Classifications

• • 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
  • 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
  • C10G31/09—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
  • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
  • C10G31/10—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for with the aid of centrifugal force
• • 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
  • 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
  • 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
  • C10M175/0075—Working-up used lubricants to recover useful products ; Cleaning synthetic oil based
• • 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
  • C10M175/02—Working-up used lubricants to recover useful products ; Cleaning mineral-oil based
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B3/00—Refining fats or fatty oils
  • C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
• • 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
  • 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
  • C10G2300/1022—Fischer-Tropsch products
• • 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
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/205—Metal content

Definitions

• the present invention relates to a process for treating or purifying a hydrocarbon feed comprising pollutant compounds, undesirable or requiring to be removed, in particular to allow the use of the hydrocarbon feedstock thus purified.
• the invention also relates to the treatment of this charge by means of a transformation agent.
• the process according to the invention can be implemented for the treatment of waste oils, such as motor oils, hydraulic oils, gear oils or industrial oils, and mixtures thereof, in particular to regenerate them. in a lubricating base of commercial quality identical to the original product for a new use.
• This type of treatment may be referred to as "re-refining or regenerating used oils".
• the field of the invention is therefore that of the regeneration of hydrocarbon feedstocks, such as used or used oils such as motor oils, hydraulic oils, gear oils or industrial oils, and mixtures thereof.
• An oil corresponds, conventionally to a mixture of hydrocarbons also comprising various additives reinforcing the intrinsic properties of this oil or providing additional properties for a specific use.
• additives commonly used in oils, in particular in motor oils mention may be made of:
• antioxidant additives • antioxidant additives whose function is to slow the oxidation of the oil and thus extend its life;
• Dispersant additives for example alkyl-succimides, which serve to suspend in the oil solid impurities present in the engine oil such as soot, dust, wear metals;
• Anti-wear additives contributing to forming a protective film on the surfaces of the parts in contact with said oil, for example organometallic compounds such as zinc alkyl-dithio-phosphates;
• Antirust additives for example sulfonates or phenolates, viscosity index improvers or anti-foam additives, etc.
• the oils are subjected to stresses that will cause their degradation leading to an increase in the contaminant content of said oils, these contaminants may be derived from a degradation of the aforementioned additives, such as 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.
• additives such as 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
• Finishing operations essentially to obtain a discolored oil, for example, by adsorption of said oils on activated bleaching grounds or by catalytic hydrogenation.
• Another solution may be to add an adjuvant to the oil to be treated, which will make it possible to reduce the viscosity of the liquid to be filtered.
• This adjuvant may be a liquid organic solvent such as propane, hexane, heptane or any other organic solvent miscible in the oil.
• a fluid in the supercritical state such as carbon dioxide in the supercritical state, as described in the international patent application WO-00 / 521-18.
• these methods can lead to an important transition from undesirable elements in the filtrate through the filter, which is to be avoided.
• this method has the disadvantage of introducing a base in a non-depolluted load; the chemical treatment can not be total without consuming a large amount of base and generate significant amounts of waste.
• Patent Application EP-1712608 describes a process for the regeneration of used mineral oils to obtain lubricating bases. This process comprises the demetallization of the oil by means of treatment with an ammonium salt and then a double distillation in the presence of alkali hydroxides of the demetallized oil. This process can be carried out at moderate temperatures in order to preserve the installations used.
• the invention provides a process for purifying a hydrocarbon feedstock comprising additives, degradation products, contaminants or any pollutant compounds or compounds requiring to be eliminated, in particular with a view to allowing the use of the hydrocarbon feedstock as well as purified.
• the method according to the invention makes it possible to provide a solution to all or part of the problems of known methods.
• the method according to the invention allows a significant reduction in the passage of contaminant elements through the filter during the filtration treatment of a used oil, regardless of the filtration mode used.
• the process according to the invention also makes it possible to purify waste oils and thus to allow their reuse, in particular as a lubricating base.
• the process according to the invention easily adapts to the size of the deposits of used oil to be purified. It is particularly advantageous in terms of investment in equipment compared to processes using distillation under reduced pressure followed by treatment under high pressure of hydrogen, while being non-polluting compared to known processes using sulfuric acid. concentrated. In addition, it is nondestructive of the base oil molecules and avoids the chemical transformation of the feedstock because the molecules making up the base oil are not thermally or oxidatively converted.
• a first aspect of the invention therefore relates to a process for purifying a hydrocarbon feedstock, comprising one or more compounds to be eliminated, which comprises the steps of:
• the invention relates to a process comprising successively steps (a), (b), (c) and (d).
• the hydrocarbon feedstock is generally a feedstock comprising one or more hydrocarbons and optionally one or more compounds comprising carbon atoms, hydrogen atoms and which may also comprise one or more heteroatoms.
• the hydrocarbon feedstock is a mineral or mineral oil or a synthetic or synthetic oil derived from petrochemistry.
• mineral oils derived from the fractional distillation of crude oil which, properly additivated, become industrial oils, gear oils, hydraulic oils or motor oils.
• polyisobutenes As synthesis oil, mention may be made of polyisobutenes, poly- ⁇ -olefins, hydrotreated or hydroisomerized lubricating bases, IOPs or polyolefin olefins.
• the hydrocarbon feedstock is in liquid form under the conditions of implementation of the process.
• the compound (s) to be eliminated are:
• additives initially present in the unwashed or used load including dispersant additives, detergent additives, anti-wear additives, polymers; and may have been degraded in whole or in part;
• elements initially not included in the load including water, dust, soot, metal elements from eg the wear of the parts with which the load is in contact during use.
• the dispersant additives may be organic compounds comprising a polar part and a lipophilic part and may allow the suspension within the hydrocarbon feedstock of solid or colloidal elements such as dust, soot, wear metals, solid residues or colloidal oxidation. These dispersant additives generally make it possible to prevent these solid or colloidal elements from agglomeration and thus prevent the formation of deposits within the filler These dispersant additives constitute the major chemical obstacle preventing the disassembly of the used lubricant.
• the dispersing additives may for example be alkenylsuccinimide compounds, in particular of formula (1):
• R 1 represents a hydrocarbon group, or "Mannich base” type compounds, in particular of formula (2):
• R 2 represents an alkyl group
• the extraction of the light compounds present within the feed has for main purpose the elimination of fuels or water.
• the elimination of water is particularly advantageous when a ceramic filtration membrane is used.
• the extraction step is carried out under vacuum or under reduced pressure, preferably under the usual vacuum extraction conditions.
• the extraction step is carried out at a pressure customary for those skilled in the art, in particular at a pressure of less than 0.08 bar, for example less than 0.05 bar, or even less than 0.03 bar.
• the extraction step is carried out at a temperature customary for those skilled in the art, in particular at a temperature ranging from 100 to 250 ° C., for example at about 150 ° C.
• the filtration 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 filtration of the compounds 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 .
• the filter makes it possible to retain compounds or particles whose mean size, ie the mean particle diameter, ranges from 1 nm to 10 ⁇ m, in a manner that is preferably 2nm at 1 ⁇ and more preferably from 2nm to 0.1 ⁇ .
• the filtration is a frontal filtration or a tangential filtration, in particular a monophasic tangential filtration.
• the flow of charge meets or crosses the filter perpendicularly when the filtration is frontal or flows parallel to the filter surface when the filtration is tangential.
• the filtration is assisted or carried out in the presence of a fluid in the supercritical state.
• the fluid in the supercritical state can be selected from CO 2 , N 2 O, SF 6 , alkanes such as methane, ethane, propane or hexane.
• the fluid in the supercritical state is CO 2 .
• the fluid in the supercritical state may be present in an amount ranging from 2 to 60% by weight of hydrocarbon feedstock to be purified, preferably in an amount ranging from 8 to 30%, more preferably ranging from about 12 to 25%, even more preferably in an amount of about 15% to 20%, especially when this fluid is CO 2 .
• the filtration is carried out at a temperature ranging from 50 to 450 ° C., preferably from 60 to 200 ° C., more preferably ranging from 100 to 180 ° C., even more preferably from 100 to 180 ° C. approximately 15 ° C.
• the filtration is carried out at a pressure ranging from 50 to 350 bar, preferably from 100 to 250 bar, more preferably from 120 to 180 bar, even more preferred about 150 bars.
• the membrane or filter retains all the particles or compounds having a diameter greater than the average mesh size of said filter and thus make it possible to isolate a filtrate freed from these compounds or particles, or even size molecules. smaller that can be retained by polarization effect of the layer.
• the action of the fluid in the supercritical state can be implemented before, simultaneously with or after the filtration step.
• the fluid in the supercritical state generally makes it possible to reduce the viscosity of the hydrocarbon feedstock to be treated and thus allow or facilitate its filtration.
• a lowering of the viscosity by a factor of 4 to 5 is possible.
• the dissolution of the supercritical fluid in the hydrocarbon feed leads to an increase in its volume. This increase can be from a factor ranging from 1.01 to 3, in particular a factor of about 1.15.
• the monophasic tangential filtration within the process according to the invention makes it possible in particular to retain the metals or soots that would still be present in the hydrocarbon feedstock, especially in used oil, after an initial extraction step.
• the hydrocarbon feedstock may be subjected to a biphasic filtration assisted by a supercritical fluid and to separate a residue, highly viscous or solid, a purified liquid and high viscosity, generally higher or equal to 1000cSt measured at 40oC, preferably greater than or equal to 1500cSt measured at 40oC.
• the amount of CO 2 is increased to thin the retentate which has become very viscous.
• the process is in two-phase mode.
• the separated solid phase is for example of the bituminous type which is then concentrated by a factor of 10 to 100, preferably by a factor of 20 to 60.
• the majority or all of the compounds to be eliminated or undesirable within the oil to be purified is concentrated in this residue or solid phase.
• a physically and chemically inert residue is obtained which can be used for road surfacing or as a jointing material for example.
• the residue and the liquid may be subjected to an expansion to separate the supercritical fluid, in particular CO 2 , for recycling.
• CO 2 as a supercritical fluid in the process according to the invention makes it possible to greatly improve its safety, in particular by reducing the fire risks associated with conventional processes for refining used oils.
• the method according to the invention can be implemented continuously or discontinuously, that is to say batch or batch.
• the yield is generally of the order of 80 to 85% efficiency, evaporation enthalpy of about 300kJ / kg of oil, sensible heat of about 2kJ / kg of oil / K.
• the filtration may be preceded by the addition of an aggregating agent.
• an aggregating agent is of the bitumen type. It is then generally added in an amount ranging from 0.1 to 10% by weight of starting hydrocarbon feedstock, preferably in an amount ranging from 0.5 to 2% by weight of hydrocarbon feedstock, in particular in a quantity 1% by weight of hydrocarbon feedstock starting.
• the treatment of the filler by means of a transformation agent may be a bleaching, a salification, a saponification, a trapping or a chemical modification of the compounds to be eliminated. Preferably, it is a saponification.
• the treatment of the filler by means of a transformation agent is carried out by means of a hydroxide derivative of metal or alkaline earth metal used alone or in a mixture, for example NaOH or KOH, which may be used in aqueous solution, for example at about 50% by weight.
• the treatment of the feedstock by means of a transformation agent is carried out at atmospheric pressure or at higher pressures.
• the treatment of the feedstock with a transformation agent is carried out at a pressure ranging from 1 to 10 bar or alternatively from 2 to 5 bar. Conducting this treatment step at atmospheric pressure is advantageous.
• the treatment of the feedstock by means of a transformation agent is carried out at a temperature ranging from 30 to 350 ° C., preferably from 50 to 200 ° C., even more preferably from 50 to 200 ° C. about 95 to 100oC.
• the treatment of the feedstock by means of a transformation agent is carried out with stirring, preferably with vigorous stirring, or even very strong stirring.
• the separation is facilitated by the transformation of these compounds by means of or by the action of the transformation agent.
• This final step is therefore advantageously implemented following the treatment step with a transformation agent.
• the separation step is carried out by distillation of the hydrocarbon feedstock making it possible to separate the transformed compounds between the distillable fractions and the fractions made non-distillable.
• the distillation is a vacuum distillation, for example a falling film vacuum distillation or a reduced-pressure distillation in a thin layer.
• the start distillation parameters are advantageously about 19mbar for the pressure, about 240 ° C. for the medium temperature and about 50 ° C. for the temperature at the top. of column.
• these parameters are generally about 19mbar for the pressure, of about 375oC, tending towards 400oC, for the temperature of the medium and about 375oC for the temperature at the head of column.
• one of the preferred variants of the invention is a process for purifying a used oil, comprising one or more compounds to be eliminated, which comprises the steps, in particular successive steps:
• An even more preferred variant of the invention is a process for purifying a used oil, comprising the steps, in particular successive steps:
• the method according to the invention can be implemented within an installation comprising at least:
• a first unit for example a tank, in which the hydrocarbon feedstock to be purified is placed;
• a filtration unit connected to the first unit
• Figure 1 shows a schematic sectional view of an example of an installation for implementing the method of the invention.
• Figure 2 shows a schematic sectional view of an example of an installation for implementing the method of the invention.
• the used oil (HU) is the result of the draining of a new ACE E7 oil grade ACE E7 heavy duty diesel engine turbo diesel engine running 60,000km in a RVI brand truck; this type of used oil was chosen for its severity during the regeneration treatment (strong additivation and presence of a large amount of compounds derived from the degradation of diesel, see Table 1);
• the oil (HU) is brought to a temperature of 150oC in the exchanger (e1) and then introduced into the extractor (2) under a partial vacuum of 20mmHg.
• the water (E) extracted at the top is directed towards (s1), the bottom of the column is introduced into the extractor (3).
• the volatile fractions (FV) which are fuels are extracted at the top of the column and are directed to (s2); HU, free of its volatile fractions (HU-E-FV) is directed to the mixing plant (1).
• the additive (A) is heated to 150oC; it is introduced into HU-E-FV in a mixing plant (1); the additive (A) is a bitumen aggregation agent introduced at about 1% by weight.
• the mixture (HU-E-FV + A) is brought to a temperature of 150oC in the exchanger (e2).
• the fluid (C) stored in (s3) is CO2; it is heated to 150oC and 150 bar which corresponds to a supercritical state; it is introduced at the rate of 20% by weight in (f1) at the same time as the used oil (HU-E-FV + A).
• the used oil (HU-E-FV + A) is introduced into a first tangential filtration loop (f1); the transmembrane pressure of 4 bar allows the passage of the oil through the membrane.
• the retentate (R1) is introduced into a second loop (f2).
• the filtrate (F + C) is directed to the separator (d), (C) is recycled to (s3), the separated filtrate (F) is directed to the exchanger (e3).
• the retentate (R2) is introduced into a third loop (f3).
• the filtrate (F + C) is directed to the separator (c2), (C) is recycled to (s3), (F) is directed to the exchanger (e3).
• the retentate (R3) is directed to the bitumen pool (PB).
• the filtrate (F + C) is directed to the separator (c3), (C) is recycled to (s3), (F) is directed to the exchanger (e3).
• (F) is brought to a temperature of about 100oC, and is introduced into the saponification plant (4).
• Solution (S) is composed of 5% by weight of water and 5% by weight of sodium hydroxide of purity equal to 98.5%;
• (S) is introduced at 10% by weight in the saponification plant (4) with (F) where it is maintained at a reflux temperature of 95 to 100oC for several hours (4 to 7 hours) under very strong agitation.
• the mixture (F + S) is introduced into the distillation plant (5); at the start of the distillation, the pressure is 19 mm Hg with a bottom temperature of 240oC and a temperature at the top of column of 50oC; the final temperature at the top is 375oC at 19mm Hg, the bottom temperature does not exceed 400oC.
• the water is recovered from the sodium hydroxide solution (S) and then the base oil (HB) with a yield of 84%.
• the enthalpy of vaporization was calculated at 300 kJ / kg of oil and the sensible heat Cp is 2 kJ / kg / K.
• the distillation residue (R4) is sent to the bitumen pool (PB) (see Table 1 for the metal content).
• Base oil (HB) extracted at the top is directed to storage; the reduction of pollutants is total (see Table 1); traces of silicon are attributable to the use of the silicone paste used to seal the glassware; the phosphorus which was the most difficult marker to reduce has disappeared. The sodium introduced by the soda in excess does not bring pollution.
• the metal contents were analyzed by atomic adsorption spectrometry (ASTM D5185); the viscosities were measured by standard NF EN ISO 3104; nitrogen contents were measured by chemiluminescence (ASTM D 4629).
• Table 1 reduction of pollutant markers at each step After the oil treatment, a test according to EN12591 (European Union standard defining the different types of bitumen) was carried out on the retentate from ultrafiltration. Three analytical methods from this standard have been implemented; their characteristics and the results obtained are shown in Table 2.
• EN12591 European Union standard defining the different types of bitumen
• the result of the aging resistance test shows the residual presence of antioxidants that have not been completely neutralized. Additional oxidation would neutralize these antioxidant compounds. The bitumen can nevertheless be used before or after such additional treatment.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
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• Thermal Sciences (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2010
  • 2010-06-22 FR FR1054962A patent/FR2961521B1/fr not_active Expired - Fee Related
• 2011
  • 2011-06-22 WO PCT/FR2011/051434 patent/WO2011161378A1/fr active Application Filing
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