EP3121254B1 - Ölreinigung und herstellung eines zusatzes gegen spurrinnenbildung - Google Patents

Ölreinigung und herstellung eines zusatzes gegen spurrinnenbildung 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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English (en)
French (fr)
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EP3121254A1 (de
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)

Claims (9)

  1. Verfahren zur Reinigung einer Kohlenwasserstoffeinspeisung, welches die folgenden Schritte umfasst:
    (a) Reinigung der Kohlenwasserstoffeinspeisung durch Extraktion leichter Verbindungen;
    (b) Trennung der in Schritt (a) erhaltenen gereinigten Kohlenwasserstoffeinspeisung durch Filtration in Gegenwart eines überkritischen Fluids und Erhalt eines Filtrats und eines Retentats;
    (c) Reinigung des in Schritt (b) erhaltenen Filtrats durch Verseifung;
    (d) Abtrennen des in Schritt (c) erhaltenen gereinigten Filtrats durch Vakuum- oder Unterdruckdestillation und Erhalt eines gereinigten und destillierten Ausgangsmaterials und eines Destillationsrückstands;
    e) Waschen des in Schritt (d) erhaltenen Destillationsrückstands mit einer wässrigen Lösung;
    (f) Trennung des in Schritt (e) erhaltenen gewaschenen Destillationsrückstands in eine wässrige Phase und eine organische Phase
    in welchem die Kohlenwasserstoffeinspeisung wird ausgewählt aus einem Mineralöl oder einem Öl mit mineralischem Ursprung, einem synthetischen Öl oder einem Öl mit synthetischem Ursprung.
  2. Verfahren nach Anspruch 1, in welchem die Kohlenwasserstoffeinspeisung ausgewählt wird aus Mineralölen, die aus fraktionierten Destillation von Rohöl abgeleitet sind, insbesondere aus Industrieölen, Getriebeölen, Hydraulikölen oder Motorölen, gebrauchte oder verwendete.
  3. Verfahren nach einem der Ansprüche 1 oder 2, in welchem die Kohlenwasserstoffeinspeisung Verbindungen umfasst, die zu entfernen sind, ausgewählt aus Dispergieradditiven, Waschmittelzusätzen, Verschleißschutzzusätzen, Polymeren, Ruß, Metallelementen.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dessen Schritt a) durch Vakuumdestillation oder Unterdruckdestillation durchgeführt wird.
  5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem das in Schritt b) verwendete überkritische Fluid, vorzugsweise CO2, in einer Menge von etwa 2 bis 60 % oder etwa 15 bis 20 Gew.-% der zu reinigenden Kohlenwasserstoffeinspeisung vorhanden ist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dessen Schritt b)
    - eine tangentiale Filtration ist; oder
    - ist bei einer Temperatur zwischen 100 und 180°C oder einem Druck zwischen 120 und 180 bar durchgeführt.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dessen Schritt c) mittels einer Verbindung, ausgewählt aus NaOH oder KOH, allein oder in einem Gemisch durchgeführt wird.
  8. Verfahren nach einem der Ansprüche 1 bis 7, wobei das in Schritt b) erhaltene Retentat konzentriert wird.
  9. Verfahren nach einem der Ansprüche 1 bis 8, wobei die Reinigung des Schrittes a) ist durch Destillation durchgeführt, die Trennung des Scrittes b) ist durch tangentiale Filtration in Gegenwart von überkritischem CO2 durchgeführt, und die Reinigung des Schrittes c) ist durch Verseifung mit Soda in wässriger Lösung mit etwa 50 Gew.-% durchgeführt.
EP16180213.7A 2015-07-20 2016-07-19 Ölreinigung und herstellung eines zusatzes gegen spurrinnenbildung Active EP3121254B1 (de)

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FR3101256B1 (fr) * 2019-09-26 2021-11-12 Safran Ceram Procédé de traitement d’une huile chargée en HAP

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FR2735785B1 (fr) * 1995-06-22 1997-08-08 Chavet Bernard Procede de raffinage d'huiles usagees par traitement alcalin
ITMI20080581A1 (it) * 2008-04-03 2009-10-04 Eni Spa Processo per il trattamento di residui oleosi provenienti dall'industria petrolifera
FR2961521B1 (fr) * 2010-06-22 2013-07-12 Conception D Equipements Pour L Environnement Et L Ind Soc D Procede de purification d'une charge hydrocarbonee usagee

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FR3039162A1 (fr) 2017-01-27
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