EP3121254B1 - Oil purification and preparation of anti-rutting additive - Google Patents

Oil purification and preparation of anti-rutting additive Download PDF

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Publication number
EP3121254B1
EP3121254B1 EP16180213.7A EP16180213A EP3121254B1 EP 3121254 B1 EP3121254 B1 EP 3121254B1 EP 16180213 A EP16180213 A EP 16180213A EP 3121254 B1 EP3121254 B1 EP 3121254B1
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EP
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Prior art keywords
distillation
oils
hydrocarbon feedstock
oil
purified
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EP16180213.7A
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German (de)
French (fr)
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EP3121254A1 (en
Inventor
Dominique Rio
Maurice Born
Samuel Mignard
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Conception D'equipements Pour L'environnement Et L'industrie Ste
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Conception D'equipements Pour L'environnement Et L'industrie Ste
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Classifications

    • 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
    • C10G31/09—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by filtration
    • 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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/12—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one alkaline treatment step
    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/06—Vacuum distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0016—Working-up used lubricants to recover useful products ; Cleaning with the use of chemical agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
    • C10M175/0033—Working-up used lubricants to recover useful products ; Cleaning by thermal processes using distillation processes; devices therefor
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/005—Working-up used lubricants to recover useful products ; Cleaning using extraction processes; apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0058—Working-up used lubricants to recover useful products ; Cleaning by filtration and centrifugation processes; apparatus therefor
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C10G2300/1007—Used oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/011—Cloud point
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/013—Iodine value
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

Definitions

  • the invention relates to the field of purification of hydrocarbon feeds comprising one or more compounds to be removed, in particular used lubricating compositions.
  • the lubricating compositions are degraded and then comprise pollutant compounds, undesirable or to be eliminated.
  • used oils such as motor oils, hydraulic oils, gear oils or industrial oils and mixtures thereof, must be purified to regenerate them into a lubricating base of commercial quality identical to the original product. for a new use.
  • This type of treatment may be referred to as the re-refining or regeneration of waste oils.
  • the field of the invention is therefore that of the regeneration of hydrocarbon feedstocks, such as waste or used oils, in particular engine oils, hydraulic oils, gear oils or industrial oils, and mixtures thereof.
  • the invention also makes it possible to produce substances that can be reused according to their properties obtained from the purification of used oils.
  • the oils are subjected to stresses that will cause their degradation leading to an increase in the level of contaminating elements these oils, these contaminants may be derived from a degradation of the additives present in the lubricant compositions, such as the antioxidant additives; anti-wear agents; or external pollutants, such as dust; or wear metals emanating from, for example, parts with which the oil is in contact during use; or even fractions of fuel (gas oil or gasoline) more or less oxidized or thermally cracked and which may be in liquid or solid form including soot; or else contaminants related to the storage of used oils in which there are sometimes substances constituting light fractions which are generally water or chlorinated or petroleum solvents.
  • the additives present in the lubricant compositions such as the antioxidant additives; anti-wear agents; or external pollutants, such as dust; or wear metals emanating from, for example, parts with which the oil is in contact during use; or even fractions of fuel (gas oil or gasoline) more or less oxidized or thermally cracked and which may be in liquid or solid form including soo
  • the invention thus provides a method for providing a solution to all or part of the problems of the methods of the state of the art.
  • the invention relates to a process for purifying a hydrocarbon feedstock, comprising the following steps: a) purification, by extraction of the light compounds, of the hydrocarbon feedstock, b) separation, by filtration in the presence of a fluid in the state supercritical, of the purified hydrocarbon feedstock obtained in step a), and obtaining a filtrate and a retentate c) purification, by saponification, of the filtrate obtained in step b) d) separation, by distillation under vacuum or under reduced pressure, purified filtrate obtained in step c) and obtaining a purified and distilled filler and a distillation residue; e) washing, by means of an aqueous solution, the distillation residue obtained in step d), f) separating the washed distillation residue obtained at the end of step e) into an aqueous phase and a phase organic, the hydrocarbon feedstock being selected from a mineral or mineral oil or a synthetic oil or synthetic origin.
  • the hydrocarbon feedstock is chosen from mineral oils resulting from the fractional distillation of crude oil, in particular industrial oils, gear oils, hydraulic oils or used or used motor oils.
  • the hydrocarbon feedstock treated according to the process of the invention comprises one or more hydrocarbons and optionally one or more compounds comprising carbon atoms, hydrogen and which may also comprise one or more heteroatoms.
  • the hydrocarbon feedstock treated according to the process of the invention also comprises compounds to be eliminated selected from dispersant additives, detergent additives, anti-wear additives, polymers, soot, metal elements.
  • step a) of extraction of the light compounds is carried out by distillation under vacuum or under reduced pressure.
  • the extraction step a) is a flash evaporation of the light compounds.
  • step a) of the process according to the invention makes it possible to purify the hydrocarbon feedstock by distillation, preferably by distillation of the light compounds.
  • Step a) of extraction of the process according to the invention also makes it possible to eliminate water or the aqueous phase which may be present within the hydrocarbon feedstock.
  • the extraction step a) is in particular carried out at a pressure of less than 0.08 bar, for example less than 0.05 bar, or even less than 0.03 bar.
  • the stage a) extraction is carried out at a temperature ranging from 100 to 250 ° C, for example at about 150 ° C.
  • step b) of filtration of the hydrocarbon feedstock obtained in step a) in the presence of a fluid in the supercritical state is preferably carried out by means of CO 2 in the supercritical state although other gases, such as N 2 O, SF 6, methane, ethane, propane or hexane, may be suitable.
  • the CO 2 in the supercritical state is generally used in an amount ranging from about 2 to 60% or about 15 to 20% by weight of hydrocarbon feedstock to be purified.
  • step (b) is a tangential filtration.
  • step (b) is carried out at a temperature ranging from 100 to 180 ° C or at a pressure ranging from 120 to 180 bar. It can be carried out at a temperature ranging from 100 to 180 ° C. and at a pressure ranging from 120 to 180 bar.
  • Step (b) is carried out by means of a filter which may be a membrane based on metals or metal alloys such as steel, for example stainless steel, or nickel; oxides such as oxides selected from Al 2 O 3 , ZrO 2 , TiO 2 .
  • Step (b) concerns the majority of the compounds to be removed, preferably 80% or even 90% or more of the compounds to be removed are filtered.
  • the filter makes it possible to retain compounds or particles whose average size, ie the average particle diameter, ranges from 1 nm to 10 ⁇ m, preferably from 2 nm to 1 ⁇ m, and more preferred from 2 nm to 0.1 ⁇ m.
  • step b) consists in the separation, by tangential filtration in the presence of CO 2 in the supercritical state, of the hydrocarbon feedstock obtained in step a), and allows the obtaining a filtrate and a retentate.
  • Step b) makes it possible to separate the compounds to be eliminated present in the filtration retentate from the filtered hydrocarbon feedstock.
  • the filtered hydrocarbon feedstock is then treated using the transformation agent.
  • the retentate obtained in step b) comprising compounds to be eliminated can be concentrated. This concentration of the retentate can be achieved by eliminating certain compounds, in particular paraffinic compounds.
  • the filtrate obtained in step b) is purified in step c) of the feed by means of a transformation agent.
  • step c) is carried out by saponification.
  • the treatment c) by saponification is carried out using a transformation agent selected from NaOH or KOH, used alone or as a mixture.
  • the saponification is preferably carried out using NaOH.
  • step c) consists in the purification, by saponification using sodium hydroxide in aqueous solution at about 50% by weight, of the filtrate obtained in step b).
  • the step d) of separation of the purified filtrate obtained in step c) is carried out by vacuum distillation, for example by vacuum distillation with falling film or by distillation under reduced pressure in a thin layer.
  • the start-of-distillation parameters are advantageously about 19 mbar for the pressure, about 240 ° C for the medium temperature and about 50 ° C for the medium temperature. the temperature at the top of the column. At the end of distillation, these parameters are generally about 19 mbar for the pressure, about 375 ° C tending towards 400 ° C for the temperature of the medium and about 375 ° C for the temperature at the top of the column.
  • step d) consists of the separation, by distillation under vacuum or under reduced pressure, of the purified filtrate obtained in stage c) and makes it possible to obtain a purified filler and distilled and a distillation residue.
  • the purified and distilled feed obtained at the end of step (d) has characteristics identical to those of the base oils. This purified and distilled feedstock can therefore be used as a base oil in lubricating compositions.
  • Step e) consists of washing the distillation residue obtained at the end of step d).
  • step e) consists in washing, by means of an aqueous solution, the distillation residue obtained in step d).
  • the distillation residue is treated with an aqueous solution.
  • step e) is carried out with water, for example in an amount ranging from 1 to 5 times, preferably from 1 to 3 times, the volume of distillation residue obtained.
  • the mixture of the aqueous solution and the distillation residue can be stirred.
  • Step (e) can be carried out with varying amounts of aqueous solution.
  • a mixture comprising 20, 30 or 50% by weight of distillation residue supplemented to 100% by weight with aqueous solution may be advantageous.
  • Step f) of the process of the invention consists of separating the aqueous and organic phases of the washed distillation residue obtained in step e).
  • the separation of step f) can be carried out by decantation. Once the organic phase is separated, it can be dried.
  • its viscosity measured at 100 ° C. according to the ISO 3104 standard ranges from 50 to 400 mm 2 .s -1 , preferably from 100 to 200 mm 2 .s -1 .
  • step f) of the process consists of separating the washed distillation residue obtained in step e) into an aqueous phase and an organic phase.
  • the process according to the invention makes it possible to purify a hydrocarbon feedstock comprising one or more compounds to be eliminated and to obtain a purified hydrocarbon feedstock.
  • the method according to the invention makes it possible to obtain a retentate at the end of step b).
  • This retentate has particularly advantageous properties.
  • the process according to the invention makes it possible to obtain, after step f), the organic phase of the washed distillation residue.
  • a mixture of used oils from motor oils, bridge oils and gearbox oils (5000 L) from heavy vehicles was processed according to the process of the invention.
  • the used oil mixture is placed in a jacketed tank which is heated to 70 or 80 ° C and then heated by means of a heat exchanger (150 ° C).
  • the water present in the waste oil mixture is removed by flash distillation (150 ° C, 150 mbar) in a 50 L autoclave. Any light substances are then also separated from the oil mixture during evaporation. flash.
  • the waste oil mixture (4,600 L) obtained from the distillation is then filtered in the presence of CO 2 in the supercritical state (150 ° C., 150 bar) in a quantity of approximately 20% by mass of the amount of used oils entering the device.
  • microfiltration membranes product Tami Dahlia 0.14 microns
  • the injection of used oil - CO 2 mixture is made in the suction line of the centrifugal pump to maximize the mixing of the two components before filtration.
  • the waste oil flow in the plant is 165 kg / h.
  • the flow rate of the filtrate is about 125 kg / h.
  • the difference between inner and outer pressures of the filtration membranes ( ⁇ P) is less than 4 bar.
  • a filtrate (2870 L) and a filtration retentate (1550 kg) are obtained.
  • the filtration retentate is reintroduced into the filtration loop.
  • the treatment conditions are similar (150 ° C., 150 bar).
  • the amount of CO 2 is about 30% by weight of introduced retentate.
  • the recirculation rate is about 30-31 m 3 / h.
  • the charge rate is 50 kg / h and the retentate flow rate is about 43 kg / h.
  • the filtrate obtained during this reprocessing is mixed with the filtrate obtained during the filtration of the used oil mixture.
  • a total of 1,487 L filtrate and a filtration retentate (217 kg) are obtained.
  • a retentate is obtained whose density mixed with CO 2 is about 982 kg / m 3 (about 300 kg / m 3 mixed with CO 2 ).
  • a filtrate (2870 L) is obtained which is treated with sodium hydroxide (4% by weight relative to the amount of filtrate) in solution in water (4% by weight relative to the amount of filtrate) for 15 hours. hours, at a temperature of 100 ° C.
  • the mixture is distilled at reduced pressure (50 mbar) at 290 ° C using a thin-film evaporator equipped with rigid scrapers.
  • Flash evaporation is then carried out (5 mbar) followed by distillation (5 mbar and 315 ° C.). A purified oil and a distillation residue are obtained.
  • PAHs polycyclic aromatic hydrocarbon compounds
  • the characteristics and properties of the purified oil obtained according to the invention are equivalent to or greater than those of the two oils.
  • the base oil according to the invention can therefore be used in a lubricant composition, especially in a lubricant composition for a vehicle engine.
  • the distillation residue obtained after distillation was washed with water with stirring for 4 hours and then the organic phase was separated by decantation for 12 hours.
  • a paraffin oil is obtained whose viscosity measured at 100 ° C. is 150 mm 2 .s -1 . This oil can be used to lubricate gears, including open gears.
  • the filtration retentate was evaluated for its bitumen additive properties.
  • the retentate is mixed with bitumen and its resistance properties within the mixture as well as the improvement of the properties of the additive bitumen were analyzed.
  • the program is established in two phases. The first concerns the behavior of the mixture of retentate and bitumen, before and after simulation of a coating. The measures are based mainly on the assessment of the consistency of the products, in accordance with the European regulatory specifications.
  • the second phase deals with the coated material, made by mixing aggregates, bitumen and retentate. The compactibility, water stripping resistance and ability to resist rutting are evaluated.
  • the bitumen class chosen is 35/50.
  • the rate of modification of the bitumen by the retentate was set at 2.5% by weight.
  • This bitumen-type asphalt made with a 35/50 bitumen additive containing 2.5% by weight of retentate, complies with the level 2 specifications (for a Class 4 GB).
  • the mixture 35/50 bitumen and retentate (2.5% by weight) complies with the specifications of road bitumens and gives a gravel bitumen of class 4 compliant up to level 2.
  • a leaching test according to standard NF EN 12 457-2 has also been carried out.
  • a 35/50 bitumen sand was compared to the same 35/50 bitumen sand additive with 2.5% retentate.
  • the analysis of the eluate after leaching test shows a total organic carbon content (according to NF EN 1484) of 17 mg / kg for the reference sample and 31 mg / kg for the sample made from bitumen additive. Both samples have a similar chromatographic profile free of semi-volatile organic molecules detectable by this technique.
  • the addition of ultrafiltration retentate to the bitumen does not alter its behavior on contact with water: no semi-volatile substance is detectable in the leachate.
  • a demixing resistance test was carried out for the additive bitumen of the retentate according to the invention.
  • the retentate mixed with the bitumen was placed in a vertical tube and then allowed to stand for 36 hours at 180 ° C. After cooling, the softening points of the mixture from the top and bottom of the tube were measured. Softening temperatures of 51.8 ° C are obtained for the mixture coming from the upper part and 51.4 ° C for the mixture coming from the upper part. These very close temperatures confirm that no demixing took place.
  • the additive bitumen of the retentate according to the invention is therefore storage stable.
  • the resistance to rutting of the additive bitumen of the retentate according to the invention was evaluated by means of a Gamma bank according to the method NF EN 12697 part 22.
  • the rutting results are very good for the additive bitumen of the retentate according to the invention. Indeed, while the average normative value of the rut depth after 10,000 passes must be less than 10%, the bitumen additive of the retentate according to the invention allows a value of 4.6%.

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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)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Lubricants (AREA)

Description

L'invention concerne le domaine de la purification des charges hydrocarbonées comprenant un ou plusieurs composés à éliminer, notamment des compositions lubrifiantes usagées.The invention relates to the field of purification of hydrocarbon feeds comprising one or more compounds to be removed, in particular used lubricating compositions.

Lors de leur utilisation, les compositions lubrifiantes se dégradent et comprennent alors des composés polluants, indésirables ou à éliminer. Ainsi, les huiles usées, telles que les huiles de moteur, les huiles hydrauliques, les huiles d'engrenages ou les huiles industrielles ainsi que leurs mélanges, doivent être purifiées pour les régénérer en une base lubrifiante de qualité commerciale identique au produit d'origine en vue d'une nouvelle utilisation. Ce type de traitement peut être désigné par l'expression re-raffinage ou régénération des huiles usées. Le domaine de l'invention est donc celui de la régénération des charges hydrocarbonées, telles que les huiles usées ou usagées, notamment des huiles de moteur, des huiles hydrauliques, des huiles d'engrenages ou des huiles industrielles ainsi que leurs mélanges.
L'invention permet également de produire des substances pouvant être réutilisées en fonction de leurs propriétés obtenues à partir de la purification des huiles usées.In use, the lubricating compositions are degraded and then comprise pollutant compounds, undesirable or to be eliminated. Thus, used oils, such as motor oils, hydraulic oils, gear oils or industrial oils and mixtures thereof, must be purified to regenerate them into a lubricating base of commercial quality identical to the original product. for a new use. This type of treatment may be referred to as the re-refining or regeneration of waste oils. The field of the invention is therefore that of the regeneration of hydrocarbon feedstocks, such as waste or used oils, in particular engine oils, hydraulic oils, gear oils or industrial oils, and mixtures thereof.
The invention also makes it possible to produce substances that can be reused according to their properties obtained from the purification of used oils.

Lors de leur utilisation, les huiles sont soumises à des contraintes qui vont engendrer leur dégradation conduisant à une augmentation du taux d'éléments contaminants ces huiles, ces éléments contaminants pouvant provenir d'une dégradation des additifs présents dans les compositions lubrifiantes, tels que les additifs antioxydants, les agents anti-usure ; ou bien de polluants externes, tels que des poussières ; ou bien des métaux d'usure émanant, par exemple, des pièces avec lesquelles l'huile est en contact lors de son utilisation ; ou bien encore de fractions de carburant (gazole ou essence) plus ou moins oxydées ou craquées thermiquement et qui peuvent être sous formes liquide ou solide notamment de suies ; ou bien encore des contaminants liés au stockage des huiles usagées dans lesquelles sont parfois présentes des substances constituant des fractions légères qui sont généralement de l'eau ou des solvants chlorés ou pétroliers.
Il s'ensuit une huile polluée et présentant une coloration plus forte que l'huile initiale propre, d'où l'appellation d'huiles noires dans le domaine des huiles usées, en particulier du fait de la présence de produits d'oxydation ou de craquage du carburant. Pour pouvoir être réutilisable, l'huile doit être débarrassée de ces éléments contaminants et, pour ce faire, est amenée à subir des opérations de dépollution généralement similaires à celles du raffinage.During their use, the oils are subjected to stresses that will cause their degradation leading to an increase in the level of contaminating elements these oils, these contaminants may be derived from a degradation of the additives present in the lubricant compositions, such as the antioxidant additives; anti-wear agents; or external pollutants, such as dust; or wear metals emanating from, for example, parts with which the oil is in contact during use; or even fractions of fuel (gas oil or gasoline) more or less oxidized or thermally cracked and which may be in liquid or solid form including soot; or else contaminants related to the storage of used oils in which there are sometimes substances constituting light fractions which are generally water or chlorinated or petroleum solvents.
This results in a polluted oil with a stronger coloration than the original clean oil, hence the name of black oils in the field of waste oils, in particular because of the presence of oxidation products or cracking fuel. In order to be reusable, the oil must be rid of these contaminants and, for this reason, do, is brought to undergo clearance operations generally similar to those of refining.

On connait des procédés permettant de purifier des huiles usées ou des huiles usagées. En particulier, FR 2 961 521 décrit un procédé de purification d'huiles usées comprenant des additifs, des produits de dégradation, des contaminants ou des polluants.Methods are known for purifying used oils or waste oils. In particular, FR 2 961 521 discloses a process for purifying waste oils comprising additives, degradation products, contaminants or pollutants.

Toutefois, ces procédés présentent des inconvénients et ne sont donc pas satisfaisants. En particulier, les procédés connus ne permettent pas de valoriser l'ensemble des produits issus de la purification des huiles usées ou lors de la purification des huiles usagées.However, these methods have disadvantages and are therefore not satisfactory. In particular, the known processes do not make it possible to valorize all the products resulting from the purification of used oils or during the purification of used oils.

De plus ces procédés nécessitent d'importants gisements d'huiles usagées et ne sont pas adaptés à de petits territoires ou à des territoires isolés.In addition, these processes require large deposits of used oils and are not suitable for small territories or isolated territories.

L'invention fournit donc un procédé permettant d'apporter une solution à tout ou partie des problèmes des procédés de l'état de la technique.The invention thus provides a method for providing a solution to all or part of the problems of the methods of the state of the art.

L'invention concerne un procédé de purification d'une charge hydrocarbonée, comprenant les étapes suivantes :a) purification, par extraction des composés légers, de la charge hydrocarbonée ;b) séparation, par filtration en présence d'un fluide à l'état supercritique, de la charge hydrocarbonée purifiée obtenue à l'étape a), et obtention d'un filtrat et d'un retentat ;c) purification, par saponification, du filtrat obtenu à l'étape b);d) séparation, par distillation sous vide ou sous pression réduite, du filtrat purifié obtenu à l'étape c) et obtention d'une charge purifiée et distillée et d'un résidu de distillation ;
e) lavage, au moyen d'une solution aqueuse, du résidu de distillation obtenu à l'étape d) ;f) séparation du résidu de distillation lavé obtenu à l'issue de l'étape e) en une phase aqueuse et une phase organique, la charge hydrocarbonée étant choisie parmi une huile minérale ou d'origine minérale ou une huile de synthèse ou d'origine synthétique.The invention relates to a process for purifying a hydrocarbon feedstock, comprising the following steps: a) purification, by extraction of the light compounds, of the hydrocarbon feedstock, b) separation, by filtration in the presence of a fluid in the state supercritical, of the purified hydrocarbon feedstock obtained in step a), and obtaining a filtrate and a retentate c) purification, by saponification, of the filtrate obtained in step b) d) separation, by distillation under vacuum or under reduced pressure, purified filtrate obtained in step c) and obtaining a purified and distilled filler and a distillation residue;
e) washing, by means of an aqueous solution, the distillation residue obtained in step d), f) separating the washed distillation residue obtained at the end of step e) into an aqueous phase and a phase organic, the hydrocarbon feedstock being selected from a mineral or mineral oil or a synthetic oil or synthetic origin.

De préférence, la charge hydrocarbonée est choisie parmi les huiles minérales issues de la distillation fractionnée du pétrole brut, notamment les huiles industrielles, les huiles d'engrenages, les huiles hydrauliques ou les huiles de moteur, usées ou usagées.Preferably, the hydrocarbon feedstock is chosen from mineral oils resulting from the fractional distillation of crude oil, in particular industrial oils, gear oils, hydraulic oils or used or used motor oils.

De manière avantageuse, les composés légers selon l'invention sont définis comme étant les composés volatils contenus dans la charge hydrocarbonée. Il s'agit par exemple de l'eau, de l'essence, des solvants, ou encore une partie de la coupe gazole.Advantageously, the light compounds according to the invention are defined as being the volatile compounds contained in the hydrocarbon feedstock. This is for example water, gasoline, solvents, or a portion of the diesel cut.

Généralement, la charge hydrocarbonée traitée selon le procédé de l'invention comprend un ou plusieurs hydrocarbures et éventuellement un ou plusieurs composés comprenant des atomes de carbone, d'hydrogène et qui peuvent également comprendre un ou plusieurs hétéroatomes. Généralement, la charge hydrocarbonée traitée selon le procédé de l'invention comprend également des composés à éliminer choisis parmi des additifs dispersants, des additifs détergents, des additifs anti-usure, des polymères, des suies, des éléments métalliques.Generally, the hydrocarbon feedstock treated according to the process of the invention comprises one or more hydrocarbons and optionally one or more compounds comprising carbon atoms, hydrogen and which may also comprise one or more heteroatoms. Generally, the hydrocarbon feedstock treated according to the process of the invention also comprises compounds to be eliminated selected from dispersant additives, detergent additives, anti-wear additives, polymers, soot, metal elements.

De manière préférée, l'étape a) d'extraction des composés légers est effectuée par distillation sous vide ou sous pression réduite. De manière avantageuse, l'étape a) d'extraction est une évaporation flash des composés légers.Preferably, step a) of extraction of the light compounds is carried out by distillation under vacuum or under reduced pressure. Advantageously, the extraction step a) is a flash evaporation of the light compounds.

Selon un mode de réalisation préféré, l'étape a) du procédé selon l'invention permet de purifier la charge hydrocarbonée par distillation, de préférence par distillation des composés légers.According to a preferred embodiment, step a) of the process according to the invention makes it possible to purify the hydrocarbon feedstock by distillation, preferably by distillation of the light compounds.

L'étape a) d'extraction du procédé selon l'invention permet également d'éliminer de l'eau ou la phase aqueuse qui peut être présente au sein de la charge hydrocarbonée.Step a) of extraction of the process according to the invention also makes it possible to eliminate water or the aqueous phase which may be present within the hydrocarbon feedstock.

L'étape a) d'extraction est notamment réalisée à une pression inférieure à 0,08 bar, par exemple inférieure à 0,05 bar, voire inférieure à 0,03 bar. Généralement, l'étape a) d'extraction est réalisée à une température allant de 100 à 250 °C, par exemple à environ 150 °C.The extraction step a) is in particular carried out at a pressure of less than 0.08 bar, for example less than 0.05 bar, or even less than 0.03 bar. Generally, the stage a) extraction is carried out at a temperature ranging from 100 to 250 ° C, for example at about 150 ° C.

Selon l'invention, l'étape b) de filtration de la charge hydrocarbonée obtenue à l'étape a) en présence d'un fluide à l'état supercritique est de préférence mise en oeuvre au moyen de CO2 à l'état supercritique bien que d'autres gaz, tels N2O, SF6, le méthane, l'éthane, le propane ou l'hexane, puissent convenir. Lors de l'étape (b), le CO2 à l'état supercritique est généralement mis en oeuvre en une quantité allant d'environ 2 à 60 % ou d'environ 15 à 20 % en masse de charge hydrocarbonée à purifier.
De manière préférée pour le procédé selon l'invention, l'étape (b) est une filtration tangentielle. De manière également préférée pour le procédé selon l'invention, l'étape (b) est réalisée à une température allant de 100 à 180 °C ou à une pression allant de 120 à 180 bar. Elle peut être réalisée à une température allant de 100 à 180 °C et à une pression allant de 120 à 180 bar.
L'étape (b) est réalisée au moyen d'un filtre qui peut être une membrane à base de métaux ou d'alliages métalliques tels que l'acier, par exemple l'acier inoxydable, ou le nickel ; d'oxydes tels que des oxydes choisis parmi Al2O3, ZrO2, TiO2.
L'étape (b) concerne la majorité des composés à éliminer, de préférence 80% voire 90% ou plus des composés à éliminer sont filtrés. Avantageusement, le filtre permet de retenir des composés ou des particules dont la taille moyenne, c'est-à-dire le diamètre moyen de particules, va de 1 nm à 10 µm, de manière préférée de 2 nm à 1 µm et de manière plus préférée de 2 nm à 0,1 µm.
D'une manière préférée selon l'invention, l'étape b) consiste en la séparation, par filtration tangentielle en présence de CO2 à l'état supercritique, de la charge hydrocarbonée obtenue à l'étape a), et permet l'obtention d'un filtrat et d'un rétentat.According to the invention, step b) of filtration of the hydrocarbon feedstock obtained in step a) in the presence of a fluid in the supercritical state is preferably carried out by means of CO 2 in the supercritical state although other gases, such as N 2 O, SF 6, methane, ethane, propane or hexane, may be suitable. During step (b), the CO 2 in the supercritical state is generally used in an amount ranging from about 2 to 60% or about 15 to 20% by weight of hydrocarbon feedstock to be purified.
In a preferred manner for the process according to the invention, step (b) is a tangential filtration. Also preferably for the process according to the invention, step (b) is carried out at a temperature ranging from 100 to 180 ° C or at a pressure ranging from 120 to 180 bar. It can be carried out at a temperature ranging from 100 to 180 ° C. and at a pressure ranging from 120 to 180 bar.
Step (b) is carried out by means of a filter which may be a membrane based on metals or metal alloys such as steel, for example stainless steel, or nickel; oxides such as oxides selected from Al 2 O 3 , ZrO 2 , TiO 2 .
Step (b) concerns the majority of the compounds to be removed, preferably 80% or even 90% or more of the compounds to be removed are filtered. Advantageously, the filter makes it possible to retain compounds or particles whose average size, ie the average particle diameter, ranges from 1 nm to 10 μm, preferably from 2 nm to 1 μm, and more preferred from 2 nm to 0.1 μm.
In a preferred manner according to the invention, step b) consists in the separation, by tangential filtration in the presence of CO 2 in the supercritical state, of the hydrocarbon feedstock obtained in step a), and allows the obtaining a filtrate and a retentate.

L'étape b) permet de séparer les composés à éliminer présents au sein du rétentat de filtration de la charge hydrocarbonée filtrée. La charge hydrocarbonée filtrée est alors traitée au moyen de l'agent de transformation.
De manière avantageuse, le rétentat obtenu à l'étape b) comprenant des composés à éliminer peut être concentré. Cette concentration du rétentat peut être réalisée en éliminant certains composés, en particulier des composés paraffiniques.Step b) makes it possible to separate the compounds to be eliminated present in the filtration retentate from the filtered hydrocarbon feedstock. The filtered hydrocarbon feedstock is then treated using the transformation agent.
Advantageously, the retentate obtained in step b) comprising compounds to be eliminated can be concentrated. This concentration of the retentate can be achieved by eliminating certain compounds, in particular paraffinic compounds.

De manière préférée, le filtrat obtenu à l'étape b) est purifié lors de l'étape c) de la charge au moyen d'un agent de transformation. De préférence, l'étape c) est réalisée par saponification. De préférence, le traitement c) par saponification est réalisé au moyen d'un agent de transformation choisi parmi NaOH ou KOH, utilisé seul ou en mélange. La saponification est préférentiellement réalisée au moyen de NaOH.Preferably, the filtrate obtained in step b) is purified in step c) of the feed by means of a transformation agent. Preferably, step c) is carried out by saponification. Preferably, the treatment c) by saponification is carried out using a transformation agent selected from NaOH or KOH, used alone or as a mixture. The saponification is preferably carried out using NaOH.

D'une manière préférée selon l'invention, l'étape c) consiste en la purification, par saponification au moyen de soude en solution aqueuse à environ 50% en masse, du filtrat obtenu à l'étape b).In a preferred manner according to the invention, step c) consists in the purification, by saponification using sodium hydroxide in aqueous solution at about 50% by weight, of the filtrate obtained in step b).

L'étape d) de séparation du filtrat purifié obtenu à l'étape c) est réalisée par distillation sous vide, par exemple par distillation sous vide à film tombant ou par distillation sous pression réduite en couche mince. Lors de la mise en oeuvre d'une distillation à film tombant, les paramètres de début de distillation sont avantageusement d'environ 19 mbar pour la pression, d'environ 240 °C pour la température du milieu et d'environ 50 °C pour la température en tête de colonne. En fin de distillation, ces paramètres sont généralement d'environ 19 mbar pour la pression, d'environ 375 °C tendant vers 400 °C pour la température du milieu et d'environ 375 °C pour la température en tête de colonne.
D'une manière préférée selon l'invention, l'étape d) consiste en la séparation, par distillation sous vide ou sous pression réduite, du filtrat purifié obtenu à l'étape c) et permet l'obtention d'une charge purifiée et distillée et d'un résidu de distillation. Avantageusement, la charge purifiée et distillée obtenue à l'issue de l'étape (d) possède des caractéristiques identiques à celles des huiles de base. Cette charge purifiée et distillée peut donc être utilisée comme huile de base au sein de compositions lubrifiantes.The step d) of separation of the purified filtrate obtained in step c) is carried out by vacuum distillation, for example by vacuum distillation with falling film or by distillation under reduced pressure in a thin layer. When performing a falling film distillation, the start-of-distillation parameters are advantageously about 19 mbar for the pressure, about 240 ° C for the medium temperature and about 50 ° C for the medium temperature. the temperature at the top of the column. At the end of distillation, these parameters are generally about 19 mbar for the pressure, about 375 ° C tending towards 400 ° C for the temperature of the medium and about 375 ° C for the temperature at the top of the column.
In a preferred manner according to the invention, step d) consists of the separation, by distillation under vacuum or under reduced pressure, of the purified filtrate obtained in stage c) and makes it possible to obtain a purified filler and distilled and a distillation residue. Advantageously, the purified and distilled feed obtained at the end of step (d) has characteristics identical to those of the base oils. This purified and distilled feedstock can therefore be used as a base oil in lubricating compositions.

L'étape e) consiste en le lavage du résidu de distillation obtenu à l'issue de l'étape d). D'une manière préférée selon l'invention, l'étape e) consiste en le lavage, au moyen d'une solution aqueuse, du résidu de distillation obtenu à l'étape d).
Lors de l'étape e), le résidu de distillation est traité au moyen d'une solution aqueuse. De manière préférée, l'étape e) est réalisée avec de l'eau, par exemple en une quantité allant de 1 à 5 fois, de préférence de 1 à 3 fois, le volume de résidu de distillation obtenu. Le mélange de la solution aqueuse et du résidu de distillation peut être agité.
L'étape (e) peut être mise en oeuvre avec des quantités variable de solution aqueuse. Un mélange comprenant 20, 30 ou 50 % en poids de résidu de distillation complété à 100 % en poids par de la solution aqueuse peut être avantageux.Step e) consists of washing the distillation residue obtained at the end of step d). In a preferred manner according to the invention, step e) consists in washing, by means of an aqueous solution, the distillation residue obtained in step d).
In step e), the distillation residue is treated with an aqueous solution. Preferably, step e) is carried out with water, for example in an amount ranging from 1 to 5 times, preferably from 1 to 3 times, the volume of distillation residue obtained. The mixture of the aqueous solution and the distillation residue can be stirred.
Step (e) can be carried out with varying amounts of aqueous solution. A mixture comprising 20, 30 or 50% by weight of distillation residue supplemented to 100% by weight with aqueous solution may be advantageous.

L'étape f) du procédé de l'invention consiste en la séparation des phases aqueuse et organique du résidu de distillation lavé obtenu à l'étape e). La séparation de l'étape f) peut être réalisée par décantation. Une fois la phase organique séparée, elle peut être séchée. Avantageusement, sa viscosité mesurée à 100 °C selon la norme ISO 3104 va de 50 à 400 mm2.s-1, de préférence de 100 à 200 mm2.s-1.Step f) of the process of the invention consists of separating the aqueous and organic phases of the washed distillation residue obtained in step e). The separation of step f) can be carried out by decantation. Once the organic phase is separated, it can be dried. Advantageously, its viscosity measured at 100 ° C. according to the ISO 3104 standard ranges from 50 to 400 mm 2 .s -1 , preferably from 100 to 200 mm 2 .s -1 .

D'une manière préférée selon l'invention, l'étape f) du procédé consiste en la séparation du résidu de distillation lavé obtenu à l'étape e) en une phase aqueuse et une phase organique.In a preferred manner according to the invention, step f) of the process consists of separating the washed distillation residue obtained in step e) into an aqueous phase and an organic phase.

Les caractéristiques particulières ou préférées du procédé selon l'invention peuvent être combinées les unes aux autres de manières à définir des variantes du procédé selon l'invention. En particulier les combinaisons spécifiques des caractéristiques préférées définissent des variantes préférées du procédé selon l'invention.The particular or preferred features of the method according to the invention can be combined with each other in ways to define variants of the method according to the invention. In particular, the specific combinations of the preferred characteristics define preferred variants of the process according to the invention.

De manière préférée, le procédé selon l'invention comprend les étapes successives :

  1. a) d'extraire par distillation sous vide ou sous pression réduite, des composés légers présents au sein de la charge hydrocarbonée comprenant un ou plusieurs composés à éliminer ;
  2. b) de filtrer les composés à éliminer de manière tangentielle en présence de CO2 à l'état supercritique ;
  3. c) de séparer le rétentat comprenant des composés à éliminer et de traiter la charge filtrée au moyen de soude en solution aqueuse à environ 50% en masse ;
  4. d) de séparer les composés transformés de la charge hydrocarbonée purifiée par distillation sous vide ou sous pression réduite et de séparer le résidu de distillation ;
  5. e) de laver le résidu de distillation au moyen d'une solution aqueuse ;
  6. f) de séparer la phase aqueuse et la phase organique du résidu de distillation lavé.
In a preferred manner, the process according to the invention comprises the successive steps:
  1. a) extracting by distillation under vacuum or under reduced pressure, light compounds present in the hydrocarbon feedstock comprising one or more compounds to be removed;
  2. b) filtering the compounds to be removed tangentially in the presence of CO 2 in the supercritical state;
  3. c) separating the retentate comprising compounds to be removed and treating the load filtered with soda in aqueous solution at about 50% by weight;
  4. d) separating the transformed compounds from the purified hydrocarbon feedstock by distillation under vacuum or under reduced pressure and separating the distillation residue;
  5. e) washing the distillation residue with an aqueous solution;
  6. f) separating the aqueous phase and the organic phase from the washed distillation residue.

Selon un mode de réalisation préféré, le procédé de l'invention comprend les étapes suivantes :

  1. a) distillation de la charge hydrocarbonée ;
  2. b) séparation, par filtration tangentielle tangentielle en présence de CO2 à l'état supercritique, de la charge hydrocarbonée purifiée obtenue à l'étape a), et obtention d'un filtrat et d'un rétentat ;
  3. c) purification, par saponification au moyen de soude en solution aqueuse à environ 50% en masse, du filtrat obtenu à l'étape b) ;
  4. d) séparation, par distillation sous vide ou sous pression réduite, du filtrat purifié obtenu à l'étape c) et obtention d'une charge purifiée et distillée et d'un résidu de distillation ;
  5. e) lavage, au moyen d'une solution aqueuse, du résidu de distillation obtenu à l'étape d) ;
  6. f) séparation du résidu de distillation lavé obtenu à l'étape e) en une phase aqueuse et une phase organique.
According to a preferred embodiment, the method of the invention comprises the following steps:
  1. a) distillation of the hydrocarbon feedstock;
  2. b) separation, by tangential tangential filtration in the presence of CO 2 in the supercritical state, of the purified hydrocarbon feed obtained in step a), and obtaining a filtrate and a retentate;
  3. c) purification, by saponification with sodium hydroxide in aqueous solution at about 50% by weight, of the filtrate obtained in step b);
  4. d) separating, by distillation under vacuum or under reduced pressure, the purified filtrate obtained in step c) and obtaining a purified and distilled feedstock and a distillation residue;
  5. e) washing, with an aqueous solution, the distillation residue obtained in step d);
  6. f) separating the washed distillation residue obtained in step e) into an aqueous phase and an organic phase.

Par ailleurs le procédé selon l'invention peut être mis en oeuvre au sein d'une installation comprenant au moins :

  • une première unité, par exemple une cuve, dans laquelle est placée la charge hydrocarbonée à purifier ;
  • une unité de filtration reliée à la première unité ; et
  • une unité de collecte du rétentat et une unité de collecte du filtrat de l'étape b) reliées toutes deux à l'unité de filtration.
Moreover, the method according to the invention can be implemented within an installation comprising at least:
  • a first unit, for example a tank, in which is placed the hydrocarbon feedstock to be purified;
  • a filtration unit connected to the first unit; and
  • a retentate collection unit and a filtrate collection unit of step b) both connected to the filtration unit.

De manière particulièrement avantageuse, le procédé selon l'invention permet de purifier une charge hydrocarbonée comprenant un ou plusieurs composés à éliminer et d'obtenir une charge hydrocarbonée purifiée.In a particularly advantageous manner, the process according to the invention makes it possible to purify a hydrocarbon feedstock comprising one or more compounds to be eliminated and to obtain a purified hydrocarbon feedstock.

De manière également avantageuse, le procédé selon l'invention permet d'obtenir un rétentat à l'issue de l'étape b). Ce rétentat possède des propriétés particulièrement avantageuses.Also advantageously, the method according to the invention makes it possible to obtain a retentate at the end of step b). This retentate has particularly advantageous properties.

De manière également avantageuse, le procédé selon l'invention permet d'obtenir à l'issue de l'étape f) la phase organique du résidu de distillation lavé.Also advantageously, the process according to the invention makes it possible to obtain, after step f), the organic phase of the washed distillation residue.

Les différents aspects de l'invention sont illustrés par les exemples qui suivent.The various aspects of the invention are illustrated by the following examples.

Exemple :Example:

Un mélange d'huiles usagées issu d'huiles de moteurs, d'huiles de ponts et d'huiles de boîtes de vitesses (5 000 L) provenant de véhicules poids lourds a été traité selon le procédé de l'invention. Le mélange d'huiles usagées est placé dans une cuve à double enveloppe qui est chauffée à 70 ou 80 °C puis chauffé au moyen d'un échangeur (150 °C).A mixture of used oils from motor oils, bridge oils and gearbox oils (5000 L) from heavy vehicles was processed according to the process of the invention. The used oil mixture is placed in a jacketed tank which is heated to 70 or 80 ° C and then heated by means of a heat exchanger (150 ° C).

L'eau présente dans le mélange d'huiles usagées est éliminée par une distillation flash (150 °C, 150 mbar) dans un autoclave de 50 L. Les éventuelles substances légères sont alors également séparées du mélange d'huile lors de l'évaporation flash.The water present in the waste oil mixture is removed by flash distillation (150 ° C, 150 mbar) in a 50 L autoclave. Any light substances are then also separated from the oil mixture during evaporation. flash.

Le mélange d'huiles usagés (4 600 L) issu de la distillation est ensuite filtré en présence de CO2 à l'état supercritique (150 °C, 150 bar) en une quantité d'environ 20 % en masse de la quantité d'huiles usagées entrant dans le dispositif.The waste oil mixture (4,600 L) obtained from the distillation is then filtered in the presence of CO 2 in the supercritical state (150 ° C., 150 bar) in a quantity of approximately 20% by mass of the amount of used oils entering the device.

Quinze membranes de microfiltration (produit Tami de Dahlia 0,14 µm) sont disposées dans une boucle de recirculation équipée d'une pompe centrifuge de grande capacité volumique. L'injection du mélange huiles usagées - CO2 est faite dans la ligne d'aspiration de la pompe centrifuge afin de maximiser le mélange des deux composantes avant la filtration. Le débit d'huiles usagées dans l'installation est de 165 kg/h. Le débit du filtrat et d'environ 125 kg/h. La différence entre pressions intérieure et extérieure des membranes de filtration (ΔP) est inférieure à 4 bar. On obtient un filtrat (2 870 L) et un rétentat de filtration (1 550 kg).Fifteen microfiltration membranes (product Tami Dahlia 0.14 microns) are arranged in a recirculation loop equipped with a centrifugal pump of large volume capacity. The injection of used oil - CO 2 mixture is made in the suction line of the centrifugal pump to maximize the mixing of the two components before filtration. The waste oil flow in the plant is 165 kg / h. The flow rate of the filtrate is about 125 kg / h. The difference between inner and outer pressures of the filtration membranes (ΔP) is less than 4 bar. A filtrate (2870 L) and a filtration retentate (1550 kg) are obtained.

Le rétentat de filtration est réintroduit dans la boucle de filtration. Les conditions de traitement sont similaires (150 °C, 150 bar). La quantité de CO2 est d'environ 30 % en masse de rétentat introduit. La vitesse de recirculation est d'environ 30-31 m3/h. Le débit de charge est de 50 kg/h et le débit de rétentat retraité est d'environ 43 kg/h.The filtration retentate is reintroduced into the filtration loop. The treatment conditions are similar (150 ° C., 150 bar). The amount of CO 2 is about 30% by weight of introduced retentate. The recirculation rate is about 30-31 m 3 / h. The charge rate is 50 kg / h and the retentate flow rate is about 43 kg / h.

Le filtrat obtenu lors de ce retraitement est mélangé au filtrat obtenu lors de la filtration du mélange d'huiles usagées.The filtrate obtained during this reprocessing is mixed with the filtrate obtained during the filtration of the used oil mixture.

On obtient une quantité totale de filtrat de 1 487 L et un rétentat de filtration (217 kg). On obtient un rétentat dont la masse volumique en mélange avec du CO2 est d'environ 982 kg/m3 (environ 300 kg/m3 en mélange avec du CO2).A total of 1,487 L filtrate and a filtration retentate (217 kg) are obtained. A retentate is obtained whose density mixed with CO 2 is about 982 kg / m 3 (about 300 kg / m 3 mixed with CO 2 ).

Les caractéristiques physico-chimiques du mélange d'huiles usagées, du rétentat et du filtrat sont présentées dans le tableau 1. Les quantités (A en mg), concentration (B en % en poids) et abattement (C en % en poids) des différents éléments chimiques sont également présentés dans le tableau 1. Tableau 1 Mélange d'huiles Rétentat Filtrat Viscosité cinématique à 40 °C 40,5 mm2.s-1 431 mm2.s-1 27,1 mm2.s-1 Viscosité cinématique à 100 °C 7,12 mm2.s-1 59,3 mm2.s-1 5 mm2.s-1 Indice de viscosité 138 209 109 Éléments présents (mg) A (mg) A (mg) B (%) A (mg) C (%) Li 0 3 / 0 / B 119 605 508 66 44,5 Na 60 372 620 8 86,7 Mg 48 210 438 12 75,0 Al 11 68 618 1 90,9 Si 112 251 224 80 28,6 P 523 1 484 284 320 38,8 S 6 434 9 047 141 5 194 19,3 K 50 324 648 8 84,0 Ca 874 5 233 599 157 82,0 Ti 2 15 750 0 100,0 V 0 1 / 0 / Cr 2 16 800 0 100,0 Mn 4 20 500 1 75,0 Fe 115 618 537 28 75,7 Ni 1 6 600 1 0 Cu 17 63 371 9 47,1 Zn 526 2 132 405 197 62,5 Mo 16 104 650 0 100,0 Ag 0 0 / 0 / Cd 0 1 / 0 / Sn 1 6 600 0 100,0 Sb 0 0 / 0 / Ba 9 56 622 1 88,9 Pb 7 12 171 7 0 Bi 0 0 / 0 / The physico-chemical characteristics of the used oil mixture, the retentate and the filtrate are presented in Table 1. The amounts (A in mg), concentration (B in% by weight) and abatement (C in% by weight) of the different chemical elements are also presented in Table 1. <u> Table 1 </ u> Blend of oils retentate filtrate Kinematic viscosity at 40 ° C 40.5 mm 2 .s -1 431 mm 2 .s -1 27.1 mm 2 .s -1 Kinematic viscosity at 100 ° C 7.12 mm 2 .s- 1 59.3 mm 2 .s -1 5 mm 2 .s -1 Viscosity index 138 209 109 Present elements (mg) A (mg) A (mg) B (%) A (mg) C (%) Li 0 3 / 0 / B 119 605 508 66 44.5 N / A 60 372 620 8 86.7 mg 48 210 438 12 75.0 al 11 68 618 1 90.9 Yes 112 251 224 80 28.6 P 523 1,484 284 320 38.8 S 6,434 9,047 141 5,194 19.3 K 50 324 648 8 84.0 It 874 5,233 599 157 82.0 Ti 2 15 750 0 100.0 V 0 1 / 0 / Cr 2 16 800 0 100.0 mn 4 20 500 1 75.0 Fe 115 618 537 28 75.7 Or 1 6 600 1 0 Cu 17 63 371 9 47.1 Zn 526 2,132 405 197 62.5 MB 16 104 650 0 100.0 Ag 0 0 / 0 / CD 0 1 / 0 / Sn 1 6 600 0 100.0 Sb 0 0 / 0 / Ba 9 56 622 1 88.9 Pb 7 12 171 7 0 Bi 0 0 / 0 /

On obtient un filtrat (2 870 L) qui est traité au moyen de soude (4 % en poids par rapport à la quantité de filtrat) en solution dans l'eau (4 % en poids par rapport à la quantité de filtrat) pendant 15 heures, à une température de 100 °C.A filtrate (2870 L) is obtained which is treated with sodium hydroxide (4% by weight relative to the amount of filtrate) in solution in water (4% by weight relative to the amount of filtrate) for 15 hours. hours, at a temperature of 100 ° C.

Puis, le mélange est distillé à pression réduite (50 mbar), à 290 °C, au moyen d'un évaporateur à film mince équipé de racleurs rigides.Then, the mixture is distilled at reduced pressure (50 mbar) at 290 ° C using a thin-film evaporator equipped with rigid scrapers.

Une évaporation flash est ensuite mise en oeuvre (5 mbar) suivie d'une distillation (5 mbar et 315 °C). On obtient une huile purifiée et un résidu de distillation. Flash evaporation is then carried out (5 mbar) followed by distillation (5 mbar and 315 ° C.). A purified oil and a distillation residue are obtained.

L'huile purifiée obtenue après distillation est analysée et comparée à deux huiles commerciales (une huile de base raffinée et une huile de base régénérée):

  • ▪ spectrométries Infra-rouge,
  • ▪ analyse élémentaire et teneurs en métaux,
  • ▪ analyse élémentaire : carbone, hydrogène, soufre, azote, oxygène, métaux et métalloïdes,
  • ▪ caractéristiques techniques: couleur, viscosité (plusieurs déterminations à températures variées), point d'écoulement, point éclair, résidu Conradson, teneur en eau, indice d'acide, indice d'iode, point d'aniline, distillation simulée et réelle des hydrocarbures, masse volumique.
The purified oil obtained after distillation is analyzed and compared with two commercial oils (a refined base oil and a regenerated base oil):
  • ▪ Infra-red spectrometries,
  • ▪ elemental analysis and metal contents,
  • ▪ elemental analysis: carbon, hydrogen, sulfur, nitrogen, oxygen, metals and metalloids,
  • ▪ technical characteristics: color, viscosity (several determinations at various temperatures), pour point, flash point, Conradson residue, water content, acid number, iodine number, aniline point, simulated and actual distillation hydrocarbons, density.

Les caractéristiques et les propriétés de l'huile purifiée obtenue selon l'invention sont présentées dans le tableau 2. Tableau 2 Viscosité cinématique à 40 °C (NF EN ISO 3104) mm2.s-1 29,16 Viscosité cinématique à 100 °C (NF EN ISO 3104) mm2.s-1 5,238 Indice de viscosité (NF ISO 2909 - mode de calcul B) / 111 Point d'écoulement (NFT 60-105) °C -18 Point éclair vase ouvert (Cléveland) (NF EN ISO 2 592) °C 228 Résidu Conradson (NF EN ISO 10870) % m/m <10 Teneur en eau (Karl Fischer) % m/m <0,1 Indice d'acide (NF EN ISO 6 618) mg(KOH).g-1 0,01 Indice d'iode (NF EN ISO 3 961) g/100 g 5,1 Point aniline (ASTM D611) °C 106,40 The characteristics and the properties of the purified oil obtained according to the invention are presented in Table 2. <u> Table 2 </ u> Kinematic viscosity at 40 ° C (NF EN ISO 3104) mm 2 .s -1 29,16 Kinematic viscosity at 100 ° C (NF EN ISO 3104) mm 2 .s -1 5,238 Viscosity index (NF ISO 2909 - calculation method B) / 111 Pour point (NFT 60-105) ° C -18 Open cup flash point (Cléveland) (NF EN ISO 2,592) ° C 228 Residue Conradson (NF EN ISO 10870) % m / m <10 Moisture content (Karl Fischer) % m / m <0.1 Acid number (NF EN ISO 6 618) mg (KOH) .g -1 0.01 Iodine number (NF EN ISO 3 961) g / 100 g 5.1 Aniline point (ASTM D611) ° C 106.40

Les teneurs en composés hydrocarbures aromatiques polycycliques (HAP) ont été analysées par chromatographie (HPLC et détection en UV-fluorimétrie). Ils ont été comparés à ceux obtenus par analyse d'une huile régénérée selon une méthode de l'état de la technique (huile EH). Les résultats sont présentés dans le tableau 3. Tableau 3 HAP Huile régénérée (mg/kg) Score tox. Huile selon l'invention (mg/kg) Score tox. Naphtalene 0,40 0,0004 0,31 0,0003 Acenaphtylene 0,50 0,0005 0,20 0,0002 Acenaphtene 0,19 0,0002 0,05 5E-05 Fluorene 0,61 0,0006 0,15 0,0002 Phenanthrene 5,00 0,005 4,00 0,004 Anthracene 0,42 0,0042 0,24 0,0024 Fluoranthene 1,40 0,0014 1,50 0,0015 Pyrene 4,70 0,0047 5,50 0,0055 Benzo (a) anthracene 0,77 0,077 1,80 0,18 Chrysene 0,73 0,0073 1,10 0,011 Benzo (b) fluoranthene 3,40 0,34 1,50 0,15 Benzo (k) fluoranthene 0,50 0,05 0,33 0,033 Benzo (a) pyrene 4,40 4,4 0,49 0,49 Indeno 1,2,3 (c,d) pyrene 2,80 0,28 0,44 0,044 Dibenzo (a,h) anthracene 0,64 0,64 0,25 0,25 Dibenzo (g,h,i) perylene 13,00 0,13 3,50 0,035 Contenu extrait HAP 0,80 / 0,70 / TEQ (% en poids) / 5,9413 / 1,2071 The contents of polycyclic aromatic hydrocarbon compounds (PAHs) were analyzed by chromatography (HPLC and detection in UV-fluorimetry). They were compared with those obtained by analysis of a regenerated oil according to a method of the state of the art (oil EH). The results are shown in Table 3. <u> Table 3 </ u> PDT Regenerated oil (mg / kg) Tox Score Oil according to the invention (mg / kg) Tox Score naphthalene 0.40 0.0004 0.31 0.0003 acenaphthylene 0.50 0.0005 0.20 0.0002 acenaphtene 0.19 0.0002 0.05 5E-05 fluorene 0.61 0.0006 0.15 0.0002 phenanthrene 5.00 0.005 4.00 0,004 anthracene 0.42 0.0042 0.24 0.0024 fluoranthene 1.40 0.0014 1.50 0.0015 Pyrene 4.70 0.0047 5.50 0.0055 Benzo (a) anthracene 0.77 0.077 1.80 0.18 cHRYSENE 0.73 0.0073 1.10 0,011 Benzo (b) fluoranthene 3.40 0.34 1.50 0.15 Benzo (k) fluoranthene 0.50 0.05 0.33 0.033 Benzo (a) pyrene 4.40 4.4 0.49 0.49 Indeno 1,2,3 (c, d) pyrene 2.80 0.28 0.44 0.044 Dibenzo (a, h) anthracene 0.64 0.64 0.25 0.25 Dibenzo (g, h, i) perylene 13,00 0.13 3.50 0,035 Content extracted HAP 0.80 / 0.70 / TEQ (% by weight) / 5.9413 / 1.2071

Les caractéristiques et les propriétés de l'huile purifiée obtenue selon l'invention sont équivalentes ou supérieures à celles des deux huiles. L'huile de base selon l'invention peut donc être utilisée dans une composition lubrifiante, notamment dans une composition lubrifiante pour moteur de véhicule.The characteristics and properties of the purified oil obtained according to the invention are equivalent to or greater than those of the two oils. The base oil according to the invention can therefore be used in a lubricant composition, especially in a lubricant composition for a vehicle engine.

Le résidu de distillation obtenu après distillation a été lavé avec de l'eau sous agitation durant 4 heures puis la phase organique a été séparée par décantation durant 12 heures. On obtient une huile de paraffine dont la viscosité mesurée à 100 °C est de 150 mm2.s-1. Cette huile peut être utilisée pour lubrifier des engrenages, notamment des engrenages ouverts.The distillation residue obtained after distillation was washed with water with stirring for 4 hours and then the organic phase was separated by decantation for 12 hours. A paraffin oil is obtained whose viscosity measured at 100 ° C. is 150 mm 2 .s -1 . This oil can be used to lubricate gears, including open gears.

Par ailleurs, le rétentat de filtration a été évalué pour ses propriétés d'additif pour bitume. Le rétentat est mélangé avec du bitume puis ses propriétés de tenue au sein du mélange ainsi que l'amélioration des propriétés du bitume additivé ont été analysées.
Le programme est établi en deux phases. La première concerne le comportement du mélange de rétentat et de bitume, avant et après simulation d'un l'enrobage. Les mesures reposent principalement sur l'évaluation de la consistance des produits, conformément aux spécifications réglementaires européennes. La seconde phase traite du matériau enrobé, fabriqué par malaxage de granulats, d'un bitume et du rétentat. La compactibilité, la résistance au désenrobage par l'eau et la capacité à résister à l'ornièrage sont évaluées.
La classe de bitume choisi est 35/50. Le taux de modification du bitume par le rétentat a été fixé à 2,5% en poids.In addition, the filtration retentate was evaluated for its bitumen additive properties. The retentate is mixed with bitumen and its resistance properties within the mixture as well as the improvement of the properties of the additive bitumen were analyzed.
The program is established in two phases. The first concerns the behavior of the mixture of retentate and bitumen, before and after simulation of a coating. The measures are based mainly on the assessment of the consistency of the products, in accordance with the European regulatory specifications. The second phase deals with the coated material, made by mixing aggregates, bitumen and retentate. The compactibility, water stripping resistance and ability to resist rutting are evaluated.
The bitumen class chosen is 35/50. The rate of modification of the bitumen by the retentate was set at 2.5% by weight.

Les mesures de module complexe montrent que le mélange rétentat et bitume est rhéologiquement simple. Ceci traduit une bonne compatibilité des deux matériaux.Complex modulus measurements show that the retentate and bitumen mixture is rheologically simple. This reflects a good compatibility of the two materials.

Cet enrobé, de type Grave bitume, réalisé avec un bitume 35/50 additivé à 2,5 % en poids de rétentat, est conforme aux spécifications de niveau 2 (pour une GB de classe 4).
Le mélange bitume 35/50 et rétentat (2,5 % en poids) est conforme aux spécifications des bitumes routiers et donne un enrobé de type Grave bitume de classe 4 conforme jusqu'au niveau 2.This bitumen-type asphalt, made with a 35/50 bitumen additive containing 2.5% by weight of retentate, complies with the level 2 specifications (for a Class 4 GB).
The mixture 35/50 bitumen and retentate (2.5% by weight) complies with the specifications of road bitumens and gives a gravel bitumen of class 4 compliant up to level 2.

Un essai de lixiviation selon la norme NF EN 12 457-2 a également été réalisé. Un sable bitume 35/50 a été comparé au même sable bitume 35/50 additivé avec 2,5% de rétentat. L'analyse de l'éluat après test de lixiviation montre une teneur en carbone organique total (selon NF EN 1484) de 17 mg/kg pour l'échantillon de référence et de 31 mg/kg pour l'échantillon réalisé à partir de bitume additivé.
Les deux échantillons présentent un profil chromatographique similaire exempt de molécules organiques semi-volatiles détectables par cette technique. En conséquence, l'ajout au bitume de rétentat d'ultrafiltration n'altère pas son comportement au contact de l'eau : aucune substance semi-volatile n'est détectable dans le lixiviat.A leaching test according to standard NF EN 12 457-2 has also been carried out. A 35/50 bitumen sand was compared to the same 35/50 bitumen sand additive with 2.5% retentate. The analysis of the eluate after leaching test shows a total organic carbon content (according to NF EN 1484) of 17 mg / kg for the reference sample and 31 mg / kg for the sample made from bitumen additive.
Both samples have a similar chromatographic profile free of semi-volatile organic molecules detectable by this technique. As a result, the addition of ultrafiltration retentate to the bitumen does not alter its behavior on contact with water: no semi-volatile substance is detectable in the leachate.

Un test de résistance à la démixtion a été réalisé pour le bitume additivé du rétentat selon l'invention.
Le rétentat mélangé au bitume a été placé dans un tube vertical puis laissé au repos durant 36 heures à 180 °C. Après refroidissement, les points de ramollissement du mélange issu des parties haute et basse du tube ont été mesurés. On obtient des températures de ramollissement de 51,8 °C pour le mélange issu de la partie haute et de 51,4 °C pour le mélange issu de la partie haute.
Ces températures très proches confirment qu'aucune démixtion n'a eu lieu. Le bitume additivé du rétentat selon l'invention est donc stable au stockage.A demixing resistance test was carried out for the additive bitumen of the retentate according to the invention.
The retentate mixed with the bitumen was placed in a vertical tube and then allowed to stand for 36 hours at 180 ° C. After cooling, the softening points of the mixture from the top and bottom of the tube were measured. Softening temperatures of 51.8 ° C are obtained for the mixture coming from the upper part and 51.4 ° C for the mixture coming from the upper part.
These very close temperatures confirm that no demixing took place. The additive bitumen of the retentate according to the invention is therefore storage stable.

La résistance à l'orniérage du bitume additivé du rétentat selon l'invention a été évaluée au moyen d'un banc Gamma selon la méthode NF EN 12697 partie 22.
Les résultats d'orniérage sont très bons pour le bitume additivé du rétentat selon l'invention. En effet, alors que la valeur normative moyenne de la profondeur d'ornière après 10 000 passages doit être inférieure à 10 %, le bitume additivé du rétentat selon l'invention permet une valeur de 4,6 %.The resistance to rutting of the additive bitumen of the retentate according to the invention was evaluated by means of a Gamma bank according to the method NF EN 12697 part 22.
The rutting results are very good for the additive bitumen of the retentate according to the invention. Indeed, while the average normative value of the rut depth after 10,000 passes must be less than 10%, the bitumen additive of the retentate according to the invention allows a value of 4.6%.

Claims (9)

  1. A process for purifying a hydrocarbon feed, comprising the steps of:
    a) Purification, by extraction of the light compounds, of the hydrocarbon feedstock;
    b) separation, by filtration in the presence of a fluid in the supercritical state, of the purified hydrocarbon feedstock obtained in step a), and obtaining a filtrate and a retentate;
    c) purification, by saponification, of the filtrate obtained in step b);
    d) Separation, by distillation under vacuum or under reduced pressure, of the purified filtrate obtained in step c) and obtaining a purified and distilled feedstock and a distillation residue;
    e) Washing, using an aqueous solution, of the distillation residue obtained in step d);
    f) Separation of the washed distillation residue obtained in step e) into an aqueous phase and an organic phase,
    The hydrocarbon feedstock being chosen from a mineral oil or an oil of mineral origin or an oil which is synthetic or of synthetic origin.
  2. Method according to claim 1 wherein the hydrocarbon feedstock is selected from mineral oils from the fractional distillation of crude oil, including industrial oils, gear oils, hydraulic oils or motor oils, used or old.
  3. Method according to claim 1 or 2, wherein the hydrocarbon feedstock comprises compounds to eliminate selected from dispersant additives, detergent additives, antiwear additives, polymers, soot, metallic elements.
  4. Method according to any of claims 1 to 3, wherein step a) is performed by distillation under vacuum or under reduced pressure.
  5. Method according to any of claims 1 to 4, wherein the fluid in the supercritical state used in step b), preferably CO2, is present in an amount ranging from about 2 to 60% or about 15 to 20% by weight of hydrocarbon feedstock to be purified.
  6. Method according to any of claims 1 to 5, wherein step b) is a filtration:
    - Tangential; or
    - Performed at a temperature ranging from 100 to 180 ° C or at a pressure ranging from 120 to 180 bar.
  7. Method according to any of claims 1 to 6, wherein step c) is carried out using a compound selected from NaOH or KOH, used alone or in admixture.
  8. Method according to any of claims 1 to 7, wherein the retentate obtained in step b) is concentrated.
  9. Method according to any of claims 1 to 8, wherein the purification of step a) is performed by distillation and the separation of step b) is performed by tangential filtration in the presence of CO2 in the supercritical state, and the purification of step c) is performed by saponification using sodium hydroxide in aqueous solution at about 50% by weight.
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