Bio-based diluent for metal liquid-liquid extraction for battery recycling

Abstract

The present invention relates to the use of a hydrocarbon fluid comprising at least 75% by weight of isoalkanes and less than 100 ppm by weight of aromatics, measured according to the OECD 301B standard, as a diluent for metal liquid-liquid extraction, and more particularly to a hydrometallurgical process for battery recycling, said hydrocarbon fluid comprising at least 75% by weight of isoalkanes and less than 100 ppm by weight of aromatics, relative to the total weight of the hydrocarbon fluid, the biodegradation rate is at least 60% on the 28th day.

Description

Technical Field

[0001] The present invention relates to the use of bio-based isoparaffinic fluids as diluents for liquid-liquid extraction of metals, more particularly to their use in hydrometallurgical processes for battery recycling. The present invention also relates to a hydrometallurgical process comprising at least one liquid-liquid extraction step and at least one recovery step of at least one metal. Background Art

[0002] Global lithium-ion battery production will grow exponentially in the coming years, especially with the development of electric vehicles. According to the International Energy Agency (IEA), the number of electric vehicles in circulation is expected to reach at least 145 million by 2030.

[0003] The expansion in the number of batteries leads to an increase in recycling demand.

[0004] Currently, battery recycling methods that have been developed and industrialized usually use hydrometallurgical steps, which are technologies for extracting / recovering and purifying metals. Liquid-liquid extraction is performed by dissolving the extractant itself in a diluent.

[0005] In prior art methods, the diluent is a hydrocarbon solvent from refining, typically kerosene or dearomatized aliphatic products. The use of such diluents in battery recycling methods results in the use of non-renewable materials, which contradicts the goal of reducing environmental impact.

[0006] The object of the present invention is to provide a readily biodegradable bio-based hydrocarbon fluid as a diluent for liquid-liquid extraction of metals, in particular for recycling electrodes in batteries by hydrometallurgical methods. Summary of the invention

[0007] The present invention relates to the use of a hydrocarbon fluid as a diluent for metal liquid-liquid extraction, the hydrocarbon fluid comprising at least 75% by weight of isoparaffins and less than 100 ppm by weight of aromatics, relative to the total weight of the hydrocarbon fluid, and the hydrocarbon fluid having a biodegradability of at least 60% at 28 days measured according to the OECD 301B standard.

[0008] According to a preferred embodiment, the hydrocarbon fluid comprises, relative to the total weight of the hydrocarbon fluid:

[0009] at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, of isoparaffins, and / or

[0010] - up to 20% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, of normal alkanes, and / or

[0011] - up to 1% by weight of cycloalkanes, and / or

[0012] - Less than 50 ppm by weight of aromatics.

[0013] Preferably, the hydrocarbon fluid has:

[0014] a flash point according to standard ASTM D93 of greater than or equal to 80° C., preferably greater than or equal to 110° C., preferably greater than or equal to 120° C., or even greater than or equal to 140° C., and / or

[0015] The kinematic viscosity at -40°C is less than or equal to 5 cSt, preferably less than or equal to 4 cSt, and / or

[0016] the biogenic carbon content is at least 90% by weight, preferably at least 95% by weight, still more preferably at least 97% by weight, relative to the total weight of carbon atoms of the hydrocarbon fluid.

[0017] According to a preferred embodiment, the hydrocarbon fluid has:

[0018] - the initial boiling point and the final boiling point are 200°C to 400°C, preferably 240°C to 350°C, and more preferably 250°C to 340°C, and / or

[0019] - The difference between the final boiling point and the initial boiling point is 10°C to 80°C, preferably 20°C to 50°C.

[0020] According to a preferred embodiment, the hydrocarbon fluid comprises, relative to the total weight of the hydrocarbon fluid:

[0021] - 30% to 60% by weight of C15 isoparaffins and 30% to 60% by weight of C16 isoparaffins, or

[0022] - 5 to 15% by weight of C15 isoparaffins, 30 to 60% by weight of C16 isoparaffins, 10 to 30% by weight of C17 isoparaffins and 10 to 30% by weight of C18 isoparaffins,

[0023] -10 to 30% by weight of C17 isoparaffins and 60 to 90% by weight of C18 isoparaffins.

[0024] According to one embodiment, the hydrocarbon fluid of the present invention has a flash point of 80° C. to 95° C. (ASTM D93) and comprises, relative to the total weight of the hydrocarbon fluid:

[0025] Relative to the total weight of the hydrocarbon fluid,

[0026] - 0.5 to 15% by weight of isoparaffins having less than 13 carbon atoms,

[0027] - 5 to 25% by weight of C13 isoparaffins, and

[0028] - 5 to 30% by weight of C14 isoparaffins, and

[0029] - 5 to 30% by weight of C15 isoparaffins, and

[0030] - 25 to 50% by weight of C16 isoparaffins, and

[0031] - 10 to 25% by weight of isoparaffins having more than 16 carbon atoms,

[0032] Preferably, the fluid comprises from 75% to 90% by weight of isoparaffins, preferably from 10% to 25% by weight of normal paraffins, relative to the total weight of the fluid.

[0033] According to one embodiment, the hydrocarbon fluid is used in admixture with 0.01 wt % to 5 wt % of one or more antioxidant additives relative to the total weight of the hydrocarbon fluid and the antioxidant additives.

[0034] Preferably, the fluid is used as a diluent in a hydrometallurgical process comprising at least one liquid-liquid extraction of a metal using an extraction solution comprising the diluent and at least one extractant. Preferably, the metal is derived from the recycling of one or more batteries.

[0035] The present invention also relates to a metal liquid-liquid extraction method, which comprises at least one step of contacting a solution of metal M with an extraction solvent, wherein the extraction solvent comprises at least one diluent and at least one extractant, wherein the diluent is a hydrocarbon fluid, wherein the hydrocarbon fluid comprises at least 75% by weight of isoparaffins and less than 100 ppm by weight of aromatics relative to the total weight of the hydrocarbon fluid, and wherein the hydrocarbon fluid has a biodegradability of at least 60% at 28 days as measured according to the OECD 301B standard.

[0036] The present invention also relates to a hydrometallurgical method for battery recycling, the method comprising:

[0037] - a step of dissolving a metal present in at least one cell, in particular in an electrode of said at least one cell, so as to obtain a solution of the metal M,

[0038] - optionally, a step of clarifying the solution of the metal M to remove residues not dissolved in the metal solution,

[0039] - The metal liquid-liquid extraction method of the present invention.

[0040] Preferably, the hydrocarbon fluid used in the metal liquid-liquid extraction method of the present invention or in the hydrometallurgical method for battery recycling of the present invention comprises one or more of the following characteristics:

[0041] - said hydrocarbon fluid comprises, relative to the total weight of said hydrocarbon fluid:

[0042] o at least 80% by weight, preferably at least 90% by weight, and more preferably at least 95% by weight of isoparaffins,

[0043] and / or

[0044] o up to 20% by weight, preferably up to 10% by weight, and more preferably up to 5% by weight, of normal alkanes,

[0045] and / or

[0046] o Up to 1% by weight of cycloalkanes, and / or

[0047] ○ Less than 50 ppm by weight of aromatics,

[0048] - The hydrocarbon fluid has:

[0049] o a flash point according to standard ASTM D93 of greater than or equal to 80° C., preferably greater than or equal to 110° C., preferably greater than or equal to 120° C., or even greater than or equal to 140° C., and / or

[0050] ○ The kinematic viscosity at 40°C is less than or equal to 5 cSt, preferably less than or equal to 4 cSt, and / or

[0051] o The biogenic carbon content is at least 90% by weight, preferably at least 95% by weight, and more preferably at least 97% by weight, relative to the total weight of carbon atoms of the hydrocarbon fluid;

[0052] - The hydrocarbon fluid has:

[0053] ○ The initial boiling point and the final boiling point are 200°C to 400°C, preferably 240°C to 350°C, and more preferably 250°C

[0054] to 340°C, and / or

[0055] ○ The difference between the final boiling point and the initial boiling point is 10°C to 80°C, preferably 20°C to 50°C,

[0056] - said hydrocarbon fluid comprises, relative to the total weight of said hydrocarbon fluid:

[0057] o 30 wt% to 60 wt% C15 isoparaffins and 30 wt% to 60 wt% C16 isoparaffins, or

[0058] o 5 to 15 wt% of C15 isoparaffins, 30 to 60 wt% of C16 isoparaffins, 10 to 30 wt% of C17 isoparaffins and 10 to 30 wt% of C18 isoparaffins,

[0059] o 10 to 30 wt% of C17 isoparaffins and 60 to 90 wt% of C18 isoparaffins,

[0060] - the hydrocarbon fluid has a flash point of 80°C to 95°C and comprises, relative to the total weight of the hydrocarbon fluid:

[0061] Relative to the total weight of the hydrocarbon fluid,

[0062] o 0.5 to 15% by weight of isoparaffins having less than 13 carbon atoms,

[0063] o 5 to 25 wt% C13 isoparaffins, and

[0064] o 5 to 30 wt% C14 isoparaffins, and

[0065] o 5 to 30 wt% C15 isoparaffins, and

[0066] o 25 to 50 wt% C16 isoparaffins, and

[0067] o 10 to 25% by weight of isoparaffins having more than 16 carbon atoms,

[0068] Preferably, the fluid comprises from 75% to 90% by weight of isoparaffins, preferably from 10% to 25% by weight of normal paraffins, relative to the total weight of the fluid.

[0069] The low density of the hydrocarbon fluids of the present invention, more particularly, the density is lower than that of hydrocarbon solvents of petroleum origin (fossil), which makes them particularly effective as diluents for metal liquid-liquid extraction.

[0070] The hydrocarbon fluids of the present invention are particularly stable. In fact, they have excellent thermal stability, excellent oxidation stability and excellent UV stability, which makes it possible to extend the life of the diluent, thereby minimizing the steps of changing the diluent.

[0071] The low volatility of the hydrocarbon fluids of the present invention at a given flash point makes it possible to reduce fluid losses due to evaporation, thereby improving the productivity and performance of the process.

[0072] The present invention can provide a bio-based diluent having excellent extraction performance when used in an extraction solvent containing a metal extractant.

[0073] Thus, the hydrocarbon fluids defined in the present invention have good compatibility with metal extractants, more particularly metals for use in batteries.

[0074] In fact, the inventors have found that hydrocarbon fluids as defined in the present invention have metal diluent / extractant pairs with good extractability for metals, in particular with excellent selectivity for the metals of interest.

[0075] More specifically, the present invention proposes a battery recycling method using a diluent of bio-based origin, thereby having less impact on the environment, enabling selective recovery and reuse of metals and improving yield. DETAILED DESCRIPTION

[0076] The present invention relates to the use of a hydrocarbon fluid as a diluent for liquid-liquid extraction of metals, more particularly in a hydrometallurgical process, the hydrocarbon fluid comprising at least 75% by weight of isoparaffins and less than 100 ppm by weight of aromatics relative to the total weight of the hydrocarbon fluid, the hydrocarbon fluid having a biodegradability of at least 60% at 28 days measured according to the OECD 301B standard.

[0077] Another subject of the invention is a metal liquid-liquid extraction process comprising at least one step of contacting a solution of a metal M with an extraction solvent comprising at least one diluent and at least one extractant, the diluent being a hydrocarbon fluid comprising at least 75% by weight of isoparaffins and less than 100 ppm by weight of aromatics relative to the total weight of the hydrocarbon fluid, the hydrocarbon fluid having a biodegradability of at least 60% at 28 days, measured according to the OECD 301B standard.

[0078] Finally, the subject of the invention is a hydrometallurgical process for recycling one or more batteries, said process comprising:

[0079] - a step of dissolving a metal present in at least one cell, in particular in an electrode of said at least one cell, so as to obtain a solution of the metal M,

[0080] - optionally, a step of clarifying the solution of the metal M to remove residues not dissolved in the metal solution,

[0081] - a step of metal liquid-liquid extraction, comprising at least one step of contacting a solution of the metal M with an extraction solvent, the extraction solvent comprising at least one diluent and at least one extractant, the diluent being a hydrocarbon fluid, the hydrocarbon fluid comprising at least 75% by weight of isoparaffins and less than 100 ppm by weight of aromatics relative to the total weight of the hydrocarbon fluid, the hydrocarbon fluid having a biodegradability of at least 60% at 28 days measured according to the OECD 301B standard.

[0082] The hydrocarbon fluids used in the present invention are generally of bio-based origin.

[0083] Firstly, it should be noted that in the following description and claims, the expression "comprising between" should be understood to include the mentioned boundaries.

[0084] The term "paraffin" as defined in the present invention includes iso-alkanes and normal-alkanes.

[0085] The term "isoalkane" as defined in the present invention refers to acyclic branched alkanes.

[0086] The term "normal alkane" as defined in the present invention refers to a straight-chain non-cyclic alkane.

[0087] The term "cycloalkane" as defined herein refers to cyclic (non-aromatic) alkanes.

[0088] Hydrocarbon fluids used as diluents:

[0089] The hydrocarbon fluid used in the present invention contains at least 75% by weight of isoparaffins, preferably at least 80% by weight of isoparaffins, further preferably at least 90% by weight of isoparaffins, or even at least 95% by weight of isoparaffins, relative to the total weight of the hydrocarbon fluid.

[0090] The hydrocarbon fluid used in the present invention contains normal alkanes in an amount less than or equal to 25% by weight, preferably less than or equal to 20% by weight, further preferably less than or equal to 10% by weight, or even less than or equal to 5% by weight of normal alkanes, relative to the total weight of the hydrocarbon fluid.

[0091] Preferably, the mass ratio of isoparaffins to normal paraffins in the hydrocarbon fluid used in the present invention is at least 4:1, preferably at least 9:1, more preferably at least 12:1, preferably at least 15:1, or even at least 19:1.

[0092] Preferably, the hydrocarbon fluid used in the present invention contains cycloparaffin compounds in an amount less than or equal to 1%, preferably less than or equal to 0.5%, more preferably less than or equal to 100 ppm by weight relative to the total weight of the hydrocarbon fluid.

[0093] According to one embodiment, the hydrocarbon fluid used in the present invention contains at least 80 wt% of isoparaffins, less than 20 wt% of normal paraffins, less than 1 wt% of cycloparaffins and less than 100 wtppm of aromatics, relative to the total weight of the hydrocarbon fluid.

[0094] According to one embodiment, the hydrocarbon fluid used in the present invention contains 90% to 100% by weight of isoparaffins and 0% to 10% by weight of normal paraffins, preferably 95% to 100% by weight of isoparaffins and 0% to 5% by weight of normal paraffins, and more preferably 98% to 100% by weight of isoparaffins and 0% to 2% by weight of normal paraffins, relative to the total weight of the hydrocarbon fluid.

[0095] According to a preferred embodiment, the hydrocarbon fluid used in the present invention contains 90% to 100% by weight of isoalkanes, 0% to 10% by weight of normal alkanes and less than or equal to 1% by weight of cycloalkanes, relative to the total weight of the hydrocarbon fluid.

[0096] Preferably, the hydrocarbon fluid used in the present invention contains 95% to 100% by weight of isoparaffins, 0% to 5% by weight of normal paraffins and less than or equal to 0.5% by weight of cycloparaffins, relative to the total weight of the hydrocarbon fluid.

[0097] More preferably, the hydrocarbon fluid used in the present invention contains 98 to 100% by weight of isoparaffins, 0 to 2% by weight of normal paraffins and less than or equal to 100 ppm by weight of cycloparaffins, relative to the total weight of the hydrocarbon fluid.

[0098] The weight content of iso-alkanes, normal-alkanes and cycloalkanes can be determined according to any method known to those skilled in the art, for example by gas chromatography.

[0099] The hydrocarbon fluid used in the present invention contains less than 100 ppm by weight of aromatic hydrocarbons, preferably less than 50 ppm by weight of aromatic hydrocarbons, and more preferably less than 20 ppm by weight of aromatic hydrocarbons, relative to the total weight of the hydrocarbon fluid.

[0100] The aromatics content can be determined by any method known to those skilled in the art, for example by UV spectroscopy.

[0101] According to a preferred embodiment, the hydrocarbon fluid used in the present invention comprises 90% to 100% by weight of isoparaffins, 0% to 10% by weight of normal paraffins, 1% by weight of cycloparaffins, and 100 ppm by weight of aromatic compounds. Preferably, the hydrocarbon fluid used in the present invention comprises 95% to 100% by weight of isoparaffins, 0% to 5% by weight of normal paraffins, 0.5% by weight of cycloparaffins, and 50 ppm by weight of aromatic compounds. Also preferably, the hydrocarbon fluid used in the present invention comprises 95% to 100% by weight of isoparaffins, 0% to 5% by weight of normal paraffins, and 100 ppm by weight of aromatic compounds. More preferably, the hydrocarbon fluid used in the present invention comprises 98 to 100% by weight of isoparaffins, 0 to 2% by weight of normal paraffins, 100 ppm by weight of cycloparaffins and 100 ppm by weight of aromatic compounds.

[0102] According to one embodiment, the biogenic carbon content of the hydrocarbon fluid used in the present invention is at least 90% by weight, preferably at least 95% by weight, and more preferably at least 97% by weight, relative to the total weight of carbon atoms of the hydrocarbon.

[0103] The content of biogenic carbon (also called biogenic carbon) can be determined according to the ASTM D6866 standard established in 2020.

[0104] According to one embodiment, the hydrocarbon fluid used in the present invention contains at least 80 weight % of isoalkanes, less than 20 weight % of normal alkanes, less than 1 weight % of cycloalkanes and less than 100 weight ppm of aromatics, relative to the total weight of the hydrocarbon fluid, and the weight content of biogenic carbon is at least 90% relative to the total weight of carbon atoms in the hydrocarbon fluid.

[0105] According to one embodiment, the hydrocarbon fluid used in the present invention contains at least 90 weight % of isoalkanes, less than 10 weight % of normal alkanes, less than 1 weight % of cycloalkanes and less than 100 weight ppm of aromatics, relative to the total weight of the hydrocarbon fluid, and the weight content of biogenic carbon is at least 90% relative to the total weight of carbon atoms in the hydrocarbon fluid.

[0106] The hydrocarbon fluids used in the present invention also preferably have very low sulfur-containing compounds, typically less than or equal to 5 ppm, preferably less than or equal to 3 ppm, and more preferably less than or equal to 0.5 ppm by weight, which is too low to be detected by conventional low sulfur content analyzers.

[0107] The flash point of the hydrocarbon fluid used in the present invention according to standard ASTM D93 is also preferably greater than or equal to 80° C., preferably greater than or equal to 110° C., preferably greater than or equal to 120° C., and more preferably greater than or equal to 140° C. A high flash point (generally greater than 110° C.) makes it possible to overcome safety problems during storage and transportation, while preventing the overly sensitive flammability of hydrocarbon fluids.

[0108] According to one embodiment, the hydrocarbon fluid used in the invention has a flash point according to the ASTM D93 standard of 80 to 105° C. The inventors have observed that this flash point range enables further improvement of diluent performance within the framework of liquid-liquid extraction, more particularly battery recycling.

[0109] The vapor pressure of the hydrocarbon fluid used in the present invention at 20° C. is also preferably 0.01 kPa or less.

[0110] According to one embodiment, the hydrocarbon fluid used in the present invention also preferably has a flash point greater than or equal to 110° C. according to standard ASTM D93 and a vapor pressure less than or equal to 0.01 kPa at 20° C.

[0111] Preferably, the hydrocarbon fluid used in the present invention has a flash point of 120° C. or more and a vapor pressure of 0.01 kPa or less at 20° C. or less.

[0112] More preferably, the hydrocarbon fluid used in the present invention has a flash point of 140° C. or higher and a vapor pressure of 0.01 kPa or lower at 20° C.

[0113] Furthermore, the hydrocarbon fluid used in the present invention preferably has a kinematic viscosity at 40° C. measured according to standard ASTM D445 of less than or equal to 5 cSt, preferably less than or equal to 4 cSt.

[0114] Preferably, the initial boiling point and the final boiling point of the hydrocarbon fluid used in the present invention are 200°C to 400°C, preferably 240°C to 350°C, more preferably 250°C to 340°C.

[0115] The boiling point can be determined according to standard ASTM D86.

[0116] Preferably, the difference between the final boiling point and the initial boiling point is 10°C to 80°C, preferably 20°C to 50°C.

[0117] According to one embodiment, the hydrocarbon fluid used in the present invention contains at least 80 wt% of isoparaffins, less than 1 wt% of cycloparaffins and less than 100 wtppm of aromatics, and has initial and final boiling points of 200 to 400°C.

[0118] According to a particularly preferred embodiment, the hydrocarbon fluid used in the present invention contains at least 95 wt% of isoparaffins and less than 100 wtppm of aromatics, and has an initial boiling point and a final boiling point of 200°C to 400°C.

[0119] According to a particularly preferred embodiment, the hydrocarbon fluid used in the present invention contains at least 95 wt% of isoparaffins and less than 100 wtppm of aromatics, and has an initial boiling point and a final boiling point of 250°C to 340°C.

[0120] According to a particularly preferred embodiment, the hydrocarbon fluid used in the present invention contains at least 95% by weight of isoparaffins and less than 100 ppm by weight of aromatics, and has an initial boiling point and a final boiling point of 200°C to 400°C, and a difference between the final boiling point and the initial boiling point of 10°C to 80°C.

[0121] According to a particularly preferred embodiment, the hydrocarbon fluid used in the present invention contains at least 80 wt% of isoparaffins and less than 100 wtppm of aromatics, and has an initial boiling point and a final boiling point of 250°C to 340°C, and a difference between the final boiling point and the initial boiling point of 10°C to 80°C.

[0122] According to a particularly preferred embodiment, the hydrocarbon fluid used in the present invention contains at least 95% by weight of isoparaffins and less than 100 ppm by weight of aromatics, and has an initial boiling point and a final boiling point of 250°C to 340°C, and a difference between the final boiling point and the initial boiling point of 10°C to 80°C.

[0123] According to a particularly preferred embodiment, the hydrocarbon fluid used in the present invention contains at least 95 wt% of isoparaffins and less than 100 wtppm of aromatics, and has an initial boiling point and a final boiling point of 250°C to 340°C, and a difference between the final boiling point and the initial boiling point of 20°C to 50°C.

[0124] According to one embodiment, the hydrocarbon fluid used in the present invention comprises, relative to the total weight of the hydrocarbon fluid:

[0125] - 20% to 80% by weight of C15 isoparaffins and 20% to 80% by weight of C16 isoparaffins, wherein the fluid may also contain isoparaffins having less than 14 carbon atoms and / or isoparaffins having more than 17 carbon atoms; or

[0126] - 3% to 20% by weight of C15 isoparaffins, 20% to 70% by weight of C16 isoparaffins, 5% to 40% by weight of C17 isoparaffins and 5% to 40% by weight of C18 isoparaffins, wherein the fluid may optionally contain isoparaffins having less than 14 carbon atoms and / or isoparaffins having more than 19 carbon atoms; or

[0127] - 5 to 40% by weight of C17 isoparaffins and 60 to 95% by weight of C18 isoparaffins, wherein the fluid may optionally contain isoparaffins having less than 16 carbon atoms and / or isoparaffins having more than 19 carbon atoms.

[0128] According to a specific embodiment, the hydrocarbon fluid used in the present invention comprises, relative to the total weight of the hydrocarbon fluid:

[0129] - 30% to 60% by weight of C15 isoparaffins and 30% to 60% by weight of C16 isoparaffins, wherein the fluid may contain isoparaffins having less than 14 carbon atoms and / or isoparaffins having more than 17 carbon atoms; or

[0130] - 5 to 15% by weight of C15 isoparaffins, 30 to 60% by weight of C16 isoparaffins, 10 to 30% by weight of C17 isoparaffins and 10 to 30% by weight of C18 isoparaffins, wherein the fluid may optionally contain isoparaffins having less than 14 carbon atoms and / or isoparaffins having more than 19 carbon atoms; or

[0131] - 10% to 30% by weight of C17 isoparaffins and 60% to 90% by weight of C18 isoparaffins, wherein the fluid may optionally contain isoparaffins having less than 16 carbon atoms and / or isoparaffins having more than 19 carbon atoms.

[0132] The term "CX isoparaffin" refers to an isoparaffin containing X carbon atoms.

[0133] According to one embodiment, the hydrocarbon fluid used in the present invention contains 5 to 15 wt% of C15 isoparaffins, 30 to 60 wt% of C16 isoparaffins, 10 to 30 wt% of C17 isoparaffins and 10 to 30 wt% of C18 isoparaffins, relative to the total weight of the hydrocarbon fluid, and the weight content of aromatics is less than 100 ppm.

[0134] According to one embodiment, the hydrocarbon fluid used in the present invention has an initial boiling point and a final boiling point of 240°C to 300°C, and contains 5% to 15% by weight of C15 isoparaffins, 30% to 60% by weight of C16 isoparaffins, 10% to 30% by weight of C17 isoparaffins and 10% to 30% by weight of C18 isoparaffins relative to the total weight of the hydrocarbon fluid, and the weight content of aromatic hydrocarbons is less than 100 ppm.

[0135] According to one embodiment, the hydrocarbon fluid used in the present invention contains 10 to 30 wt% of C17 isoparaffins and 60 to 90 wt% of C18 isoparaffins relative to the total weight of the hydrocarbon fluid, and the weight content of aromatics is less than 100 ppm.

[0136] According to one embodiment, the hydrocarbon fluid used in the present invention has an initial boiling point and a final boiling point of 260°C to 340°C, and contains 10% to 30% by weight of C17 isoparaffins and 60% to 90% by weight of C18 isoparaffins relative to the total weight of the hydrocarbon fluid, and the weight content of aromatic hydrocarbons is less than 100 ppm.

[0137] According to one embodiment, the hydrocarbon fluid used in the present invention contains 5% to 15% by weight of C15 isoparaffins, 30% to 60% by weight of C16 isoparaffins, 10% to 30% by weight of C17 isoparaffins and 10% to 30% by weight of C18 isoparaffins, relative to the total weight of the hydrocarbon fluid, and the weight content of aromatic hydrocarbons is less than 100 ppm, and the weight content of biochar relative to the total weight of carbon atoms of the hydrocarbon fluid is at least 95%.

[0138] According to one embodiment, the hydrocarbon fluid used in the present invention has an initial boiling point and a final boiling point of 240°C to 300°C, and contains 5% to 15% by weight of C15 isoparaffins, 30% to 60% by weight of C16 isoparaffins, 10% to 30% by weight of C17 isoparaffins and 10% to 30% by weight of C18 isoparaffins relative to the total weight of the hydrocarbon fluid, and the weight content of aromatic hydrocarbons is less than 100 ppm, and the weight content of biochar relative to the total weight of carbon atoms of the hydrocarbon fluid is at least 95%.

[0139] According to one embodiment, the hydrocarbon fluid used in the present invention contains 10 wt% to 30 wt% of C17 isoparaffins and 60 wt% to 90 wt% of C18 isoparaffins, relative to the total weight of the hydrocarbon fluid, and the weight content of aromatic hydrocarbons is less than 100 ppm, and the weight content of biochar relative to the total weight of carbon atoms of the hydrocarbon fluid is at least 95%.

[0140] According to one embodiment, the hydrocarbon fluid used in the present invention has an initial boiling point and a final boiling point of 260°C to 340°C, and contains 10% to 30% by weight of C17 isoparaffins and 60% to 90% by weight of C18 isoparaffins relative to the total weight of the hydrocarbon fluid, and the weight content of aromatic hydrocarbons is less than 100 ppm, and the weight content of biochar relative to the total weight of carbon atoms of the hydrocarbon fluid is at least 95%.

[0141] According to one embodiment, the hydrocarbon fluid used in the present invention contains 5 to 15 weight % of C15 isoparaffins, 30 to 60 weight % of C16 isoparaffins, 10 to 30 weight % of C17 isoparaffins and 10 to 30 weight % of C18 isoparaffins, relative to the total weight of the hydrocarbon fluid, and the weight content of aromatic hydrocarbons is less than 50 ppm, and the weight content of biochar relative to the total weight of carbon atoms of the hydrocarbon fluid is at least 90%.

[0142] According to one embodiment, the hydrocarbon fluid used in the present invention contains 10 wt% to 30 wt% of C17 isoparaffins and 60 wt% to 90 wt% of C18 isoparaffins, relative to the total weight of the hydrocarbon fluid, and the weight content of aromatic hydrocarbons is less than 50 ppm, and the weight content of biochar relative to the total weight of carbon atoms of the hydrocarbon fluid is at least 90%.

[0143] According to a particular embodiment, the hydrocarbon fluid of the present invention has a flash point of 80° C. to 95° C. (ASTM D93) and comprises, relative to the total weight of the hydrocarbon fluid:

[0144] Relative to the total weight of hydrocarbon fluid,

[0145] - 0.5 to 15% by weight of isoparaffins having less than 13 carbon atoms,

[0146] - 5 to 25% by weight of C13 isoparaffins, and

[0147] - 5 to 30% by weight of C14 isoparaffins, and

[0148] - 5 to 30% by weight of C15 isoparaffins, and

[0149] - 25 to 50% by weight of C16 isoparaffins, and

[0150] - 10 to 25% by weight of isoparaffins having more than 16 carbon atoms,

[0151] Preferably, the fluid comprises from 75% to 90% by weight of isoparaffins, preferably from 10% to 25% by weight of normal paraffins, relative to the total weight of the fluid.

[0152] The inventors have observed that hydrocarbon fluids have a particularly high performance as diluents within the framework of battery recycling as defined in the present invention.

[0153] The hydrocarbon fluids used in the present invention have a biodegradability of at least 60% at 28 days, measured according to the OECD 301 B standard. Therefore, the hydrocarbon fluids of the present invention are generally referred to as "readily biodegradable".

[0154] In contrast, a product is referred to as "inherently biodegradable" if its biodegradation rate at 28 days according to the OECD 301 standard (eg according to the OECD 301B standard) ranges from 20% to less than 60%.

[0155] According to one embodiment, the hydrocarbon fluid used in the present invention has a biodegradation rate of at least 70%, preferably at least 80%, measured at 28 days according to the OECD 301B standard.

[0156] The hydrocarbon fluid used in the present invention has a biodegradation rate of at least 60% at 28 days, measured according to the OECD 306 standard. The OECD 306 standard is more stringent than the OECD 301B standard.

[0157] According to a particularly preferred embodiment, the hydrocarbon fluid used in the present invention contains at least 80% by weight of isoparaffins and less than 100 ppm by weight of aromatics, and has an initial boiling point and a final boiling point of 200°C to 400°C, and the hydrocarbon fluid has a biodegradability of at least 60% when measured in 28 days according to the OECD301B standard.

[0158] According to a particularly preferred embodiment, the hydrocarbon fluid used in the present invention contains at least 95% by weight of isoparaffins and less than 100 ppm by weight of aromatics, and has an initial boiling point and a final boiling point of 200°C to 400°C, and the hydrocarbon fluid has a biodegradability of at least 60% when measured in 28 days according to the OECD301B standard.

[0159] According to a particularly preferred embodiment, the hydrocarbon fluid used in the present invention contains at least 95% by weight of isoparaffins and less than 100 ppm by weight of aromatics, and has an initial boiling point and a final boiling point of 250°C to 340°C, and the hydrocarbon fluid has a biodegradability of at least 60% at 28 days measured according to the OECD301B standard.

[0160] According to a particularly preferred embodiment, the hydrocarbon fluid used in the present invention contains at least 95% by weight of isoparaffins and less than 100 ppm by weight of aromatic hydrocarbons, and has an initial boiling point and a final boiling point in the range of 250°C to 340°C, and the difference between the final boiling point and the initial boiling point is 20°C to 50°C, and the hydrocarbon fluid has a biodegradability of at least 60% at 28 days measured according to the OECD 301B standard.

[0161] According to one embodiment, the hydrocarbon fluid used in the present invention contains 5 to 15 wt% of C15 isoparaffins, 30 to 60 wt% of C16 isoparaffins, 10 to 30 wt% of C17 isoparaffins and 10 to 30 wt% of C18 isoparaffins, relative to the total weight of the hydrocarbon fluid, and the weight content of aromatic hydrocarbons is less than 100 ppm, and the hydrocarbon fluid has a biodegradability of at least 60% when measured according to the OECD 301B standard at 28 days.

[0162] According to one embodiment, the hydrocarbon fluid used in the present invention contains 10 wt% to 30 wt% of C17 isoparaffins and 60 wt% to 90 wt% of C18 isoparaffins, relative to the total weight of the hydrocarbon fluid, and the weight content of aromatic hydrocarbons is less than 100 ppm, and the hydrocarbon fluid has a biodegradation rate of at least 60% when measured in 28 days according to the OECD 301B standard.

[0163] According to a particularly preferred embodiment, the hydrocarbon fluid used in the present invention contains at least 95% by weight of isoparaffins and less than 50 ppm by weight of aromatics, and has an initial boiling point and a final boiling point of 200°C to 400°C, and the hydrocarbon fluid has a biodegradability of at least 60% when measured in 28 days according to the OECD301B standard.

[0164] According to a particularly preferred embodiment, the hydrocarbon fluid used in the present invention contains at least 95% by weight of isoparaffins and less than 50 ppm by weight of aromatics, and has an initial boiling point and a final boiling point of 250°C to 340°C, and the hydrocarbon fluid has a biodegradability of at least 60% at 28 days measured according to the OECD301B standard.

[0165] According to a particularly preferred embodiment, the hydrocarbon fluid used in the present invention contains at least 95% by weight of isoparaffins and less than 50 ppm by weight of aromatic hydrocarbons, and has an initial boiling point and a final boiling point of 250°C to 340°C, and a difference between the final boiling point and the initial boiling point of 20°C to 50°C, and the hydrocarbon fluid has a biodegradability of at least 60% at 28 days as measured according to the OECD 301B standard.

[0166] According to one embodiment, the hydrocarbon fluid used in the present invention contains 5 to 15 wt% of C15 isoparaffins, 30 to 60 wt% of C16 isoparaffins, 10 to 30 wt% of C17 isoparaffins and 10 to 30 wt% of C18 isoparaffins, relative to the total weight of the hydrocarbon fluid, and the weight content of aromatic hydrocarbons is less than 50 ppm, and the hydrocarbon fluid has a biodegradability of at least 60% when measured according to the OECD 301B standard at 28 days.

[0167] According to one embodiment, the hydrocarbon fluid used in the present invention contains 10 wt% to 30 wt% of C17 isoparaffins and 60 wt% to 90 wt% of C18 isoparaffins, relative to the total weight of the hydrocarbon fluid, and the weight content of aromatic hydrocarbons is less than 50 ppm, and the hydrocarbon fluid has a biodegradation rate of at least 60% at 28 days measured according to the OECD 301B standard.

[0168] Methods for obtaining hydrocarbon fluids:

[0169] The hydrocarbon fluid used in the present invention can be obtained in the following manner: The hydrocarbon fluid used in the present invention is a hydrocarbon fraction generally derived from biomass conversion.

[0170] From biomass conversion is meant the hydrocarbon fraction produced from raw materials of biological origin. The raw materials of organic origin may be selected from vegetable oils, animal fats, fish oils and mixtures thereof.

[0171] Preferably, the hydrocarbon fraction of biological origin is obtained by a process comprising a hydrodeoxygenation (HDO) and an isomerization (ISO) step. The hydrodeoxygenation (HDO) step results in the structural decomposition of the bio-ester or triglyceride components, the removal of oxygen-containing, phosphorus-containing and sulfur-containing compounds and the hydrogenation of olefinic bonds. The products from the hydrodeoxygenation reaction are then isomerized. The fractionation step may preferably be performed after the hydrodeoxygenation and isomerization steps. Advantageously, the fraction of interest is subsequently hydrotreated and then subjected to a distillation step to obtain the specifications of the desired hydrocarbon fluid of the present invention.

[0172] The HDO / ISO method is carried out on untreated biological raw materials (also referred to as biomass or raw materials of biological origin), selected from the group consisting of vegetable oils, animal fats, fish oils and mixtures thereof. Suitable organic raw materials are, for example, rapeseed oil, canola oil, tall oil, sunflower oil, soybean oil, hemp oil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, castor oil, coconut oil, animal fats (e.g. tallow), recycled food fats, genetically modified raw materials, and organic raw materials produced by microorganisms such as algae and bacteria. Condensation products, esters or other derivatives obtained from untreated biological materials can also be used as raw materials.

[0173] Preferably, the bio-derived feedstock is an ester or triglyceride derivative. Such material is first subjected to a hydrodeoxygenation (HDO) step to decompose the structures that make up the esters or triglycerides and remove oxygen-, phosphorus- and sulfur-containing compounds, while hydrogenating the olefinic bonds. After the bio-derived feedstock is subjected to the hydrodeoxygenation (HDO) step, the resulting product is isomerized to branch the hydrocarbon chains and improve the performance of the paraffins at low temperatures.

[0174] In the HDO step, hydrogen and the biological raw material are passed through a hydrodeoxygenation catalytic bed simultaneously or in countercurrent. In the HDO step, the pressure and temperature are respectively 20 to 150 bar and 200° C. to 500° C. Conventional and known hydrodeoxygenation catalysts are used in this step. Optionally, the raw material of biological origin can be pre-hydrogenated under mild conditions to prevent secondary reactions of double bonds before the HDO step. After the hydrodeoxygenation step, the product from the reaction is subjected to an isomerization step (ISO), in which hydrogen and the product and an optional mixture of normal paraffins are passed through an isomerization catalyst bed simultaneously or in countercurrent. In the ISO step, the pressure and temperature are respectively 20 to 150 bar and 200° C. to 500° C. Conventional and known isomerization catalysts are used in this step.

[0175] Additional secondary methods (eg, intermediate mixing, cleanup, etc.) may also be used.

[0176] The products from the HDO / ISO step may optionally be separated to obtain fractions of interest.

[0177] Various HDO / ISO processes are described in the literature. Application WO2014 / 033762 describes a process comprising a prehydrogenation step, a hydrodeoxygenation (HDO) step and an isomerization step operated in countercurrent. Patent application EP1728844 describes a process for producing hydrocarbons from a mixture of compounds of plant and animal origin. The process comprises a step of pretreating the mixture to remove contaminants (e.g. alkali metal salts) and a subsequent hydrodeoxygenation (HDO) step and an isomerization step. Patent application EP2084245 describes a process for producing a hydrocarbon mixture that can be used as diesel or a diesel composition by hydrodeoxygenating a mixture of biological origin containing fatty acid esters and optionally mixed free fatty acids (e.g. vegetable oils, such as sunflower oil, rapeseed oil, canola oil, palm oil or pine oil), followed by hydroisomerization over a specific catalyst. Patent application EP2368967 describes this process and the products obtained by this process.

[0178] Advantageously, the feedstock of biological origin contains less than 15 ppm of sulfur, preferably less than 8 ppm, preferably less than 5 ppm, more preferably less than 1 ppm, according to standard EN ISO 20846. Ideally, the feedstock contains no sulfur as a bio-based feedstock.

[0179] The deoxygenated and isomerized feedstock from the HDO / ISO process is then optionally hydrogenated after fractionation to obtain the desired boiling point range.

[0180] Preferably, the hydrogenation step is a catalytic hydrogenation step carried out on the deoxygenated and isomerized biological feedstock (or fraction) at a temperature of 80°C to 180°C and a pressure of 50 bar to 160 bar.

[0181] The hydrogen used in the hydrogenation unit is typically high purity hydrogen. High purity means that the purity of the hydrogen is greater than 99%, although other grades of hydrogen can also be used.

[0182] The hydrogenation step is carried out using a catalyst. Conventional hydrogenation catalysts can be bulk catalysts or supported catalysts and can contain the following metals: nickel, platinum, palladium, rhenium, rhodium, nickel tungstate, nickel-molybdenum, molybdenum, cobalt-molybdenum. The support can be silica, alumina, silica-alumina or zeolite.

[0183] The preferred catalyst is supported on a surface area preferably of 100 m 2 / g to 200m 2 / g of nickel catalyst on alumina, or nickel bulk catalyst. The hydrogenation conditions are generally as follows:

[0184] Pressure: 50 bar to 160 bar, preferably 80 bar to 150 bar, more preferably 90 bar to 120 bar;

[0185] Temperature: 80°C to 180°C, preferably 120°C to 160°C, more preferably 150 to 160°C;

[0186] Liquid Hourly Space Velocity (LHSV): 0.2hr -1 Up to 5 hours -1 , preferably 0.4 hr -1 Up to 3 hours -1 , more preferably 0.5 hr -1 Up to 0.8hr -1 ;

[0187] Hydroprocessing rate: Applicable to the above conditions, up to 200Nm 3 / ton of raw materials to be processed.

[0188] The temperature in the reactor is generally 150°C to 160°C, the pressure is about 100 bar, and the liquid hourly space velocity is about 0.6 hr -1 The processing rate is adjusted according to the quality of the raw material to be processed and the parameters of the first hydrogenation reactor.

[0189] The hydrogenation can be carried out in one or more reactors connected in series. The reactor can contain one or more catalyst beds. The catalyst bed is usually a fixed catalyst bed.

[0190] The hydrogenation process preferably comprises two or three reactors, preferably three reactors, more preferably is carried out in three reactors connected in series.

[0191] The first reactor is used to remove sulfur compounds and hydrogenate substantially all of the unsaturated compounds and up to about 90% by weight of aromatic compounds. The product from the first reactor is substantially free of any sulfur compounds. In the second step, i.e., in the second reactor, aromatic hydrocarbons are further hydrogenated, thereby hydrogenating up to 99% by weight of aromatic hydrocarbons.

[0192] The third step in the third reactor is a finishing step to obtain an aromatics weight content of less than 100 ppm, preferably less than 50 ppm, preferably less than 20 ppm.

[0193] Reactors with two or three or more catalyst beds may be used. The catalyst may be present in each reactor in variable or substantially equal amounts; for three reactors, the amounts by weight may be, for example, 0.05-0.5 / 0.10-0.70 / 0.25-0.85, preferably 0.07-0.25 / 0.15-0.35 / 0.4-0.78, more preferably 0.10-0.20 / 0.20-0.32 / 0.48-0.70.

[0194] It is also possible to use one or two hydrogenation reactors instead of three.

[0195] The first reactor can also consist of two reactors operating alternately. This mode of operation allows the catalyst to be loaded and unloaded particularly easily: when the first reactor initially contains saturated catalyst (essentially all sulfur is trapped on and / or in the catalyst), it should be replaced frequently.

[0196] It is also possible to use a single reactor in which two, three or more catalyst beds are installed.

[0197] It may be necessary to provide a quench box in the recycling system or between reactors to cool the effluent from one reactor to another, or from one catalyst bed to another, so as to control the temperature and hydrothermal balance of each reaction. According to a preferred embodiment, there is no intermediate product to be cooled or quenched.

[0198] According to one embodiment, the products and / or separated gases from the process are at least partially recycled to the feed system of the hydrogenation reactor. This dilution helps to keep the exothermicity of the reaction within controllable limits, more particularly in the first stage. In addition, the recycling allows heat exchange before the reaction and better control of the temperature.

[0199] The effluent from the hydrogenation unit contains mainly hydrogenation products and hydrogen. A flash separator is used to separate the gas phase effluent (mainly residual hydrogen) from the liquid phase effluent (mainly hydrogenated hydrocarbon fraction). The process can be carried out using three flash separators, one at high pressure, one at medium pressure, and one at low pressure very close to atmospheric pressure.

[0200] The gaseous hydrogen collected at the top of the flash separator can be recycled in the feed system of the hydrogenation unit, or can be recycled at different stages in the hydrogenation unit between reactors.

[0201] According to one embodiment, the final product is separated at atmospheric pressure. It is then directly supplied to a vacuum fractionation unit. Preferably, the fractionation is carried out at a pressure of 10 mbar to 50 mbar, more preferably about 30 mbar.

[0202] The fractionation is carried out in such a way that various hydrocarbon fluids can be removed simultaneously from the fractionation column and their boiling points can be predetermined.

[0203] By adjusting the initial and final boiling points of the feedstock, the hydrogenation reactor, separator and fractionation unit can be directly connected without intermediate tanks. This integration of hydrogenation and fractionation will optimize heat integration, reduce the number of systems and save energy.

[0204] Therefore, according to one embodiment of the present invention, the hydrocarbon fluid used in the present invention is obtained by a process comprising subjecting a biomass that has been hydrodeoxygenated and hydroisomerized to a catalytic hydrogenation step, wherein the hydrogenation step is carried out at a temperature of 80°C to 180°C and a pressure of 50 bar to 160 bar, preferably at a temperature of 120°C to 160°C and a pressure of 80 bar to 150 bar, and further preferably at a temperature of 150°C to 160°C and a pressure of 90 bar to 120 bar.

[0205] According to a particular embodiment, the hydrocarbon fluid used in the present invention is obtained by a process comprising the following steps:

[0206] - a hydrodeoxygenation step of the biomass, followed by a hydroisomerization step of the biomass, in order to obtain a hydrodeoxygenated and hydroisomerized biomass,

[0207] a catalytic hydrogenation step carried out on the hydrodeoxygenated and hydroisomerized biomass, the hydrogenation step being carried out at a temperature ranging from 80° C. to 180° C. and a pressure ranging from 50 bar to 160 bar, preferably at a temperature ranging from 120° C. to 160° C. and a pressure ranging from 80 bar to 150 bar, more preferably at a temperature ranging from 150° C. to 160° C. and a pressure ranging from 90 bar to 120 bar,

[0208] The biomass is preferably selected from the group consisting of vegetable oils, animal fats, fish oils and mixtures thereof.

[0209] The hydrocarbon fluid used in the present invention preferably comes from the processing of raw materials of biological origin. As described below, the term "biogenic carbon" or "biochar" means that the carbon has a natural origin and comes from biological material. Biocarbon content, biogenic carbon content and biomaterial content are expressions that mean the same value. Renewable materials or biomaterials are organic materials in which the carbon comes from carbon dioxide (on a human scale) that has been recently fixed from the atmosphere by photosynthesis. Biomaterial (100% carbon of natural origin) 14 C / 12 C isotope ratio greater than 10 -12 , usually about 1.2x 10 -12 , while the ratio of fossil materials is equal to zero. In fact, on time scales of at most a few decades, the isotopes formed in the atmosphere 14 C is subsequently integrated through photosynthesis. 14 The half-life of C is 5730 years. Therefore, substances produced by photosynthesis (i.e., usually plants) must have the largest isotope. 14 C content.

[0210] additive

[0211] According to one embodiment, the hydrocarbon fluid is mixed with at least one additive before being used as a diluent.

[0212] According to one embodiment, the diluent used in the present invention comprises a hydrocarbon fluid as defined in the present invention and at least one additive, preferably at least one antioxidant additive. The antioxidant additive can generally delay the degradation of the composition during use. This degradation is generally manifested as the formation of deposits, the presence of sludge or an increase in the viscosity of the composition.

[0213] Antioxidant additives particularly act as free radical inhibitors or hydroperoxide destroyers. Commonly used antioxidant additives include phenolic antioxidant additives, amine antioxidant additives, phosphorus-sulfur antioxidant additives, etc. Some of these antioxidant additives (e.g., phosphorus-sulfur antioxidant additives) produce ash. Phenolic antioxidant additives can be ash-free, or in the form of neutral or alkaline metal salts. Antioxidant additives can be particularly selected from sterically hindered phenols, sterically hindered phenol esters and sterically hindered phenols containing thioether bridges, diphenylamine, diphenylamine substituted with at least one C1-C12 alkyl, and mixtures thereof.

[0214] According to one embodiment, the sterically hindered phenol is chosen from compounds comprising a phenolic group, wherein at least one of the carbons adjacent to the carbon atom carrying the alcohol function is substituted by at least one C1-C10 alkyl group, preferably a C1-C6 alkyl group, preferably a C4 alkyl group, preferably a tert-butyl group.

[0215] Amine compounds are another class of antioxidant additives that can be used in combination with phenolic antioxidant additives. Examples of amine compounds are aromatic amines, such as aromatic amines having the formula NR4R5R6, wherein R4 represents an aliphatic group or an aromatic group that may be substituted, R5 represents an aromatic group that may be substituted, R6 represents a hydrogen atom, an alkyl group, an aryl group, or a group of the formula R7S(O)zR8, wherein R7 represents an alkylene group or an alkenylene group, R8 represents an alkyl group, an alkenyl group, or an aryl group, and z represents 0, 1, or 2.

[0216] Sulfur-containing alkylphenols or alkali metal salts or alkaline earth metal salts thereof can also be used as antioxidant additives.

[0217] Another class of antioxidant additives are copper compounds, such as copper thiophosphates or dithiophosphates, copper salts and carboxylates, copper dithiocarbamates, copper sulfonates, copper phenates, copper acetylacetonate. Copper (I) and copper (II) salts, succinates or succinic anhydride salts can also be used.

[0218] If an antioxidant is used in the diluent, the antioxidant is preferably present in an amount of 0.01% to 3% by weight relative to the weight of the composition and preferably in an amount of 0.05% to 2% by weight relative to the weight of the diluent.

[0219] Use as diluent:

[0220] The hydrocarbon fluid, optionally mixed with one or more additives, is used as a diluent for metal liquid-liquid extraction. More particularly, the hydrocarbon fluid defined in the present invention may be used as a diluent in a hydrometallurgical process comprising at least one metal liquid-liquid extraction step.

[0221] Another subject of the invention is a metal liquid-liquid extraction process comprising at least one step of contacting a solution of a metal M with an extraction solvent comprising at least one diluent and at least one extractant, the diluent being a hydrocarbon fluid as defined in the invention.

[0222] Generally, within the framework of the present invention, metal liquid-liquid extraction comprises a step of contacting a solution of the metal M with an extraction solvent comprising an extractant and a diluent, the diluent being a hydrocarbon fluid as defined in the present invention.

[0223] In the framework of the present invention, the solution of metal M generally comprises at least two different metals, and the metal liquid-liquid extraction can recover at least one metal, preferably at least two metals, respectively, from the solution of metal M. The metals can be, for example, selected from nickel, copper, cadmium, cobalt, manganese, lithium and zinc, and mixtures thereof, including alloys of the metals.

[0224] The metal in solution M may be in the form of metal oxides and / or metal hydroxides.

[0225] A person skilled in the art can select the extractant according to the metal present in the solution of metal M.

[0226] Typically, the extractant is miscible with the hydrocarbon fluid.

[0227] According to one embodiment, the extractant is selected from oximes containing one or two alkyl groups and phosphorous acids that may contain one or more alkyl groups, the alkyl groups preferably having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms, and the extractant is preferably selected from ketoximes having alkyl groups and phosphinic acids that may contain one or more alkyl groups, the alkyl groups preferably having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms.

[0228] As non-limiting examples, among the extractants, mention may be made of Solvay's Series of extractants or from BASF Series of extractants.

[0229] The solution of metal M may come, for example, from a step of dissolving a metal from a battery, more particularly an electrode of a battery.

[0230] Hydrometallurgical methods for battery recycling

[0231] Another subject of the invention is a hydrometallurgical process for recycling one or more batteries, said process comprising:

[0232] - a step of dissolving a metal present in at least one cell, in particular in an electrode of said at least one cell, so as to obtain a solution of the metal M,

[0233] - optionally, a step of clarifying the solution of the metal M to remove residues not dissolved in the metal solution,

[0234] - a step of metal liquid-liquid extraction, comprising at least one step of contacting the optionally clarified solution of the metal M with an extraction solvent, said extraction solvent comprising at least one diluent and at least one extractant, said diluent being a hydrocarbon fluid comprising at least 75% by weight of isoparaffins and less than 100 ppm by weight of aromatics relative to the total weight of the hydrocarbon fluid, said hydrocarbon fluid having a biodegradability of at least 60% at 28 days measured according to the OECD 301B standard.

[0235] Preferably, the method is performed on a lithium-ion battery.

[0236] The method generally allows for the recovery and reuse of metals present in batteries, particularly in battery electrodes.

[0237] Dissolution Steps

[0238] Within the framework of the present invention, it is generally preferred to dissolve the components to be recycled, in particular the electrodes of the battery, by leaching.

[0239] A solution comprising metals is thus obtained, the solution of metal M generally comprising at least two metals of different nature. Hydrometallurgical methods will then make it possible to recover separately said at least two metals of different nature.

[0240] The metal present in the solution of metal M may, for example, be chosen from nickel, copper, cadmium, cobalt, manganese, lithium and zinc, and mixtures thereof, including alloys of said metals.

[0241] For the dissolution step, a solution L is chosen that dissolves the metals present, more particularly the metals to be recovered. The solution L used for dissolution may, for example, be chosen from acids, bases, oxidizing agents or reducing agents.

[0242] Thus, the solution of metal M may contain the metal in the form of an oxide or a hydroxide.

[0243] Clarification Steps

[0244] The hydrometallurgical process of the invention may optionally comprise a clarification step to remove solid residues present in the solution of the metal M.

[0245] This optional clarification step can optionally be performed by decantation and / or centrifugation and / or filtration.

[0246] Liquid-Liquid Extraction Steps

[0247] The hydrometallurgical process of the invention comprises a step of liquid-liquid extraction of the metal, which comprises, after an optional clarification step, at least one step of contacting the solution of the metal M with an extraction solvent.

[0248] The extraction solvent comprises at least one diluent and at least one extractant.

[0249] The diluent is a hydrocarbon fluid as defined in the present invention.

[0250] A person skilled in the art can select the extractant according to the metal present in the solution of metal M.

[0251] Typically, the extractant is miscible with the hydrocarbon fluid.

[0252] According to one embodiment, the extractant is selected from oximes containing one or two alkyl groups and phosphorous acids that may contain one or more alkyl groups, the alkyl groups preferably having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms, preferably selected from ketoximes with alkyl groups and phosphinic acids that may contain one or more alkyl groups, the alkyl groups preferably having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms.

[0253] As non-limiting examples, among the extractants, mention may be made of Solvay's Series of extractants or from BASF Series of extractants.

[0254] The process of the invention may comprise at least one subsequent step of recovering at least one metal, preferably at least two metals of different nature.

[0255] Preferably, said subsequent recovery step is followed by a purification step of said recovered metal or metals.

[0256] Example

[0257] In the remainder of the description, examples are given to illustrate the invention and are not intended to limit the scope thereof in any way.

[0258] According to the process of the present invention, three hydrocarbon fluids are produced by subjecting biomass to HDO / ISO followed by a hydrogenation step.

[0259] Table 1 shows the physical and chemical properties of the hydrocarbon fluids.

[0260] [Table 1]

[0261] Fluid 1 Fluid 2 Fluid 3 Isoparaffins (weight / weight) % 98.9 95.1 96.2 Normal alkanes (weight / weight) % 1.1 4.9 3.8 Cycloalkanes (weight / weight) % 0 0 0 Aromatics (ppm) <20 <20 <20 Sulfur (ppm) 0.1 0.1 0.11 C13 (isomeric) 0.66 0 0 C14 (Isomerization) 4.15 0.12 0 C15 (Isomerization) 48.35 11.45 0 C16 (isomeric) 42.80 47.89 1.58 C17 (Isomerization) 2.52 18.57 14.17 C18 (Isomerization) 0.38 17.07 79.69 C19 (Isomerization) 0 0 0.12 C20 (Isomeric) 0 0 0.38 C27 (Isomeric) 0 0 0.29 Biocarbon content (%) 97 97 98 Initial boiling point (℃) 247.0 259.5 293.6 Boiling point 5% (℃) 255.7 270.2 296.7 Boiling point 50% (℃) 258.9 274.5 298.5 Boiling point 95% (℃) 266.8 286.4 305.3 Final boiling point(℃) 269.0 287.5 324.1 Biodegradation rate (28 days) (%) 89 89 89 Refractive index at 20°C 1.4336 1.4357 1.4394 <![CDATA[Density at 15°C (kg / m 3 )]]> 776.4 780.3 787.2 Flash point(℃) 115 125 149 Pour point(℃) -81 -60 -45 Kinematic viscosity at 40℃(cSt) 2.49 2.94 3.87 Vapor pressure at 20℃(kPa) <0.01 <0.01 <0.01

[0262] The above properties are measured using the following standards and methods: - Flash point: EN ISO 2719,

[0263] Density at -15°C: EN ISO 1185,

[0264] -Pour point: EN ISO 3016,

[0265] Viscosity at -40°C: EN ISO 3104,

[0266] - Boiling point: ASTM D86,

[0267] -Biodegradation rate: OECD 301B method, -Pour point: ASTM D5950

[0268] The hydrocarbon fluid of the present invention thus has excellent properties, particularly in terms of flash point, density, volatility and conductivity, so that excellent properties can be obtained when it is used as a diluent in an extraction solvent containing an extractant. Therefore, the extraction solvent used in the present invention enables the selective recovery and reuse of metals present in the battery during the recycling process of the battery.

Claims

1. A use of a hydrocarbon fluid as a diluent for metal liquid-liquid extraction, wherein the hydrocarbon fluid comprises at least 75% by weight of isoparaffins and less than 100 ppm by weight of aromatics, relative to the total weight of the hydrocarbon fluid, and the hydrocarbon fluid has a biodegradability of at least 60% at 28 days measured according to OECD 301B standard.

2. The use according to claim 1, wherein Relative to the total weight of the hydrocarbon fluid, the hydrocarbon fluid comprises: at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, of isoparaffins, and / or - up to 20% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, of normal alkanes, and / or - up to 1% by weight of cycloalkanes, and / or - Less than 50 ppm by weight of aromatics.

3. The use according to claim 1 or 2, wherein The hydrocarbon fluid comprises: a flash point according to standard ASTM D93 of greater than or equal to 80° C., preferably greater than or equal to 110° C., preferably greater than or equal to 120° C., or even greater than or equal to 140° C., and / or The kinematic viscosity at -40°C is less than or equal to 5 cSt, preferably less than or equal to 4 cSt, and / or the biogenic carbon content is at least 90% by weight, preferably at least 95% by weight, still more preferably at least 97% by weight, relative to the total weight of carbon atoms of the hydrocarbon fluid.

4. The use according to any one of claims 1 to 3, wherein The hydrocarbon fluid comprises: - the initial boiling point and the final boiling point are 200°C to 400°C, preferably 240°C to 350°C, and more preferably 250°C to 340°C, and / or - The difference between the final boiling point and the initial boiling point is 10°C to 80°C, preferably 20°C to 50°C.

5. The use according to any one of claims 1 to 4, wherein Relative to the total weight of the hydrocarbon fluid, the hydrocarbon fluid comprises: - 30% to 60% by weight of C15 isoparaffins and 30% to 60% by weight of C16 isoparaffins, or - 5 to 15% by weight of C15 isoparaffins, 30 to 60% by weight of C16 isoparaffins, 10 to 30% by weight of C17 isoparaffins and 10 to 30% by weight of C18 isoparaffins, - 10 to 30% by weight of C17 isoparaffins and 60 to 90% by weight of C18 isoparaffins.

6. The use according to any one of claims 1 to 5, wherein The hydrocarbon fluid is used in admixture with 0.01 wt % to 5 wt % of one or more antioxidant additives relative to the total weight of the hydrocarbon fluid and the antioxidant additives.

7. Use according to any one of claims 1 to 6 as a diluent in a hydrometallurgical process comprising at least one liquid-liquid extraction of a metal using an extraction solution comprising the diluent and at least one extractant.

8. The use according to claim 7, wherein The metals are obtained from recycling one or more batteries.

9. A metal liquid-liquid extraction method comprising at least one step of contacting a solution of metal M with an extraction solvent, the extraction solvent comprising at least one diluent and at least one extractant, the diluent being a hydrocarbon fluid comprising at least 75% by weight of isoparaffins and less than 100 ppm by weight of aromatics relative to the total weight of the hydrocarbon fluid, the hydrocarbon fluid having a biodegradability of at least 60% at 28 days measured according to OECD 301B standard.

10. A hydrometallurgical method for battery recycling, the method comprising: - a step of dissolving a metal present in at least one cell, in particular in an electrode of said at least one cell, so as to obtain a solution of the metal M, - optionally, a step of clarifying the solution of the metal M to remove residues not dissolved in the metal solution, -The metal liquid-liquid extraction method according to claim 9.

11. The metal liquid-liquid extraction method according to claim 9 or the hydrometallurgical method for battery recycling according to claim 10, wherein: The hydrocarbon fluid is as claimed in any one of claims 2 to 5.