US3761398A - Method of treating sulfur containing mineral oils to reduce their sulfur content - Google Patents

Method of treating sulfur containing mineral oils to reduce their sulfur content Download PDF

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Publication number
US3761398A
US3761398A US00109892A US3761398DA US3761398A US 3761398 A US3761398 A US 3761398A US 00109892 A US00109892 A US 00109892A US 3761398D A US3761398D A US 3761398DA US 3761398 A US3761398 A US 3761398A
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United States
Prior art keywords
sulfur
oil
water
superheated water
extraction
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Expired - Lifetime
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US00109892A
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English (en)
Inventor
E Munekata
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EIJI MUNEKATA JA
EISUKE MUNEKATA JA
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Individual
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Priority claimed from JP1266470A external-priority patent/JPS506004B1/ja
Priority claimed from JP4517970A external-priority patent/JPS5030643B1/ja
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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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/08—Inorganic compounds only

Definitions

  • An additional object of the present invention is to provide an extraction apparatus suitable for carrying out the novel method.
  • the sulfur compounds contained in mineral oils can be dissolved in superheated water, the amount of the dissolved sulfur compounds is governed by the law of distribution between mineral oils and superheated water. By the law of distribution a higher concentration of sulfur compounds will dissolve into the oil phase than in the water phase. The absolute amount of sulfur compounds dissolved into water, however, increases if the amount of water is increased in proportion to the amount of oil. The total amount of dissolved sulfur compounds is further increased if the oil and water are brought in contact counter-currently.
  • Extraction towers may be used in an industrial scale. However, it may be more effective to use extraction vessels which are connected in series, and operate the method by a counter-current extraction of the oil with. superheated water.
  • superheated water and hot mineral oil do not easily mix with each other. It is there- 5 Claims 3,761,398 Patented Sept. 25, 1973 fore essential to adjust the fluidity of both liquids, so that the superheated water and hot mineral oil intimately contact each other.
  • the inventors recommend two methods, i.e.
  • the inventors have decided to adjust the relative specific gravities of the mineral oil and superheated water for achieving satisfactory counter-current flow, and the inventors find no contradiction as to the explanation on counter-current extraction from the viewpoint of relative fluidity, because what the specific gravity and the fluidity mean here are compatible.
  • the inventors are of an opinion that the adjustrnent of the difference of the specific gravity is a basically important condition for the execution of superheated water extraction based on the counter-current contact technique. It is also a fact that liquid with a small specific gravity has a high fluidity, while a liquid with a large specific gravity has a low fluidity as far as petroleum mineral oils are concerned, within the range of this invention. Therefore, the inventors lay greater weight on the specific gravity of the mineral oils and the superheated water in determining the working conditions of the method and less weight on fiuidities of the liquids.
  • the required difference of the specific gravity is found to be difficult to obtain, when superheated water is used, it is recommended to facilitate the adjustment of the difference of the specific gravity by appropriate adjustment of the specific gravity of the sulfur containing oil.
  • the inventors recommend use of superheated water itself for treatment of sulfur-containing lighter oils and use of superheated water solutions for the treatment of sulfur-containing heavier oils.
  • the changes in the specific gravities of mineral oils and water with temperature are not always parallel. For example, the specific gravity of superheated water falls more rapidly with rising temperature than that of mineral oils; above a certain temperature, water has a specific gravity which is smaller than that of mineral oils. Thus, at the higher temperatures it becomes necessary to use water solutions.
  • the temperature used in the superheated water extraction method according to this invention is more than 100 C. As the preferable range of this temperature is 100 to 350 C., both sulfur-containing mineral oil and superheated water must be kept at this temperature.
  • the extraction tower must be maintained at a pressure much higher than the total pressure of both partial pressure of vapor of water and partial pressure of the vapor of mineral oil. By so doing, the boiling of either water or oil inside the extraction tower can be supressed, which otherwise would disturb the regular counter-current flow of the liquids.
  • the quantitative relations between the sulfur-containing mineral oils and superheated water or superheated water solution, the relations between differences of specific gravities as well as the temperature conditions for the extraction, must be determined for each experiment independently.
  • FIG. 1 A preferred embodiment of the invention has been chosen for purposes of illustration and description and is shown in the accompanying drawing.
  • the drawing illustrates a case whereby the extraction is made not by a multiple of extraction vessels but by an extraction tower.
  • Reference numeral 1 indicates a superheated vertical extraction tower, resistant to a high pressure, having an inlet 2 for the superheated water at its upper part, and an inlet 3 for hot mineral oil at its lower part.
  • Tower 1 also includes an outlet 4 of the desulfurized mineral oil at its top, and an outlet 5 for the sulfur-containing superheated Water at its bottom.
  • the superheated water extraction tower 1 is either filled with inert filler materials or has an agitating mechanism inside in order to sufficiently bring both superheated water and the mineral oil, which is dispersed in the superheated water, in counter-current contact.
  • Reference numeral 10 indicates a water tank and reference numeral 11 a mineral oil tank containing the mineral oil which is to be treated. Tanks 10 and 11 are connected via pressure pumps 8 and 9 to the tower 1. These pumps are connected further to the interior of the superheated water extraction tower 1 via a heat exchanger 7 and heater 6.
  • An outlet 4 for the desulfurized oil and an outlet 5 of the sulfur-containcontaining superheated water are connected by pipes via heat exchanger 7 to the pressure recovery mechanism attached to pumps 9 and 8.
  • water or water solution and sulfurcontaining mineral oil stored in the water tank 10 and the oil tank 11 respectively will be fed into the heat exchanger 7 by the pumps 8 and 9, where they are pre heated as the result of the heat exchange with the desulfurized mineral oil and sulfur-containing superheated water or sulfur-containing water solution which were already treated in the extraction tower 1. They will then be forwarded to the heater 6 where they are heated to the appropriate temperature for the treatment and fed into superheated water extraction tower 1 through superheated water inlet 2 and hot mineral oil inlet 3 at a pressure determined by the pressure pumps 8 and 9.
  • Superheated water or superheated water solution as well as hot mineral oil fed into the extraction tower 1 are brought into counter-current contact, extracted, treated and recovered through the outlets 4 and 5, wherefrom they are conveyed via heat exchanger 7 to the desulfurized oil receiving tank 13 and the sulfur-containing water receiving tank 12 to be stored.
  • the desulfurized mineral oil is obtained.
  • the operation pressure of the pumps 8 and 9 must be maintained at a level which is high enough to suppress boiling of either the water or the oil.
  • the pressure required is the grand total of the partial pressure of superheated water and the partial pressure of hot mineral oil found in the extraction column, plus the pressure of the pump required for transporting the fluid in the equipment, plus the pressure for pressurizing the extraction tower as a safety measure in order to prevent bumping.
  • high pressure is employed in the extraction, one of the features of this invention is to recover the energy possessed by the pressure of the fluids discharged from the tower.
  • a recovering apparatus is attached to the pressure pumps 8 and 9 in order to recover the pressure of desulfurized mineral oil and sulfur-containing superheated water or sulfur-containing superheated water solution coming from the outlets 4 and 5 and flowing out of heat exchanger 7.
  • the recovered heat energy pre-heats the raw materials which will become superheated water or superheated water solution and hot mineral oil to be fed into the extraction tower and thereby saves the heat.
  • the pressure energy recovering apparatus is installed in the pressure pumps 8 and 9, and takes the form of, for example, a turbine operated by the pressure of the fluids discharged from the tower.
  • the turbine may be geared to the motors of the pumps 8 and 9 for the purpose of saving the energy required by the motors of the pressure pumps.
  • EXAMPLE 1 A heavy oil with sulfur content 3.4% and specific gravity 0.97 was charged into an autoclave together with water in an amount equal to twice that of said heavy oil. After agitation for about 20 minutes at a temperature of 300 C., the contents were allowed to settle, so that the water phase separated from the oil phase and the two phases were separated. At this time, the sulfur content of the substance in the oil phase was 2.0%, and the sulfur content in the heavy oil dropped down to about 40%.
  • EXAMPLE 2 Vacuum distilled gas oil (650-1000 F.) having a sulfur content of 2.5% and a specific gravity 0.92 was extracted by superheated water at about 230 C. in a counter-current contact extraction column in a laboratory. The sulfur content of the light oil after the treatment was 1.5%. According to this result it is apparent that desulfurized gas oil with sulfur content less than 0.5% could be obtained in an extraction tower operated counter-currently.
  • EXAMPLE 3 A heavy oil having a sulfur content of 4.4% and specific gravity 0.99 was blended with light oil in equal amounts to prepare a sulfur-containing mineral oil of total sulfur content 2.5% and specific gravity 0.93. When examined, this blended oil was found to be far more suitable than the original heavy oil for counter-current continuous extraction. This sulfur containing mineral oil was treated in the apparatus described in the drawing with salt water solution at 300 C. A heavy oil was obtained by distilling the treated blended oil which exhibited a reduction in sulfur content.
  • a method of treating a sulfur-containing mineral oil to reduce its sulfur content comprising extracting sulfur-containing substances from said mineral oil by intimately contacting said mineral oil with super-heated aqueous liquor having a temperature above C., wherein the specific gravity of at least one of said mineral oil and said super-heated aqueous liquor is adjusted prior to treating said oil, by adding Water soluble substances and/ or colloidal substances so that the ditference between their specific gravities at the temperature of the treatment is sufficient to enable a counter-current flow.

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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)
  • Inorganic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Extraction Or Liquid Replacement (AREA)
US00109892A 1970-02-16 1971-01-26 Method of treating sulfur containing mineral oils to reduce their sulfur content Expired - Lifetime US3761398A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1266470A JPS506004B1 (sv) 1970-02-16 1970-02-16
JP4517970A JPS5030643B1 (sv) 1970-05-28 1970-05-28

Publications (1)

Publication Number Publication Date
US3761398A true US3761398A (en) 1973-09-25

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US00109892A Expired - Lifetime US3761398A (en) 1970-02-16 1971-01-26 Method of treating sulfur containing mineral oils to reduce their sulfur content

Country Status (8)

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US (1) US3761398A (sv)
CA (1) CA954465A (sv)
DE (1) DE2105710A1 (sv)
FR (1) FR2080532B1 (sv)
GB (1) GB1292426A (sv)
NL (1) NL141926B (sv)
SE (1) SE392727B (sv)
SU (1) SU488420A3 (sv)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3989618A (en) * 1974-05-31 1976-11-02 Standard Oil Company (Indiana) Process for upgrading a hydrocarbon fraction
US4428828A (en) 1981-01-02 1984-01-31 Chevron Research Company Upgrading hydrocarbonaceous oils with an aqueous liquid
US5055179A (en) * 1988-06-13 1991-10-08 Ortech Corporation Upgrading heavy oil

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2025044C (en) * 1989-09-22 1999-12-21 Michael Siskin Process for converting and upgrading organic resource materials in aqueous environments

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3989618A (en) * 1974-05-31 1976-11-02 Standard Oil Company (Indiana) Process for upgrading a hydrocarbon fraction
US4428828A (en) 1981-01-02 1984-01-31 Chevron Research Company Upgrading hydrocarbonaceous oils with an aqueous liquid
US5055179A (en) * 1988-06-13 1991-10-08 Ortech Corporation Upgrading heavy oil

Also Published As

Publication number Publication date
NL7101755A (sv) 1971-08-18
CA954465A (en) 1974-09-10
NL141926B (nl) 1974-04-16
DE2105710A1 (de) 1971-08-26
SE392727B (sv) 1977-04-18
GB1292426A (en) 1972-10-11
SU488420A3 (ru) 1975-10-15
FR2080532B1 (sv) 1975-01-17
FR2080532A1 (sv) 1971-11-19

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