US2759873A - Sweetening of hydrocarbon oils with raw clay followed by copper sweetening - Google Patents

Sweetening of hydrocarbon oils with raw clay followed by copper sweetening Download PDF

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Publication number
US2759873A
US2759873A US294716A US29471652A US2759873A US 2759873 A US2759873 A US 2759873A US 294716 A US294716 A US 294716A US 29471652 A US29471652 A US 29471652A US 2759873 A US2759873 A US 2759873A
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United States
Prior art keywords
copper
sweetening
clay
oil
hydrocarbon oils
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Expired - Lifetime
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US294716A
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English (en)
Inventor
Mcneill Eric
Boyle Russell Ignatius
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BP PLC
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BP PLC
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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G27/00Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/08Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of copper chloride
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G25/00Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents

Definitions

  • This invention relates to the sweetening of hydrocarbon oils, that is to say to the treatment of hydrocarbon oils for the elimination of mercaptans contained therein.
  • the principal object of the present invention is to enable distillates. boiling in the range. 150? to 350 C. to be satisfactorily coppen sweetened. although it may also, be applied, to light distillates. which may, through,
  • a process for the sweetening of a petroleum distillate comprises contacting the distillate, either before or after subjecting the distillate to a known copper sweetening process, with a clay having a montmorillonite type structure.
  • the clay treatment may be carried out at temperatures ranging from atmospheric to 250 F., and preferably at a temperature within the range ISO-220 F.
  • the clay treatment is preferably carried out after copper sweetening since the amount of oil-soluble copper complex in the sweetened distillate can thereby be reduced to a lower figure.
  • clay belonging to the group known as fullers earth a particularly suitable clay be-.
  • clay a coloured compound having an odour characteristic of certain nitrogen bases, as well as other irnpurities. It has further been established that the quantities of clay required are small, being in the region of 0:050.5 lb. per gallon of oil. The clay is easily removed from the treated oil by filtration or settling and can be freed from adsorbed compounds by a variety of methods such as extraction, steaming and treatment with chemicals.
  • the process of the invention may be carried out either batchwise or continuously.
  • the oil to be treated is heated in a vessel, warmed by a jacket or coil through which. steam or hot water is circulated, to give an oil temperature in the range ISO-220 F.
  • Agitation is effected by a dry air jet, paddle, centrifugal pump or liquid jet. After agitation for a: period. of one. hour, the. oil is allowed to stand, the clay settled, and the clear oil decanted from the settled clay. If desired a filter can also be used.
  • the oil is sweetened by means of an excess of cupric chloride solution in accordance with the well-known process.
  • a continuous process may be operated by means of a pre-heater and a clay mixer followed by a thickener and filter.
  • the spent clay is then subjected to a succession of steps in order to de-oil and then remove the contaminant bodies from the clay by solvent action.
  • the subsequent copper chloride treatment can be by any of the well-known processes, in which the copper chloride is either in solution, carried on a slurry or attached to a fixed'bed of mineral.
  • EXAMPLE 1 8 litres of raw kerosine distilled from Egyptian crude oil were heated to 200 F. in a: glassflask by means of a hot water bath. To the kerosine, which was agitated by means of a small air jet, was added grams of Surrey powder supplied by the Pullers Earth Union, and the stirring was continued for one hour. The greater part of the clear kerosine was decanted from the dark brown powder, the remainder being filtered free from powder. The clear kerosine, after cooling to 70 F. still contained mercaptans and was agitated for 15 minutes with twice the volume of an aqueous solution containing copper sulphate pentahydrate 176 grams per litre and common salt 160 grams per litre. This served to convert the mercaptans to disulphides.
  • EXAMPLE 2 A kerosine distilled from Iranian crude oil and washed at once with lime water was charged, 700 ml. at a time, to a cone-bottomed air jet circulated glass vessel. This was placed in a boiling water bath. When the contents reached 200 F. 7 grams of Surrey powder from the Fullers Earth Union were added and circulation of a slurry from the bottom of the cone back to the centre of the vessel promoted by an air jet entering an external pipe sealed to the base of the cone. This was continued for 30 minutes, after which the contents of the vessel were cooled and filtered. Sweetening was completed by means of a solution containing 176 grams per litre of CuSO4.5H2O and 160 grams per litre of sodium chloride using the necessary precautions to prevent contamination of the sweetened oil with copper compounds.
  • Table 2 of this blend were charged to a flask immersed in a steam-heated water bath, and when the temperature of the contents reached 195 F., grams of Surrey powder were added and agitation, by means of an air jet, continued for one hour. The contents of the flask were allowed to cool and were decanted from the clay, the remaining oil being recovered by filtration. The resulting product, which was of improved colour, was sweetened using a solution containing:
  • the resulting product was suitable for inclusion as a component of an aero turbine fuel under the British Specification DERD.2482.
  • Aprocess according to claim 1 wherein the amount and resulted in poor colour stability.
  • a number of exof clay used is between 0.05 and 0.5 lb. per gallon of periments were made in which the copper contaminated distillate. sweetened kerosine was mixed at room temperature with 5.
  • a process according to claim 1, wherein the disan improvement in colour stability took place with intillate is an aero turbine fuel of boiling range 100 to 250 creased treatment.
  • a process for the sweetening of a petroleum dis- 25 References cued m the file of thls patent tillate comprising contacting the distillate with an agent UNITED STATES PATENTS consisting of a raw clay having montmorillonite type 2,204,234 Schulze June 11, 1940 structure at an elevated temperature in the range of be- 2,227,089 Hopper Dec. 31, 1940 tween atmospheric to about 250 F., and subjecting the 2,329,930 Nebeck Sept. 21, 1943 contacted distillate to a copper sweetening process. 30 2,503,627 McBride et a1. Apr. 11, 1950

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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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
US294716A 1951-07-05 1952-06-20 Sweetening of hydrocarbon oils with raw clay followed by copper sweetening Expired - Lifetime US2759873A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB15981/51A GB723530A (en) 1951-07-05 1951-07-05 Improvements relating to the sweetening of hydrocarbon oils

Publications (1)

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US2759873A true US2759873A (en) 1956-08-21

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Family Applications (1)

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US294716A Expired - Lifetime US2759873A (en) 1951-07-05 1952-06-20 Sweetening of hydrocarbon oils with raw clay followed by copper sweetening

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US (1) US2759873A (US07655746-20100202-C00011.png)
BE (1) BE512629A (US07655746-20100202-C00011.png)
DE (1) DE954542C (US07655746-20100202-C00011.png)
FR (1) FR1065324A (US07655746-20100202-C00011.png)
GB (1) GB723530A (US07655746-20100202-C00011.png)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2825884A (en) * 1953-05-14 1958-03-04 Ravtheon Mfg Company Echo ranging devices
US3305479A (en) * 1964-10-16 1967-02-21 Standard Oil Co Copper chloride sweetening process
US20080296204A1 (en) * 2007-06-04 2008-12-04 Emirates National Oil Company Limited (Enoc) Llc Process for treating hydrocarbon liquid compositions
US9956502B2 (en) 2014-08-29 2018-05-01 Uop Llc Fixed bed apparatus with support structure and methods for processing hydrocarbons using the same
CN111024474A (zh) * 2019-11-19 2020-04-17 中国地质调查局西安地质调查中心 针对含硫地区油气化探样品芳烃类物质测定的前处理方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2204234A (en) * 1938-11-09 1940-06-11 Phillips Petroleum Co Treatment of hydrocarbon oils
US2227089A (en) * 1938-02-07 1940-12-31 Union Oil Co Treatment of hydrocarbon oil
US2329930A (en) * 1941-05-19 1943-09-21 Universal Oil Prod Co Process for sweetening hydrocarbon distillates
US2503627A (en) * 1949-04-27 1950-04-11 Phillips Petroleum Co Removal of mercaptans from gasoline

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR613817A (US07655746-20100202-C00011.png) * 1926-11-30
US1687992A (en) * 1926-05-29 1928-10-16 Gray Processes Corp Refining of hydrocarbon oils
US2081309A (en) * 1935-03-18 1937-05-25 Phillips Petroleum Co Process for treating oils
US2102878A (en) * 1936-05-23 1937-12-21 Universal Oil Prod Co Treatment of hydrocarbon oils
US2122795A (en) * 1936-06-15 1938-07-05 Union Oil Co Method of stabilizing sulphur containing petroleum oils
FR844849A (fr) * 1938-10-12 1939-08-02 Phillips Petroleum Co Perfectionnements au traitement des huiles hydrocarbonées

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2227089A (en) * 1938-02-07 1940-12-31 Union Oil Co Treatment of hydrocarbon oil
US2204234A (en) * 1938-11-09 1940-06-11 Phillips Petroleum Co Treatment of hydrocarbon oils
US2329930A (en) * 1941-05-19 1943-09-21 Universal Oil Prod Co Process for sweetening hydrocarbon distillates
US2503627A (en) * 1949-04-27 1950-04-11 Phillips Petroleum Co Removal of mercaptans from gasoline

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2825884A (en) * 1953-05-14 1958-03-04 Ravtheon Mfg Company Echo ranging devices
US3305479A (en) * 1964-10-16 1967-02-21 Standard Oil Co Copper chloride sweetening process
US20080296204A1 (en) * 2007-06-04 2008-12-04 Emirates National Oil Company Limited (Enoc) Llc Process for treating hydrocarbon liquid compositions
US7691258B2 (en) * 2007-06-04 2010-04-06 Emirates National Oil Company Limited (Enoc) Llc Process for treating hydrocarbon liquid compositions
US9956502B2 (en) 2014-08-29 2018-05-01 Uop Llc Fixed bed apparatus with support structure and methods for processing hydrocarbons using the same
CN111024474A (zh) * 2019-11-19 2020-04-17 中国地质调查局西安地质调查中心 针对含硫地区油气化探样品芳烃类物质测定的前处理方法

Also Published As

Publication number Publication date
BE512629A (US07655746-20100202-C00011.png)
DE954542C (de) 1956-12-20
FR1065324A (fr) 1954-05-24
GB723530A (en) 1955-02-09

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