METHOD FOR SOLVOLYSING TYRES WITH RECYCLING OF A HYDROCARBON FRACTION COMPRISING AROMATIC COMPOUNDS
20230331991 · 2023-10-19
Assignee
Inventors
Cpc classification
C09C1/482
CHEMISTRY; METALLURGY
C10B53/07
CHEMISTRY; METALLURGY
International classification
C10B53/07
CHEMISTRY; METALLURGY
Abstract
The invention relates to a process for converting used tyres to obtain carbon black, comprising the following steps: a) sending a solid feedstock based on used tires to a reaction zone in the presence of a liquid solvent to obtain a vapor effluent and a first liquid effluent comprising the carbon black, b) sending the liquid effluent to a filtration and washing unit to obtain a filtered and washed carbon black cake and a second liquid effluent; c) sending said vapor effluent and the second liquid effluent to a fractionation zone to obtain at least one hydrocarbon cut; d) sending said hydrocarbon cut obtained at the end of step c) to the reaction zone as liquid solvent of step a); e) drying the carbon black cake.
Claims
1. A process for converting used tyres to obtain carbon black, comprising at least the following steps: a) sending a solid feedstock (100) based on used tires to a reaction zone (80) in the presence of a liquid solvent (760) comprising aromatic compounds to at least partly dissolve said solid feedstock and to thermally decompose said at least partially dissolved solid feedstock at a temperature below or equal to 425° C. and at a pressure of less than 1.5 MPa in order to obtain a gaseous effluent (310) and a first liquid effluent (320) comprising carbon black, the weight ratio between the liquid solvent (760) and the solid feedstock (100) being greater than 3 weight/weight; b) sending the first liquid effluent (320) obtained in step a) to a filtration and washing zone (40) in the presence of a washing solvent in order to obtain a filtered and washed carbon black cake (430) and a second liquid effluent (410); c) sending, at least in part, said gaseous effluent (310) obtained at the end of step a) and, at least in part, the second liquid effluent (410) obtained at the end of step b) to a fractionation zone (70) to obtain at least one hydrocarbon cut (730) having a content of aromatic compounds of greater than 30% by weight relative to the total weight of said hydrocarbon cut, and further having: a content of C5-C10 hydrocarbon compounds of less than 20% by weight relative to the total weight of the hydrocarbon cut; and a content of C40+ hydrocarbon compounds of less than 5% by weight relative to the total weight of said hydrocarbon cut; d) sending, at least in part, said hydrocarbon cut (730) obtained at the end of step c) to the reaction zone (80) as liquid solvent (760) of step a); e) drying the filtered and washed carbon black cake (430) obtained at the end of step b) at a temperature of between 50° C. and 200° C. to recover the carbon black.
2. The process as claimed in claim 1, wherein, before step a), said solid feedstock (100) is sent to a pretreatment unit (10) to at least partly remove the textile fibers and metal wires contained in said solid feedstock (100).
3. The process as claimed in claim 1, wherein sFIGtep a) comprises the following substeps: a1) sending said solid feedstock (100) and said liquid solvent (760) to a first stirred reactor (20) to at least partly dissolve said solid feedstock (100); a2) sending said at least partly dissolved solid feedstock obtained at the end of step a1) to a second stirred reactor (30) to thermally decompose said solid feedstock at a temperature below or equal to 425° C. and to obtain a liquid effluent containing carbon black particles in suspension.
4. The process as claimed in claim 1, wherein the content of aromatic compounds in the hydrocarbon cut (730) is greater than 40% by weight relative to the total weight of said cut.
5. The process as claimed in claim 1, wherein the content of C5-C10 hydrocarbon compounds in the hydrocarbon cut (730) is less than 10% by weight relative to the total weight of said cut.
6. The process as claimed in claim 1, wherein the content of C40+ hydrocarbon compounds in the hydrocarbon cut (730) is less than 3% by weight relative to the total weight of said cut.
7. The process as claimed in claim 1, wherein the viscosity of the second liquid effluent (410) at 100° C. is less than 10 cP as measured according to the standard ASTM D3236.
8. The process as claimed in claim 1, wherein, in step c), a light cut (720) is also obtained, the final boiling point of which is preferentially between 250° C. and 325° C.
9. The process as claimed in claim 8, wherein the light cut (720) is sent at least in part upstream to a distillation column (90) to obtain at least one light cut (910), the final boiling point of which is below or equal to 200° C.
10. The process as claimed in claim 9, wherein said light cut (910), the final boiling point of which is below or equal to 200° C., is sent at least in part to the filtration/washing zone (40) as washing solvent according to step b) of said process.
11. The process as claimed in claim 1, wherein step b) comprises the following substeps: b1) filtering the liquid effluent (320) in a washing and filtration device (41) to obtain a filtered carbon black cake and a liquid fraction (425); b2) washing the filtered carbon black cake obtained at the end of step b1) in the presence of a washing solvent to obtain a filtered and washed carbon black cake (430) and a washing stream (405).
12. The process as claimed in claim 11, wherein the washing stream (405) is sent to an intermediate fractionation unit (42) to obtain a cut (610) which is recycled at least in part upstream of the washing and filtration device (41) as washing solvent.
13. The process as claimed in claim 1, wherein the hydrocarbon cut (730) has a content of C10-C20 hydrocarbon compounds of between 20% and 65% by weight relative to the total weight of the hydrocarbon cut.
14. The process as claimed in claim 1, wherein the hydrocarbon cut (730) has a content of C20-C40 hydrocarbon compounds of between 30% and 80% by weight relative to the total weight of the hydrocarbon cut.
15. The process as claimed in claim 1, wherein the hydrocarbon cut (730) has an initial boiling point of between 50° C. and 325° C. and a final boiling point of between 350° C. and 520° C.
Description
LIST OF FIGURES
[0033]
[0034]
DETAILED DESCRIPTION
[0035] Cn hydrocarbon cut is understood to mean a cut comprising hydrocarbons having n carbon atoms.
[0036] Cn+ cut is understood to mean a cut comprising hydrocarbons having at least n carbon atoms.
[0037] With reference to
[0045] The solid feedstock 100 used in the context of the present invention is advantageously based on tires resulting from the processing of used tires which may originate from any source, for instance light vehicles (LV) or heavy goods vehicles (HGV). Said solid feedstock may advantageously be in the form of tyre granules, i.e. in the form of particles less than 6 mm in size. Preferably, said solid feedstock 100 is substantially free of textile fibers and metal wires, and/or of ground tyre materials, i.e. pieces of ground tyres, with a characteristic size generally between 1 cm and 20 cm. Thus, according to a preferred embodiment according to the invention, the solid feedstock 100 is sent to a pretreatment unit 10 in order to remove textile fibers and metal wires 110 from the solid feedstock 100. Such a pretreatment unit is well known to those skilled in the art and can consist of grinders of various types (i.e. a rotary shear, a shredder, a granulator, a rechipper), a magnetic separator, or else a vibrating screen, a separation table.
[0046] According to step a) of the conversion process, the rubber which is contained in the solid feedstock 100 is dissolved in contact with the liquid solvent 760 and then is thermally decomposed. The origin and composition of the liquid solvent 760 will be described in detail below. Step a) is preferably carried out at a temperature below or equal to 425° C., preferably at a temperature of between 375° C. and 425° C., and at a pressure of less than 1.5 Mpa, preferably between 0.8 MPa and 1.2 MPa. At the end of step a), the at least one gaseous effluent 310 is obtained and the first liquid effluent 320 comprising carbon black, and optionally solids 210 contained in the used tires, such as metal wires or textile fibers, which are released and separated from the liquid effluent 320 obtained at the end of this step.
[0047] The first liquid effluent 320 comprising the carbon black 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 filtered and washed carbon black cake 430 and the second liquid effluent 410. In one embodiment according to the invention, the viscosity of the second liquid effluent 410 measured at 100° C. is less than 10 cP, preferentially less than 5 cP, more preferentially less than 3 cP, as measured according to the standard ASTM D3236.
[0048] The filtration and washing unit can comprise any device allowing the filtration of the carbon black particles contained in the first liquid effluent 320. Such a device may for example be in the form of a rotary filter operating preferentially at a temperature between 50° C. and 200° C. During step b), the carbon black cake is washed using a washing solvent.
[0049] In one embodiment according to the invention, the washing solvent used during step b) is a solvent external to the process 800, as shown in
[0050] In another embodiment according to the invention, the washing solvent used during step b) is composed, at least partly, of a light cut 720 obtained at the end of step c). More particularly, with reference to
[0051] The filtered and washed carbon black cake 430 is sent to a drying unit 50 operating at a temperature of between 50° C. and 200° C., preferably between 50° C. and 150° C. in order to recover the carbon black 520 (i.e. step e) of the process according to the invention). Advantageously, the vapor effluent 510 from the drying unit 50 comprising the washing solvent is recycled to the washing/filtration unit 40.
[0052] According to an essential feature of the conversion process according to the invention, 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. step c) of the process according to the invention) to produce at least one hydrocarbon cut 730 comprising a content of aromatic compounds of greater than 30% by weight relative to the total weight of said hydrocarbon fraction 730, and further comprising at least: [0053] a content of C5-C10 hydrocarbon compounds of less than 20% by weight relative to the total weight of the hydrocarbon cut 730, preferably less than 10% by weight, more preferentially between 1% and 8% by weight; and [0054] a content of C40+ hydrocarbon compounds of less than 5% by weight relative to the total weight of said hydrocarbon cut 730, preferably less than 3% by weight, more preferentially less than 1% by weight, and even more preferentially less than 0.5% by weight.
[0055] Advantageously, the hydrocarbon cut 730 also has 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 preferentially between 45% and 65% by weight.
[0056] Advantageously, the hydrocarbon cut 730 also has 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 preferentially between 30% and 55% by weight.
[0057] Advantageously, the hydrocarbon cut 730 has an initial boiling point of between 50° C. and 325° C., preferably between 50° C. and 250° C., and a final boiling point of between 350° C. and 520° C., preferably between 350° C. and 450° C.
[0058] Specifically, the applicant has observed that the use of such a recycled hydrocarbon cut as a liquid solvent 760 of the reaction zone 80 (i.e. step d) of the process according to the invention), with a content rich in aromatic compounds, low in C40+ compounds (vacuum residues), and a content of C5-C10 hydrocarbon compounds (gasoline) that is not too high, and using a solvent/solid feedstock weight ratio of greater than 3 weight/weight, preferably between 3 and 10 weight/weight, more preferentially between 4 and 7 weight/weight, synergistically allows better dissolution and decomposition of the solid feedstock 100 thus maximizing the production of carbon black. This results notably in a shorter filtration time of the carbon black in the washing/filtration zone 40.
[0059] Advantageously, the fractionation zone 70 also makes it possible to obtain noncondensable gases 710, light cut 720, the final boiling point of which is preferentially between 250° C. and 325° C., and a heavy cut 740, the initial boiling point of which is preferentially between 350° C. and 450° C. Advantageously, the light cut 720 can be sent, at least in part, as washing solvent to the washing and filtration zone 40 to obtain the filtered and washed carbon black cake 430. Advantageously, the light cut 720 has a content of C10- hydrocarbon compounds of greater than 60% by weight relative to the total weight of the light cut 720.
[0060] Advantageously, the heavy cut 740 has a content of C40+ hydrocarbon compounds of greater than 60% by weight relative to the total weight of the heavy cut 740.
[0061] According to the invention, a fraction of the hydrocarbon cut 730 is sent, at least in part, to the reaction zone 80 of step a) as liquid solvent 760, the other part 750 being advantageously sent out of the process according to the invention as an upgradable product. The weight ratio between the liquid solvent 760 and the flow of the solid feedstock 100 injected into the reaction zone 80 is greater than 3 weight/weight (w/w), preferably between 3 and 10 weight/weight, more preferentially between 4 and 7 weight/weight. Specifically, one of the features of the liquid solvent 760 is that it contains a content of aromatics of greater than 30% by weight relative to the total weight of said liquid solvent 760, making it possible to effectively dissolve the solid feedstock 100 and to effectively reduce the viscosity of the reaction medium 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 given the limited production of gas and light hydrocarbons in the reaction zone 80 and the low content of C10- hydrocarbon compounds in the hydrocarbon cut 730.
[0062] In order to better understand the invention, the description given below as an application example relates to a process for converting used tyres which makes it possible to maximize the the recovery of carbon black. With reference to
[0063] At the end of the reaction in the second stirred reactor 30, the first liquid effluent 320 containing the carbon black particles in suspension and the gaseous effluent 310 are obtained. The first liquid effluent 320 is then sent to the filtration and washing zone 40, comprising a rotary filter 41 and an intermediate fractionation unit 42 (cf.
[0064] The gaseous effluent 310 leaving the reaction zone 80 via the second reactor 30, and the second liquid effluent 410 from the washing/filtration zone 40 are then sent to the fractionation zone 70. The fractionation zone 70 may consist of heat exchangers, gas-liquid separator drums, a distillation column containing a top take-off, a bottom take-off and a side take-off, or a sequence of several distillation columns, such as a sequence of a distillation column at atmospheric pressure operating with a top take-off and a bottom take-off, followed by a distillation column operating under a low vacuum. This fractionation zone 70 makes it possible in particular to produce the hydrocarbon cut 730 comprising a content of aromatic compounds of greater than 30% by weight relative to the total weight of said hydrocarbon cut 730, preferentially greater than 40% by weight, and further having: [0065] a content of C5-C10 hydrocarbon compounds of less than 20% by weight relative to the total weight of the hydrocarbon cut 730, preferably less than 10% by weight, more preferentially between 1% and 8% by weight; and [0066] a content of C40+ hydrocarbon compounds of less than 5% by weight relative to the total weight of said hydrocarbon cut 730, preferably less than 3% by weight, more preferentially less than 1% by weight, and even more preferentially less than 0.5% by weight; [0067] at least a portion of which can be recycled as a liquid solvent 760 to the reaction zone 80, it being possible for the other portion 750 to be upgraded as product. Preferably, the hydrocarbon cut is sent to the first reactor 20 of the reaction zone 80 as liquid solvent.
[0068] This fractionation zone 70 also makes it possible to obtain noncondensable gases 710, the light cut 720, the final boiling point of which is preferentially between 250° C. and 325° C., and the heavy cut 740, the initial boiling point of which is preferentially between 350° C. and 450° C. Advantageously, the light cut 720 can be sent, at least in part, as washing solvent to the washing and filtration device 41 of the washing and filtration zone 40 to obtain the filtered and washed carbon black cake 430.
[0069] During the start-up of the facility, in the absence of production of a stabilized intermediate cut, i.e. the hydrocarbon cut 730, it is possible temporarily to use an imported solvent which will preferentially be constituted of a content of aromatic molecules of greater than 40% by weight relative to the total weight of the cut. This cut may thus be constituted, for example, of conversion effluents from the process of fluid catalytic cracking (FCC) of middle distillate (light cycle oil (LCO)) or of heavy distillate (heavy cycle oil (HCO)), for example.
EXAMPLES
[0070] The examples that follow illustrate preferential embodiments of the process according to the present invention without, however, limiting the scope thereof. The process used for illustrating the invention is in accordance with that described in
[0071] In a first example, in accordance with the invention, use is made of used tire granules (solid feedstock), produced by granulators using grinders, which originate from heavy goods vehicle tires and the grains resulting from the grinding have a size close to 2 millimeters. The tire granules result from a pretreatment unit 10 and are free of textile and metal fibers. The granules 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 portion of the hydrocarbon cut 730 is used as liquid solvent 760, the composition of which is shown in table 1 below. The amount of solid feedstock treated is 100 kg/h. The amount of solvent that is recycled to the reactor 20 is 500 kg/h, corresponding to a solvent/granule weight ratio equal to 5 w/w. In the reactor 20, the temperature is maintained equal to 290° C., which makes it possible to dissolve the granules. The liquid fractions and the carbon black in suspension are then sent to the reactor 30 where the temperature is maintained equal to 400° C. for one hour. At the outlet of the reactor 30, 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 rotary filter 41 operating at 140° C. The filtered carbon black is washed with toluene. 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 carbon black 430 is sent to a drying unit 50 operating at 150° C. for 24 hours to recover the filtered, washed and dried carbon black 520.
[0072] In examples 2 to 5, not in accordance with the invention, the steps of the conversion process and the operating conditions are identical to those of example 1, except for the following features: [0073] examples 2 and 3: the content of C40+ hydrocarbon compounds (vacuum residues (VR)) in the liquid solvent 760 is outside the range according to the invention; [0074] example 4: the content of C5-C10 hydrocarbon compounds (gasoline) in the hydrocarbon cut 760 is outside the range according to the invention; [0075] example 5: the solvent/solid feedstock weight ratio is outside the range according to the invention.
TABLE-US-00001 Examples 1 2 3 4 5 Temperature of the reactor 30 °C 400 400 400 400 400 Pressure of the reactor 30 MPa 0.9 0.9 0.9 0.9 0.9 Flow rate of feedstock 100 kg/h 100 100 100 100 100 Liquid solvent 760 /feedstock 100 w/w 5 5 5 5 1.8 Flow rate of recycle stream 760 kg/h 500 500 500 500 179 Hydrocarbon cut 760 Gas wt% 0.2 0.2 0.1 1.1 0.1 Gasoline (C5-205° C.) wt% 6.6 6.2 5.3 26.2 4.5 Gas oil (205-370° C.) wt% 59.3 52.6 40.9 56.6 62.3 VGO (370-520° C.) wt% 33.6 33.1 33.6 15.9 32.8 VR (520° C.+) wt% 0.4 8.0 20.0 0.2 0.3 Gaseous effluent 310 kg/h 85 73 54 393 47 Liquid effluent 320 kg/h 515 527 546 207 232 Solids in liquid effluent 320 wt% 7.3 7.2 6.9 18.2 16.2 Viscosity of the second liquid effluent 410 at 50° C. cP 6.2 12.0 28.8 12.0 12.0 Viscosity of the second liquid effluent 410 at 100° C. cP 2.3 3.8 7.4 3.7 3.8 Time to filter the carbon black Base Base x 4 Base x 8 Base x 4 Base x 4
[0076] By comparing the results in terms of carbon black filtration time relative to example 1 according to the invention, it is found that when the content of C40+ hydrocarbon compounds (vacuum residue) is 8% by weight in the hydrocarbon cut 730 relative to the total weight of said cut (example 2), the carbon black filtration time is 4 times longer, or even 8 times longer when the content of C40+ hydrocarbon compounds is 20% by weight (example 3). Furthermore, when the content of C5-C10 hydrocarbon compounds (gasoline) is 26% by weight in the hydrocarbon cut 730, the carbon black filtration time is 4 times longer (example 4). Finally, a liquid solvent 760 / solid feedstock 100 weight ratio that is not optimized significantly lengthens the carbon black filtration time (example 5).