Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/44—Carbon
  • C09C1/48—Carbon black
  • C09C1/482—Preparation from used rubber products, e.g. tyres
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/44—Carbon
  • C09C1/48—Carbon black
  • C09C1/56—Treatment of carbon black ; Purification
• • 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
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
  • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
• • 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
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
• • 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
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
  • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/19—Oil-absorption capacity, e.g. DBP values
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/80—Compositional purity
• • 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

Definitions

• the present invention relates to the field of carbonaceous materials of the carbon black type, in particular so-called “recovered” carbon blacks (or rCB for “recovered carbon black” according to Anglo-Saxon terminology) obtained by thermochemical transformation of tires at the end of their life. life. It also relates to a process for preparing these rCBs via a process of solvolysis of used tires with recycling of a hydrocarbon cut comprising aromatic compounds.
• Tires are mainly made up of rubbers for their elastic property (mixture of elastomers such as cross-linked natural and synthetic rubbers, with added additives such as silica, resin, sulfur, zinc oxide, carbon black, etc.) and fibers textiles and metals for their reinforcing property.
• Carbon blacks or CB for “Carbon Black” according to Anglo-Saxon terminology
• CB Carbon Black
• They are used in particular in the formulations of rubbers to improve the resistance of the latter (in terms of solidity and lifespan), to limit the deformation of tires with use and to facilitate heat transfer between the tires and the ground during rolling. They are generally obtained by incomplete combustion of hydrocarbons or vegetable oils and there are more than 35 grades, marketed and used as filler (mainly for the formulation of pneumatic rubbers). Their quality differs depending on their intrinsic properties.
• carbon blacks are characterized by high elemental carbon contents (>90% by weight relative to the total weight of the carbon black) and may contain other chemical elements such as hydrogen, oxygen, nitrogen and sulfur which are chemically linked to carbon. They generally appear in the form of black powders made up of elementary graphitic particles (more or less well crystallized) and quasi-spherical (10 to 500 nm), forming aggregates (100 to 1000 nm) which can themselves gather under the form of agglomerates (1 to 100 ⁇ m), all of which can then be transformed into granules (0.1 to 1 mm).
• the size of the elementary particles and the structure of the objects will largely impact the capacity of carbon blacks to disperse in an elastomeric matrix and therefore, ultimately, the reinforcing properties of the latter within a tire.
• the “specific surface” (or SBET) parameter determined by nitrogen physisorption, is characteristic of the size of elementary particles and provides information on the surface area of carbon black. potentially interacting with the elastomeric matrix.
• the structure of a carbon black is characterized, for its part, by the capacity of the latter to develop a porosity capable of being filled by a paraffinic oil, and therefore ultimately by an elastomeric matrix.
• a structure index equivalent to an oil adsorption index, is then determined, the associated analytical method being the OAN method for “Oil Adsorption Number” according to Anglo-Saxon terminology.
• Each carbon black is then associated with an acronym of the type NXYZ, where In summary, there is an SBET / OAN structure index relationship which makes it possible to classify the various carbon blacks according to their grade and their reinforcing or non-reinforcing character. For example, carbon blacks N110, N 120 and N234, very good reinforcing additives, are characterized by a high specific surface area and structure index. Depending on their intrinsic properties, carbon blacks will be used to formulate different rubbers, which are themselves used in the different constituent elements of a tire.
• tires When recycled, tires are generally initially crushed to obtain either shredded tires still containing some of the textile and metal fibers (typically pieces of 1 to 10 cm), or aggregates (generally less than 6 mm in size). ) free of all fibers. It is then possible to convert them into gaseous, liquid and solid fractions via thermal decomposition conversion processes.
• the solid fraction obtained is mainly made up of various grades of mixed carbon blacks, with the addition of inorganic ashes (mainly silica type and Zn-based compounds).
• the thermal decomposition of the “elastomer” fraction generates carbon compounds of varied nature (various decomposition products possibly recondensed) likely to be deposited on the surface of the carbon blacks.
• the rCB represents the entire solid fraction made up of initial carbon blacks mixed and modified on the surface by various carbonaceous deposits (decomposition products and/or elastomer residues), as well as inorganic ashes.
• the intrinsic properties of an rCB therefore depend on the elements that constitute it.
• the chemical composition of the rCBs, the agglomeration rate of the aggregates and their structure, and consequently the redispersion properties of the rCBs in an elastomeric matrix can be drastically modified compared to those of the initial carbon blacks depending on the composition of the treated end-of-life tires (choice of load) and the planned recycling process.
• pyrolysis processes are very frequently encountered (J. Yu et al., Frontiers of Environmental Science & Engineering, 2020, 14, 2, 7982; SQ Li et al., Ind. Eng. Chem. Res. 2004, 43, 5133; EP2661475).
• rCBs obtained post-pyrolysis are all characterized by the significant presence of carbonaceous deposits on the surface of the initial carbon blacks.
• XPS X-ray Photoelectron Spectroscopy
• ESCA Electrode Spectroscopy for Chemical Analysis
• this surface analysis makes it possible to define the elementary chemical composition of a material and thus determine the present contents of C, O, N, S, Si, Al, Zn, etc.
• the precise analysis of the spectrum associated with the carbon element provides information on the chemical environment of the carbon atoms constituting the rCB (thesis Ludovic Moulin: Valorization of recovered carbon black, process-product relationship . Process engineering. autoimmune des Mines d’Albi-Carmaux, 2018).
• These carbonaceous deposits are largely responsible for the agglomeration phenomena linking the various structures of the rCB at different scales: the solid leaving the reactor is often present in the form of blocks of several millimeters / centimeters which must then be finely ground in order to reuse it (in particular as an adjuvant for the formulation of new gums), which requires a significant energy expenditure.
• liquid fractions can be used to produce new hydrocarbon cuts (naphtha, gasoline, kerosene, diesel, vacuum distillate, residues), used in refineries to produce fuels or in petrochemicals to produce bases then used to develop plastic materials.
• Said process consists of recycling a load of used tires at a temperature less than or equal to 400°C and at a pressure less than 1.5 MPa, via bringing said load into contact with a solvent consisting of at least one hydrocarbon cut. comprising a content rich in aromatic compounds, poor in C40+ compounds (vacuum residues) and a moderate content of C5-C10 hydrocarbon compounds (gasoline), said solvent being able to come from the process itself (recycle).
• Said process is also characterized by a mass ratio between the liquid solvent and the specific filler, that is to say by a mass ratio greater than 3 weight/weight.
• the operating conditions, the composition of the hydrocarbon cut and the solvent/solid filler mass ratio as defined make it possible to maximize the production of rCB via better dissolution/decomposition of the solid filler while limiting the presence of carbonaceous residues in the final rCB .
• such a process limits the formation of gas to contents of between 1 and 7% by weight of the load to be treated.
• the present invention relates to a recovered carbon black (rCB) comprising carbon black, inorganic ashes, and carbonaceous residues resulting from the decomposition of tire rubbers and/or elastomeric residues, characterized in that said content of carbonaceous residues, determined in relation to the percentage of area of the peak Ci measured by X-ray photoelectron spectroscopy, is less than or equal to 1% of said area of the peak Ci, said percentage of area of the peak Ci being calculated in relation to the total area of the Co to Cs peaks.
• rCB recovered carbon black
• said recovered carbon black comprises between 50% and 98% by weight of carbon element relative to the total weight of said recovered black carbon.
• said recovered carbon black comprises between 0.5 and 4% by weight of oxygen element relative to the total weight of said recovered black carbon. According to one or more embodiments, said recovered carbon black comprises between 0.2 and 3% by weight of hydrogen element relative to the total weight of said recovered black carbon.
• said recovered carbon black comprises between 0.5 and 6% by weight of sulfur element per total weight of said recovered carbon black.
• said recovered carbon black comprises a content of extracted volatile organic compounds of between 0.2 and 20% by weight relative to the total weight of said recovered carbon black.
• said recovered carbon black comprises an inorganic ash content of between 4 and 50% by weight relative to the total weight of said recovered carbon black.
• said recovered carbon black comprises a specific surface area of between 30 and 150 m 2 /g.
• said recovered carbon black comprises a structure index, determined by the OAN analytical method in accordance with standard ASTM D2414, of between 55 and 110.10' 5 m 3 /kg.
• said content of carbonaceous residues, calculated relative to the % area of peak Ci measured by photoelectron spectroscopy, is between 0.001% and 0.05% area of peak Ci, said percentage of peak area Ci being calculated relative to the total area of the peaks Co to Cs.
• Another subject relates to a process for converting used tires to obtain recovered carbon black (rCB) according to the invention, said process comprising at least the following steps: a) sending a solid load based on used tires into an area reaction in the presence of a liquid solvent comprising aromatic compounds to dissolve at least partly said solid filler and thermally decompose said solid filler at least partially dissolved at a temperature below 400°C and at a pressure less than 1.5 MPa in order to obtain a gaseous effluent and a first liquid effluent comprising carbon black, the mass ratio between the liquid solvent and the solid filler being greater than 3 weight/weight; b) the first liquid effluent obtained in step a) is sent to a filtration and washing zone in the presence of a washing solvent in order to obtain a filtered and washed carbon black cake and a second liquid effluent, said step b) being carried out at a temperature between 55°C and 95°C; c) at least partly said gaseous effluent obtained at the
• step a) comprises the following sub-steps: a1) said solid charge and said liquid solvent are sent into a first stirred reactor to dissolve at least partially said solid charge; a2) said solid charge, at least partly dissolved, obtained at the end of step a1) is sent into a second stirred reactor to thermally decompose said solid charge at a temperature less than or equal to 400°C and obtain a liquid effluent containing carbon black particles in suspension.
• the content of C40+ hydrocarbon compounds in the hydrocarbon cut is less than 3% by weight relative to the total weight of said cut.
• Another object according to the invention relates to a recovered carbon black (rCB) obtained by a process for converting used tires comprising at least the following steps: a) a solid load based on used tires is sent into a reaction zone in the presence of a liquid solvent comprising aromatic compounds to dissolve at least partly said solid load and thermally decompose said solid load at least partially dissolved at a lower temperature at 400°C and at a pressure less than 1.5 MPa in order to obtain a gaseous effluent and a first liquid effluent comprising carbon black, the mass ratio between the liquid solvent and the solid filler being greater than 3 weight/weight ; b) the first liquid effluent obtained in step a) is sent to a filtration and washing zone in the presence of a washing solvent in order to obtain a filtered and washed carbon black cake and a second liquid effluent, said step b) being carried out at a temperature between 55°C and 95°C; c) at least partly said gaseous effluent obtained at
• Figure 1 is a schematic representation of an embodiment of obtaining a carbon black according to the invention.
• FIG 2 is a schematic representation of the process shown in Figure 1 in which the reaction zone and the filtration and washing zone of the process are more detailed. Detailed description of the invention
• Cn+ cut we mean a cut comprising hydrocarbons with at least n carbon atoms.
• the BET specific surface area is measured by nitrogen physisorption.
• the BET specific surface area is measured by nitrogen physisorption according to standard ASTM D3663-03 as described in Rouquerol F.; Rouquerol J.; Singh K. “Adsorption by Powders & Porous Solids: Principle, methodology and applications”, Academic Press, 1999.
• Thermogravimetric analysis is a technique widely used and well known by those skilled in the art, both for measuring the humidity level, the volatile rate and the ash content of rCB.
• the protocol used is derived from the ISO9924-2 standard used mainly for unvulcanized vulcanizates and blends.
• a first rise in temperature, from 25°C to 600°C under nitrogen, makes it possible to measure the water content (loss of mass in % between 25°C and 150°C) and the content of volatiles and/or pyrolyzable phase (loss mass between 150°C and 600°C).
• the sample is then cooled under nitrogen to 400°C.
• the rCB comprises between 0.2 and 4% by weight of oxygen element relative to the total weight of the rCB, preferably between 0.4 and 3% by weight, and even more preferably between 0.8 and 2.7 % weight. More particularly, the rCB comprises between 0.2 and 3% by weight of hydrogen element relative to the total weight of the rCB, preferably between 0.4 and 2.5% by weight, and even more preferably between 0.5 and 1 .5% weight.
• the rCB comprises between 0.05 and 1% by weight of nitrogen element relative to the total weight of the rCB, preferably between 0.1 and 0.7% by weight, and even more preferably between 0.15 and 0. .4% weight.
• the rCB comprises between 0.5 and 6% by weight of sulfur element per total weight of the rCB, preferably between 1.5 and 5% by weight, and even more preferably between 2 and 3.5% by weight.
• the rCB according to the invention also comprises inorganic ashes.
• Inorganic ashes consist of at least the atomic element Si, mainly present in its oxidized form SiC>2 (silica), and at least the element zinc, mainly present in its oxidized form ZnO (zinc oxide) and/or its ZnS sulphide form (zinc sulphide), preferably in its ZnS sulphide form.
• the application of a specific heat treatment (at least 950°C in air, by ATG analysis) makes it possible to quantify the inorganic ash content present in the rCB according to the invention.
• the inorganic ash content is advantageously between 4 and 50% by weight relative to the total weight of the rCB, preferably between 8 and 40% by weight, and even more preferably between 10 and 30% by weight.
• the rCB according to the invention may also contain other heteroelements at elemental contents less than 1% by weight relative to the total weight of the rCB, preferably less than 0.5% by weight and even more preferably less than 0 .2% weight.
• Said heteroelements can be, for example and non-exhaustively, the elements Al, Ca, Mg, Cl, Fe, K, Br, Co, Ti and P. Measuring the content of these elements can be carried out by X-ray fluorescence.
• the rCB according to the invention comprises a specific surface area, determined by nitrogen physisorption, of between 30 and 150 m 2 /g, preferably between 50 and 90 m 2 /g and even more preferably between 50 and 75 m 2 /g.
• the structure index determined by the OAN analytical method in accordance with standard ASTM D2414, is between 55 and 110.10 -5 m 3 /kg, preferably between 55 and 90.10' 5 m 3 /kg.
• the carbon black (CB) contained in recovered carbon black (rCB) may include several grades of commercial carbon blacks, taken alone or in mixtures.
• the recovered carbon black (rCB) can be obtained by a used tire conversion process comprising at least the following steps: a) a solid charge based on used tires is sent to a reaction zone in the presence of a liquid solvent comprising aromatic compounds for at least partially dissolving said solid filler and thermally decomposing said at least partially dissolved solid filler at a temperature below 400°C and at a pressure below 1.5 MPa in order to obtain a gaseous effluent and a first liquid effluent comprising carbon black, the mass ratio between the liquid solvent and the solid filler being greater than 3 weight/weight; b) the first liquid effluent obtained in step a) is sent to a filtration and washing zone in the presence of a washing solvent in order to obtain a filtered and washed carbon black cake and a second liquid effluent, said step b) being carried out at a temperature between 55°C and 95°C; c) at least partly said gaseous effluent obtained at the end of step a) and at least partly
• step c) a content of C40+ hydrocarbon compounds less than 5% by weight relative to the total weight of said hydrocarbon cut; d) at least part of said hydrocarbon cut obtained at the end of step c) is sent into the reaction zone as liquid solvent of step a); e) the filtered and washed carbon black cake obtained at the end of step b) is dried at a temperature between 50 and 200°C to recover the carbon black.
• the present invention also relates to the process for preparing rCB according to the invention from used tires.
• Said preparation process is a conversion process and, more specifically, a process for solvolysis of used tires which comprises, referring to Figure 1 associated with an embodiment according to the invention, at least the following steps: a) a solid load 100 based on used tires is sent into a reaction zone 80 in the presence of a liquid solvent 760 comprising aromatic compounds to dissolve at least partly said solid load and thermally decompose said solid load at least partially dissolved at a temperature less than 400°C, preferably between 365°C and 395°C, and even more preferably between 380°C and 395°C, and at a pressure less than 1.5 MPa, preferably between 0.2 and 1.2 MPa, in order to obtain at least one gaseous effluent 310 and a first liquid effluent 320 comprising the rCB according to the invention, the mass ratio between the liquid solvent 730 and the solid filler 100 being greater than 3 weight/weight
• step c) said hydrocarbon cut 730 obtained at the end of step c) is sent at least in part into the reaction zone 80 as liquid solvent 760 from step a); e) the filtered and washed rCB cake according to the invention 430 obtained at the end of step b) is dried in a drying zone 50 at a temperature between 50°C and 200°C, preferably for a sufficient duration so that the content of washing solvent in the dried cake is less than 0.5% by weight relative to the total weight of said dried cake.
• the drying time is between 10 minutes and 36 hours, more
• the solid filler 100 used in the context of the present invention is advantageously based on tires resulting from the treatment of used tires which can come from any origin, such as light vehicles (LV) or heavy goods vehicles (PL) for example.
• Said solid filler can advantageously be in the form of tire aggregates, ie in the form of particles of sizes less than 6 mm.
• said solid filler 100 is substantially free of textile fibers and metal wires, and/or tire shreds, ie pieces of crushed tires, of characteristic size generally between 1 cm and 20 cm.
• the solid load 100 is sent to a pretreatment unit 10 in order to eliminate the textile fibers and the metal wires 110 from the solid load 100.
• Such a pretreatment unit is well known to those skilled in the art and can consist of crushers of different types (ie a rotary shear, a shredder crusher, a granulator, a refiner crusher), a magnetic separator, or even a vibrating sieve, separation table.
• crushers of different types (ie a rotary shear, a shredder crusher, a granulator, a refiner crusher), a magnetic separator, or even a vibrating sieve, separation table.
• Step a) is preferably carried out at a temperature below 400°C, preferably between 365°C and 395°C, and even more preferably between 380°C and 395°C, and at a pressure below 1.5 MPa, preferably between 0.2 and 1.2 MPa.
• a temperature below 400°C preferably between 365°C and 395°C, and even more preferably between 380°C and 395°C, and at a pressure below 1.5 MPa, preferably between 0.2 and 1.2 MPa.
• the first liquid effluent 320 comprising the rCB according to the invention is then sent to the filtration and washing zone 40 (i.e. step b) of the preparation process according to the invention) in order to recover the rCB cake according to the invention filtered and washed 430 and the second liquid effluent 410.
• This step is carried out at a temperature between 55°C and 95°C, preferably between 60°C and 90°C, and even more preferably between 65°C and 85°C. °C.
• the viscosity of the second liquid effluent 410 measured at 100°C is less than 10 cP, preferably less than 5 cP, more preferably less than 3 cP, as measured according to standard ASTM D3236.
• the filtration and washing unit can comprise any device allowing the filtration of the rCB particles according to the invention contained in the first liquid effluent 320.
• a device can for example be in the form of a rotating filter preferably operating at a temperature between 55°C and 95°C, preferably between 60°C and 90°C, and even more preferably between 65°C and 85°C.
• the rCB cake according to the invention is washed using a washing solvent.
• the washing solvent used during step b) is a solvent external to process 800, as shown in Figure 1.
• the solvent can be chosen from toluene or xylene, preferably xylene.
• the washing solvent used during step b) is composed of at least partly a light cut 720 obtained at the end of step c). More particularly, referring to Figure 2, a fraction of the light cut 720 can be sent to a distillation column 90 via line 725. The complementary fraction 735 of the light cut is sent outside the process according to the invention as a valuable product. At the outlet of the distillation column 90, we obtain a light cut 910 comprising aromatic compounds, whose final boiling temperature is less than or equal to 200°C, preferably less than 150°C, which can serve at least in part as a washing solvent for the filtration/washing zone 40 The heavier cut 920 can be sent outside the process as recoverable product 920.
• the filtered and washed rCB cake according to the invention 430 is sent to a drying unit 50 operating at a temperature between 50 and 200°C, preferably between 50 and 150°C in order to recover the rCB according to the invention 520 (i.e. step e) of the process according to the invention).
• the steam effluent 510 from the drying unit 50 comprising the washing solvent is recycled in the washing/filtration unit 40.
• the gaseous effluent 310 obtained at the end of step a) and the second liquid effluent 410 obtained at the end of step b) are sent to the fractionation unit 70 (i.e. the step c) of the process according to the invention) to produce at least one hydrocarbon cut 730 comprising a content of aromatic compounds greater than 30% by weight relative to the total weight of said hydrocarbon cut 730, and further comprising at least:
• the hydrocarbon cut 730 also comprises a content of C10-C20 hydrocarbon compounds of between 20 and 65% by weight relative to the total weight of the hydrocarbon cut, preferably between 30 and 65% by weight, and even more preferably between 45 and 65% by weight.
• the hydrocarbon cut 730 also comprises a content of C20-C40 hydrocarbon compounds of between 30 and 80% by weight relative to the total weight of the hydrocarbon cut, preferably between 30 and 70% by weight, and even more preferably between 30 and 55% by weight.
• the hydrocarbon cut 730 has an initial boiling temperature of between 50°C and 325°C, preferably between 50°C and 250°C, and a final boiling temperature between 350 and 520°C, preferably between 350°C and 450°C.
• the fractionation zone 70 also makes it possible to obtain non-condensable gases 710, the light cut 720 whose final boiling temperature is preferably between 250°C and 325°C, and a heavy cut 740, whose temperature initial boiling point is preferably between 350°C and 450°C.
• the light cut 720 can be sent at least in part as a washing solvent into the washing and filtration zone 40 to obtain the filtered and washed rCB cake according to the invention 430.
• the light cut 720 comprises a content of C10- hydrocarbon compounds greater than 60% by weight relative to the total weight of the light cut 720.
• the heavy cut 740 comprises a content of C40+ hydrocarbon compounds greater than 60% by weight relative to the total weight of the heavy cut 740.
• At least part of a fraction of the hydrocarbon cut 730 is sent to the reaction zone 80 of step a) as liquid solvent 760, the other part 750 being advantageously sent outside the process according to the invention as a recoverable product.
• the mass ratio between the liquid solvent 730 and the flow rate of the solid charge 100 injected into the reaction zone 80 is greater than or equal to 3 weight/weight (wt/wt), preferably between 3 and 10 wt/weight, more preferably included between 4 and 7 weight/weight.
• one of the characteristics of the liquid solvent 760 is that it contains an aromatic content greater than 30% by weight relative to the total weight of said liquid solvent 760, making it possible to effectively dissolve the solid filler 100 and effectively reduce the viscosity of the medium. reaction in the reaction zone 80.
• Another advantage of the process according to the invention is that the use of such a solvent makes it possible to remain in liquid form while limiting the pressure in the reactors to a level below 1.5 MPa counting given the limited production of gases and light hydrocarbons in the reaction zone 80 and the low content of C10- hydrocarbon compounds in the hydrocarbon cut 730.
• the description given below concerns a process for converting used tires making it possible to maximize the production of rCB while limiting the presence of carbonaceous residues in said rCB.
• the solid load 100 is sent to the pretreatment unit 10 in order to eliminate the textile fibers and metal threads 110 from the solid load 100.
• the solid load is substantially free of textile fibers and metal threads is then sent to the reaction zone 80 allowing the thermal degradation of the used tires comprising a first stirred reactor 20 supplied with liquid solvent 760 and aimed at promoting the dissolution of the tire aggregates or shreds contained in the solid load 100.
• the solvent load mass ratio liquid/solid filler is greater than or equal to 3 weight/weight, preferably between 3 and 10, more preferably between 4 and 7 weight/weight.
• the temperature in the reactor 20 is preferably between 200°C and 300°C, preferably between 250°C and 290°C.
• the ground materials or aggregates are dissolved.
• the time required to achieve this dissolution is preferably between 30 minutes and 2 hours.
• the pieces of gum, and the future rCB according to the invention which gradually frees itself from the gum, remain in suspension thanks to mechanical or hydrodynamic agitation, induced for example by an ascending flow of liquid resulting from recirculation by forced convection, or by any other means allowing the environment to be kept agitated.
• the metal wires possibly still present in the solid charge and which would not have been dissolved, sediment and leave the first stirred reactor 20 at its base via line 210. Under these conditions, the temperature is too low for the reactions of carbon-carbon cracking starts significantly and only the crosslinking bonds between polymers, such as the SS bonds linked to the vulcanization of rubbers can crack significantly.
• the liquid fraction 220 obtained containing the residual solid materials in suspension is directed to a second stirred reactor 30 in which the thermal degradation reactions are carried out under moderate temperature conditions, ie at a temperature less than or equal to 400°C, preferably between 365°C and 395°C, and even more preferably between 380°C and 395°C, and for a limited time (corresponding to the residence time of the liquid fraction in the reactor 30) preferably between 30 minutes and 2 hours, preferably between 45 minutes and 90 minutes.
• moderate temperature conditions ie at a temperature less than or equal to 400°C, preferably between 365°C and 395°C, and even more preferably between 380°C and 395°C, and for a limited time (corresponding to the residence time of the liquid fraction in the reactor 30) preferably between 30 minutes and 2 hours, preferably between 45 minutes and 90 minutes.
• the quantity of heat necessary to carry out the thermal degradation reactions can be provided by an exchanger located on a pump-around (“pump-around” according to Anglo-Saxon terminology, not shown in the figures) around the second stirred reactor 30 or by any other means such as an exchanger on the wall of the reactor or an exchanger or a furnace on the charge upstream of the reactor for example.
• Agitation in the second stirred reactor 30 is maintained using a mechanical stirring system or by the spinning system or by any other means known to those skilled in the art.
• the reactor pressure is maintained at a level below 1.5 MPa using a regulation valve (not shown in the figures).
• the first liquid effluent 320 containing the rCB particles according to the invention in suspension and the gaseous effluent 310 are obtained in the second stirred reactor 30.
• the first liquid effluent 320 is then sent to the filtration and washing 40, comprising a rotating filter 41 and an intermediate fractionation unit 42 (see Figure 2).
• the rotary filter 41 preferably operates at a temperature between 50°C and 200°C, and makes it possible to obtain an rCB cake according to the invention and a liquid fraction 425.
• washing solvent 800 such as toluene or xylene, preferably xylene
• the washing solvent 800 such as toluene or xylene, preferably xylene
• a washing flow 405 can be sent to the intermediate fractionation unit 42 to obtain a cut 610 which can be recycled at least partly upstream of the rotary filter 41 by means of the line as a complementary washing solvent, and a cut 415 which can be sent with the liquid fraction 425, in the fractionation zone 70 as a second liquid effluent 410.
• the rCB according to the invention filtered and washed 430 is then sent to the drying unit 50 operating at a temperature between 50 and 200°C, advantageously for a sufficient time so that the content of washing solvent in the dried cake is lower at 0.5% by weight relative to the total weight of said dried cake.
• the rCB according to the invention filtered, washed and dried 520 can then advantageously be pelletized (granulated) with water to form pellets of a few millimeters for example to facilitate its transport and recovery.
• the rCB thus produced can again be used in the elastomer industry as a reinforcing agent, or as a pigment for other applications in inks, plastics or paints for example, after further processing and conditioning steps of the material according to uses and applications.
• the residual washing solvent can be recovered at the outlet of the drying unit 50 and be at least partly recovered via line 510.
• the fractionation zone 70 can be constituted heat exchangers, gas-liquid separator flasks, a distillation column containing a top drawoff, a bottom drawoff and a side drawoff, or a sequence of several distillation columns, such as a sequence of a distillation column at atmospheric pressure operating with a withdrawal at the top and a withdrawal at the bottom, followed by a distillation column operating under a low vacuum.
• This fractionation zone 70 particularly makes it possible to produce the hydrocarbon cut 730 comprising a content of aromatic compounds greater than 30% by weight relative to the total weight of said hydrocarbon cut 730, preferably greater than 40% by weight, and further comprising:
• the hydrocarbon cut is sent to the first reactor 20 of the reaction zone 80 as a liquid solvent.
• This fractionation zone 70 also makes it possible to obtain the non-condensable gas 710, the light cut 720 whose final boiling temperature is preferably between 250°C and 325°C, and the heavy cut 740, whose temperature d The initial boiling point is preferably between 350°C and 450°C.
• the light cut 720 can be sent at least in part as washing solvent into the washing and filtration device 41 of the washing and filtration zone 40 to obtain the rCB cake according to the invention filtered and washed 430.
• used tire aggregates solid filler
• used tire aggregates solid filler
• the tire aggregates come from a pretreatment unit 10 and are free of textile and metal fibers.
• the aggregates are then sent continuously to a dissolution reactor where they are mixed with the liquid solvent resulting from the recycling of the hydrocarbon cut 730 from the fractionation zone 70.
• a part of the hydrocarbon cut 730 serves as liquid solvent 760, the composition of which is shown in Table 1 below.
• the quantity of solid load processed is 100 kg/h.
• the quantity of solvent which is recycled in the reactor 20 is 500 kg/h, corresponding to a solvent/aggregate mass ratio equal to 5 wt/wt.
• the temperature is maintained at 290°C, which allows the aggregates to dissolve.
• the liquid fractions and the future rCB in suspension are then directed to reactor 30 where the temperature is maintained at 385°C for one hour.
• a first liquid effluent 320 and a gaseous effluent 310 are recovered, the latter being sent entirely to the fractionation zone 70.
• the first liquid effluent 320 is sent to a rotating filter 41 operating at 80°C.
• the filtered rCB is washed with xylene at a temperature of 80°C.
• the second liquid effluent 410 collected at the outlet of the washing and filtration zone 40 is sent in its entirety to the fractionation zone 70.
• the filtered and washed rCB 430 is sent to a drying unit 50 operating at 150°C for 24 hours allowing the filtered, washed and dried rCB to be recovered 520.
• Example 2 not in accordance with the invention, the steps of the conversion process and the operating conditions are identical to those of Example 1, except with regard to the content of C40+ hydrocarbon compounds (residues under vacuum or RSV ) of the liquid solvent 760 which is outside the range according to the invention, and with regard to the step of washing the recovered carbon black (rCB) which is carried out at a temperature of 50°C.
• RSV recovery carbon black

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Carbon And Carbon Compounds (AREA)
• Compositions Of Macromolecular Compounds (AREA)
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• 2022
  • 2022-03-30 FR FR2202850A patent/FR3134106B1/fr active Active
• 2023
  • 2023-03-14 EP EP23710366.8A patent/EP4499759A1/de active Pending
  • 2023-03-14 CA CA3244634A patent/CA3244634A1/fr active Pending
  • 2023-03-14 AU AU2023246580A patent/AU2023246580A1/en active Pending
  • 2023-03-14 JP JP2024557505A patent/JP2025510967A/ja active Pending
  • 2023-03-14 WO PCT/EP2023/056441 patent/WO2023186520A1/fr not_active Ceased
  • 2023-03-14 CN CN202380031484.3A patent/CN118974179A/zh active Pending
  • 2023-03-14 KR KR1020247032279A patent/KR20240167828A/ko active Pending
  • 2023-03-14 US US18/852,028 patent/US20250206955A1/en active Pending
  • 2023-03-28 TW TW112111627A patent/TW202348552A/zh unknown

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