EP0341802A1 - Removal of metal contaminants from oil - Google Patents

Removal of metal contaminants from oil Download PDF

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Publication number
EP0341802A1
EP0341802A1 EP89300137A EP89300137A EP0341802A1 EP 0341802 A1 EP0341802 A1 EP 0341802A1 EP 89300137 A EP89300137 A EP 89300137A EP 89300137 A EP89300137 A EP 89300137A EP 0341802 A1 EP0341802 A1 EP 0341802A1
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EP
European Patent Office
Prior art keywords
oil
ppm
metal values
aqueous solution
solution
Prior art date
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Application number
EP89300137A
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German (de)
French (fr)
Inventor
Anthony George Hurter
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Individual
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Individual
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Publication of EP0341802A1 publication Critical patent/EP0341802A1/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00Working-up used lubricants to recover useful products ; Cleaning

Definitions

  • This invention relates to the removal of metal values from oil.
  • the invention relates to the removal of contaminants from vacuum residue which is the final residue oil produced by the Kellog or Synthol process.
  • the invention relates to the removal of metal values that may still be present in a lubricating or other oil.
  • a final residue oil is produced which is commonly referred to as vacuum residue.
  • This oil generally contains a significant amount of incombustible material called ash, and this is primarily the iron catalyst used in the process, together with some inorganic salts and other incombustible materials.
  • used lubricating oils contain additives and ingressed metals.
  • the vacuum residue was heated to a temperature of about l00°C and then blended with water and the aqueous phase and the aqueous/ash phases were separated by centrifuge and the oil phase recovered.
  • the ash content could be reduced from 2500ppm to about 600ppm which was satisfactory for certain purposes but for others required further treatment.
  • an oil containing an ash content is treated with an aqueous solution of an anion capable of reacting with the metal values present to form water-soluble salts, and separating the aqueous phase from the oil phase.
  • the separation is preferably carried out by centrifugation.
  • the preferred an ions for use in the present invention are halides, and particularly chlorides, or nitrates.
  • the oil is treated with a solution of ammonium chloride.
  • a solution containing nitric acid and sodium chloride is used. In both cases the solutions may be saturated with respect to chloride ions.
  • the nitric acid may be about 6 percent.
  • the reaction between the anion solution and the contaminated oil is preferably conducted at an elevated temperature, preferably at or just below the boiling point of water.
  • the solution may be heated to about 80°C prior to addition.
  • the ratio of solution to oil is about 1:9.
  • the principal metal values in vacuum residue are sodium, calcium and iron and these are easily removed according to the present invention as chlorides or nitrates.
  • This oil should then have the particulate material removed from it, by heating it to 90°C, passing it through a coarse filter and subjecting it to a high gravitational separation process such as the Alfa Laval AX 213 super centrifuge, but preferably at a G-force above 15 000 G's.
  • Filtration should then be carried out using a post-­centrifuge 5 micron filter to remove particulate matter with a specific gravity such as that it will float in the oil.
  • the feedstocks which can be used include used lubricating oil, lube oil sludge collected from lube oil circulation centrifuges, oil sludge ex tank bottoms and the residues therefrom, miscellaneous washing processes, for example, tanker cleanings and oil drum cleaning plants.
  • This oil after pre-cleaning, will typically have an ash content of between 1 and 2%, where ash is defined as the residue obtained in the ASTM D482 method ash determination.
  • Pre-treated oil (as above) is heated to a temperature of 90 - 95°C, preferably using a shell and tube steam-heated heat exchanger.
  • the oil is held in a suitably designed tank, fitted with a circulation/agitation system.
  • a 4% by volume, heated (also at a temperature of 90°C) nitric acid solution is added.
  • This nitric acid solution comprises a 28% HNO3 in water (w/w).
  • This aqueous acid/oil mixture is agitated for a period until complete contact between oil/contaminants and the acid solution occurs. This normally takes one to two hours.
  • the temperature of the mixing vessel is maintained at 90°C by internal or external heating coils.
  • a further 25% water is added at a temperature of 90C, and mixing is continued vigorously for a period ranging from five to thirty minutes.
  • This mixture is fed through an adapted high speed, three phase centrifuge which separates the oil from the contaminants.
  • the water is passed to an effluent treatment plant.
  • a further 25% of water is added to the oil obtained from step 3.5 in a tank fitted with a circulating/agitating system, maintaining the temperature at 90°C, using internal or external heating coils.
  • This mixture is fed to a high speed, three phase centrifuge. It is optional to dose the theoretical amount of caustic soda to neutralise the remaining acid component of the oil if a fully neutralised oil is required.
  • a final optional step would be to pass this oil through a high speed super-centrifuge to remove the last traces of acid.
  • Waste oil comprising of a mixture of fuel oil, lube oil sludge ex the lube purifier, lube oil additives and diesel oil BEFORE AFTER Water % 1,0 0,2 Ash % 1,7 0,13 Elemental Analysis of Contaminants Fe ppm 4 000 109 Ca ppm 4 000 18 Al ppm 100 0 Si ppm 1 000 20 Na ppm 2 000 34 Va ppm 5 0 S ppm 1 600 1 300
  • a used lubricating oil was processed as above. The results are as follows: BEFORE AFTER Ash % 1,25 0,03 Water % 5 0,10 Fe ppm 246 4 Ni ppm 1 0 Al ppm 25 0 P ppm 443 5 Si ppm 63 10 Na ppm 134 8 Ca ppm 1 417 11 V ppm 1 0 Cr ppm 9 0 S ppm 11 483 8 521

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Oil containing undesirable metal values, such as contaminated vacuum residue oil, or used lubricating oil is treated at elevated temperature, with an aqueous solution of an anion capable of reacting with the metal values to form water-soluble salts, such as chlorides or nitrates, and then separating the aqueous phase from the oil.

Description

    FIELD OF THE INVENTION
  • This invention relates to the removal of metal values from oil. In one aspect, the invention relates to the removal of contaminants from vacuum residue which is the final residue oil produced by the Kellog or Synthol process. In another aspect, the invention relates to the removal of metal values that may still be present in a lubricating or other oil.
  • BACKGROUND OF THE INVENTION
  • In the manufacture of synthetic fuel oil from coal in the Kellogg or Synthol process, a final residue oil is produced which is commonly referred to as vacuum residue. This oil generally contains a significant amount of incombustible material called ash, and this is primarily the iron catalyst used in the process, together with some inorganic salts and other incombustible materials. Similarly, used lubricating oils contain additives and ingressed metals.
  • It is an object of the present invention to remove these contaminants from the vacuum residue or other oils in order to render it useful as a fuel for firing of furnaces, or in internal combustion engines, or for other purposes where reduced contaminants is required.
  • In the process described in the Applicants's RSA Patent 85/5142 the vacuum residue was heated to a temperature of about l00°C and then blended with water and the aqueous phase and the aqueous/ash phases were separated by centrifuge and the oil phase recovered. The ash content could be reduced from 2500ppm to about 600ppm which was satisfactory for certain purposes but for others required further treatment.
  • It is a further object of the present invention to provide a method of post-treating the oil to reduce its ash content to the order of about 10ppm.
  • THE INVENTION
  • According to the invention an oil containing an ash content is treated with an aqueous solution of an anion capable of reacting with the metal values present to form water-soluble salts, and separating the aqueous phase from the oil phase.
  • The separation is preferably carried out by centrifugation.
  • The preferred an ions for use in the present invention are halides, and particularly chlorides, or nitrates. Thus, in one form of the invention the oil is treated with a solution of ammonium chloride. In another form of the invention a solution containing nitric acid and sodium chloride is used. In both cases the solutions may be saturated with respect to chloride ions. The nitric acid may be about 6 percent.
  • The reaction between the anion solution and the contaminated oil is preferably conducted at an elevated temperature, preferably at or just below the boiling point of water. The solution may be heated to about 80°C prior to addition. The ratio of solution to oil is about 1:9.
  • The principal metal values in vacuum residue are sodium, calcium and iron and these are easily removed according to the present invention as chlorides or nitrates.
  • If highly emulsified oil is required to be treated it should be demulsified or have the water removed from it by one or another method.
  • This oil should then have the particulate material removed from it, by heating it to 90°C, passing it through a coarse filter and subjecting it to a high gravitational separation process such as the Alfa Laval AX 213 super centrifuge, but preferably at a G-force above 15 000 G's.
  • Filtration should then be carried out using a post-­centrifuge 5 micron filter to remove particulate matter with a specific gravity such as that it will float in the oil.
  • The feedstocks which can be used include used lubricating oil, lube oil sludge collected from lube oil circulation centrifuges, oil sludge ex tank bottoms and the residues therefrom, miscellaneous washing processes, for example, tanker cleanings and oil drum cleaning plants.
  • This oil, after pre-cleaning, will typically have an ash content of between 1 and 2%, where ash is defined as the residue obtained in the ASTM D482 method ash determination.
  • DETAILS OF THE INVENTION
  • Pre-treated oil (as above) is heated to a temperature of 90 - 95°C, preferably using a shell and tube steam-heated heat exchanger.
  • The oil is held in a suitably designed tank, fitted with a circulation/agitation system. In this tank a 4% by volume, heated (also at a temperature of 90°C) nitric acid solution is added. This nitric acid solution comprises a 28% HNO₃ in water (w/w).
  • This aqueous acid/oil mixture is agitated for a period until complete contact between oil/contaminants and the acid solution occurs. This normally takes one to two hours. The temperature of the mixing vessel is maintained at 90°C by internal or external heating coils.
  • A further 25% water is added at a temperature of 90C, and mixing is continued vigorously for a period ranging from five to thirty minutes.
  • This mixture is fed through an adapted high speed, three phase centrifuge which separates the oil from the contaminants. The water is passed to an effluent treatment plant.
  • A further 25% of water is added to the oil obtained from step 3.5 in a tank fitted with a circulating/agitating system, maintaining the temperature at 90°C, using internal or external heating coils.
  • This mixture is fed to a high speed, three phase centrifuge. It is optional to dose the theoretical amount of caustic soda to neutralise the remaining acid component of the oil if a fully neutralised oil is required.
  • A final optional step would be to pass this oil through a high speed super-centrifuge to remove the last traces of acid.
  • EXAMPLE 1
  • Waste oil comprising of a mixture of fuel oil, lube oil sludge ex the lube purifier, lube oil additives and diesel oil
    BEFORE AFTER
    Water % 1,0 0,2
    Ash % 1,7 0,13
    Elemental Analysis of Contaminants
    Fe ppm 4 000 109
    Ca ppm 4 000 18
    Al ppm 100 0
    Si ppm 1 000 20
    Na ppm 2 000 34
    Va ppm 5 0
    S ppm 1 600 1 300
  • EXAMPLE 2
  • A used lubricating oil was processed as above. The results are as follows:
    BEFORE AFTER
    Ash % 1,25 0,03
    Water % 5 0,10
    Fe ppm 246 4
    Ni ppm 1 0
    Al ppm 25 0
    P ppm 443 5
    Si ppm 63 10
    Na ppm 134 8
    Ca ppm 1 417 11
    V ppm 1 0
    Cr ppm 9 0
    S ppm 11 483 8 521
  • EXAMPLE 3
  • A product, waxy oil 20, which is the residual oil from the synthol oil-from-coal plant was processed as above. Results are follows:
    BEFORE AFTER
    Fe ppm 560 67
    P ppm 264 102
    Na ppm 90 31
    Si ppm 7 0
    Ca ppm 219 5
    S ppm 27 15
    Ash % 0,20 0,04

Claims (10)

1. A method of removing metal values from an oil containing undesirable metal values including the step of treating the oil with an aqueous solution of an anion capable of reacting with such metal values to form water-soluble salts, and separating the aqueous phase from the oil phase.
2. The method according to claim 1 in which the anion is chosen from chloride and nitrate.
3. The method according to claim 1 in which aqueous ammonium chloride is used as the treatment aqueous solution.
4. The method according to claim 1 in which a solution of nitric acid and sodium chloride is used as the treatment aqueous solution.
5. The method according to claim 3 or claim 4 in which the solution is saturated with respect to chloride ions.
6. The method according to any of the above claims in which the ratio of treatment aqueous solution to oil is about 1:9.
7. The method according to any of the above claims in which the treatment is carried out at a temperature at or just below the boiling point of water.
8. The method according to any of the above claims substantially as described in any of the examples.
9. The method according to any of claims 1 - 7 substantially as described in the "Details of the Invention".
l0. The product of the method as claimed in any of the above claims.
EP89300137A 1988-03-15 1989-01-09 Removal of metal contaminants from oil Withdrawn EP0341802A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ZA881823 1988-03-15
ZA881823 1988-03-15

Publications (1)

Publication Number Publication Date
EP0341802A1 true EP0341802A1 (en) 1989-11-15

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EP89300137A Withdrawn EP0341802A1 (en) 1988-03-15 1989-01-09 Removal of metal contaminants from oil

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1008468A4 (en) * 1994-06-28 1996-05-07 Univ Bruxelles Method for extracting heavy metals from used oils
WO1999021946A1 (en) * 1997-10-29 1999-05-06 Metallgesellschaft Aktiengesellschaft Regeneration of acid reaction lubricant residues

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607731A (en) * 1969-04-09 1971-09-21 Quvoe Chemical Ind Inc Re-refined waste crankcase oils and method
US4204946A (en) * 1979-02-12 1980-05-27 Turbo Resources Ltd. Process for removing metal contaminants from used lubricating oils
FR2530656A1 (en) * 1982-07-23 1984-01-27 Sader Gabriel Process for the treatment of spent oils to regenerate them.
DE3514970A1 (en) * 1985-04-25 1986-10-30 Dr. Baer Verfahrenstechnik GmbH, 6230 Frankfurt Process for removing metal from metal-containing greases

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607731A (en) * 1969-04-09 1971-09-21 Quvoe Chemical Ind Inc Re-refined waste crankcase oils and method
US4204946A (en) * 1979-02-12 1980-05-27 Turbo Resources Ltd. Process for removing metal contaminants from used lubricating oils
FR2530656A1 (en) * 1982-07-23 1984-01-27 Sader Gabriel Process for the treatment of spent oils to regenerate them.
DE3514970A1 (en) * 1985-04-25 1986-10-30 Dr. Baer Verfahrenstechnik GmbH, 6230 Frankfurt Process for removing metal from metal-containing greases

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT JOURNAL, February 1986, page 179, left-column, no. 85/5142; & ZA-A-85 5142 (FUEL FIRING SYSTEMS (PTY) LTD) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1008468A4 (en) * 1994-06-28 1996-05-07 Univ Bruxelles Method for extracting heavy metals from used oils
WO1999021946A1 (en) * 1997-10-29 1999-05-06 Metallgesellschaft Aktiengesellschaft Regeneration of acid reaction lubricant residues
US6479439B1 (en) 1997-10-29 2002-11-12 Metallgesellschaft Aktiengesellschaft Regenerator of acid reaction lubricant residues

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