Publication date
BE516424A (en, 2012)

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