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    • 专利摘要:
    Method and device for depolymerizing plastic material (1), in particular used or waste plastics, wherein the plastic material (1) is melted and degassed to a plastic melt before it is fed to a depolymerization reactor (3), wherein the plastic melt is a solvent (6) is added, so that the viscosity of the depolymerization reactor (3) supplied plastic melt solution is reduced compared to the viscosity of the plastic melt.
    公开号:AT511772A1
    申请号:T632/2011
    申请日:2011-05-05
    公开日:2013-02-15
    发明作者:Wolfgang Ddipl Ing Hofer
    申请人:Omv Refining & Marketing Gmbh；
    IPC主号:
    专利说明:

    1
    The invention relates to a process for the depolymerization of plastic material, especially waste or waste plastics, wherein the plastic material is melted and degassed to a plastic melt before it is fed to a Depolymerisationsre-actuator. Furthermore, the invention relates to a device for the depolymerization of plastic material, especially waste or waste plastics, with a degassing or melting device, with which the plastic material is transferred into a plastic melt, and a depolymerization reactor.
    It is already known in principle to oil old or waste plastics in order to recycle the used or waste plastics. On the one hand, high-temperature pyrolysis processes are known for the treatment of plastics, in which the plastic material is treated in a temperature range of about 600-1,000 ° C .; On the other hand, low-temperature depolymerization processes are known in which cracking reactions are usually carried out in a temperature range of about 300-450 ° C. Particularly in the case of low-temperature depolymerization, the supply of energy to the molecules of the plastic material is problematic, since the plastic melt has a high viscosity and plastics are generally poor conductors of heat. As a result, only relatively small depolymerization reactors with a sales volume of up to approx. 6,000 tons per year could be realized so far; For larger systems, however, there are considerable problems with heat input. However, plants with a sales volume in the order of 6,000 tonnes per year are hardly economical to operate.
    From the prior art, a device for the depolymerization of waste and waste plastics, for example from WO 95/32262 is known, here for gentle heating of the reactor contents a circulation system is connected to the reactor and the reactor contents before entering a discharge line in The reactor integrated riser for the separation of coarser solid particles passes through with a correspondingly high sinking speed.
    US Pat. No. 7,771,699 B2 further discloses a device for depolymerization of organic and inorganic waste materials, which are chopped, mixed with a solvent, and a suspension is formed with the aid of water or the like, which is then fed to a depolymerization stage. Subsequently, solids are removed from this suspension.
    A very similar process, in which an aqueous suspension is fed to the depolymerization reactor, is further known from WO 2009/108761 A1.
    Furthermore, US 2008/035079 A discloses a method and a device for the depolymerization of plastic material, in which the reactor has a separating device for separating liquid plastic material from vaporous plastic material.
    A disadvantage of all known Depolymerisationsverfahren or devices that - as already mentioned - the heat transfer to the molecules of the plastic material is difficult especially for larger amounts.
    The aim of the present invention is therefore to provide a method and an apparatus of the type mentioned, with which or which of the heat input is improved in the depolymeri-sating plastic material. As a result, it should also be possible in particular to be able to reliably operate depolymerization reactors with a larger capacity and thus to depolymerize plastic material for economic reasons.
    According to the invention this is achieved in the method of the type mentioned in that the plastic melt, a solvent is added, so that the viscosity of the depolymerization reactor supplied plastic melt solution is reduced compared to the viscosity of the plastic melt.
    By adding a solvent into the degassed and molten plastic material, i. the heated, non-solid plastic material, the viscosity of the plastic melt can be reduced and thus the heat input into the plastic material in the depolymerization reactor can be improved. The plastic melt has when introducing the solvent before preferably a temperature of at least 120 ° C, in particular between 150 ° C and 300 ° C, on; in order to achieve a homogeneous solution as possible, the solvent is advantageously preheated to at least 150 ° C, in particular to substantially 200 ° C to 300 ° C. By introducing a solution in the depolymerization results in a smaller drop in the temperature gradient in the cross section of Depolymerisationsre actuator and thus a much lower risk of overheating of the plastic material in the vicinity of the reactor wall, on the outside of which usually a heating device is provided. In addition, the risk of coking the Kunststof fmaterials is reduced. Furthermore, the viscosity of the plastic melt solution can be significantly improved by the viscosity reduction compared to the pure plastic melt, as a result of which the energy expenditure for the operation of the depolymerization reactor can be reduced. Moreover, with current depolymerization reactors, it is often necessary to provide a central stirring device which is disadvantageously worn away by contaminants in the plastic melt. Due to the reduction in viscosity, it is advantageously possible borrower to dispense with a stirring device, whereby the operating and maintenance costs are reduced.
    In order to achieve a thorough mixing of the plastic material introduced into the depolymerization reactor, it is advantageous if plastic melt is continuously pumped out of the depolymerization reactor and recycled into the depolymerization reactor. In this case, a portion of the reactor contents is preferably withdrawn in a lower part of the reactor above a reactor sump and returned to the reactor for further depolymerization. With regard to a reliable mixing of the contents in the depolymerization reactor and for the generation of turbulences in the reactor, it is advantageous if conti- • ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• The molten plastic melt is pumped out of the depolymerisation reactor and returned to the depolymerisation reactor.
    In order to provide the plastic material, which is recycled via the supply circuit, with solvents and thus to create favorable conditions for a heat input in Depolymerisationsreaktor, it is advantageous if the solvent introduced into the supply circuit, preferably injected, is. If the previously degassed and molten plastic material is also introduced via the supply circuit in the depolymerization reactor, it is ensured that newly supplied plastic material and about the supply circuit pumped out of the depolymerization plastic material are first brought together and then the solvent is added to the combined melt material, so that the improved Heat input is ensured in the reactor.
    To reduce the viscosity of the plastic melt, it is particularly advantageous if a fraction obtained from crude oil is added as solvent. To ensure that the plastic material dissolves in the solvent, it is favorable if the solvent is preferably heated to about at least 150 ° C, in particular to substantially 200 ° C to 300 ° C, before it is added to the plastic melt.
    It is particularly advantageous if a heavy oil is added as the solvent. Heavy oil (so-called Heavy Fue.l. Oil (HFO) and its components) is a residual oil from the distillation and / or from cracking plants of petroleum processing, which currently finds primarily as a fuel for marine diesel engines and fuel sales. However, sales of heavy fuel oil are declining so that overcapacity exists. Consequently, heavy oil can be used as a cheap and also efficient solvent or viscosity reducing agent for the depolymerization of plastic material. In addition, some heavy oils contain fine-grained residues of catalysts, which can have a positive influence on the cracking behavior during depolymerization. 5
    In order to avoid that the solvent evaporates immediately after introduction of the plastic melt solution into the depolymerization reactor, it is advantageous if the solvent has a higher boiling point than the operating temperature in the depolymerization reactor. Accordingly, it is advantageous if the solvent, preferably the heavy oil, has a boiling end > 300 ° C, preferably > 350 ° C, has.
    It has proven to be particularly advantageous if the solvent used is a heavy oil with a content of aromatic hydrocarbons of at least 25%. In particular, heavy oils or a mixture of different heavy oils which have the number 265-xxx-x or no. 270-xxx-x in the EINECS (European Inventory of Existing Commercial Chemical Substances) classification can be used, where x represents any wildcard. Particular preference is given here to a heavy oil selected from a group comprising the following EINECs no .: 265-064-6, 265-058-3, 265-189-6, 265-045-2, 265-193-8, 265-081 -9, 270-675-6, 265-060-4.
    To improve the heat input by means of a viscosity reduction, it is advantageous if the viscosity of the plastic melt solution at a temperature of substantially 180 ° C to 240 ° C compared to the plastic melt without solvent by at least 30%, preferably at least 50%, in particular at least 80%, is reduced.
    In order to achieve expediently reusable products in the depolymerization, it is advantageous if the plastic material which is used in the method according to the invention is pre-sorted, so that only special plastic materials are fed to the demopolymerisation reactor. It is advantageous if polyolefins, in particular polyethylene and polypropylene, or polystyrene is used as the plastic material.
    A convenient temperature for the depolymerization of waste or waste plastic materials is given when the plastic material in the depolymerization at about 300 ° C to 500 ° C, preferably 350 ° C to 450 ° C, depolymerized.
    With regard to a suitable further processing of the depolymerized in the reactor plastic material, it is advantageous if the depolymerized plastic material is withdrawn in vapor form in an upper portion of the depolymerization reactor. The product mixture preferably drawn off at the top of the depolymerization reactor can then be fed to a downstream separation column, it being particularly advantageous here if the vaporous, depolymerized plastic material is separated into several products, preferably a gas stream, liquefied petroleum gas and naphtha, and a gas oil-like product ,
    In order to make the heat input into the plastic material as efficient as possible, it is advantageous if the plastic melt solution is heated prior to introduction into the depolymerization reactor. Thus, already a substantial part of the heat required for the endothermic cracking reactions in the context of depolymerization can be supplied to the plastic melt solution prior to introduction of the plastic melt solution into the depolymerization reactor.
    The device of the initially mentioned type is characterized in that a solvent introduction device is provided, via which the plastic melt is zugesetzr a solvent, so that the viscosity of the depolymerization reactor supplied plastic melt solution is reduced compared to the viscosity of the plastic melt. With the aid of the device according to the invention, the viscosity of the melt introduced into the depolymerization reactor can thus be reduced, as is the case with the process of the invention described above, and thus the heat input can be improved. For avoidance of repetition, reference is made to the advantages explained in detail in connection with the method according to the invention.
    With regard to a simple melting and gasification of the plastic material and efficient incorporation of the solvent, it is advantageous if the degassing or melting process is used as the degassing or melting step 4 ** 4 4 (· 4 Μ 4 444 «· I | · 4 44 44 * 44 4 444 an extruder is provided and the solvent introduction device has at least one metering pump.
    In order to achieve a swirling flow in the depolymerization reactor and thus to allow a continuous mixing of the contents in the reactor, it is advantageous if a supply circuit line is connected to the depolymerization reactor, via which part of the plastic melt located in the depolymerization reactor is pumped out and into the depolymerization reactor is returned. It is advantageous if the degassing or to the supply circuit line. Melting device or the solvent introduction device is connected, as this ensures that both newly introduced into the reactor plastic material and that which was pumped out via the supply line from the reactor, is mixed with the solvent, and thus the heat input is improved in the plastic melt ,
    If a heat exchanger is connected to the supply circuit line, the plastic melt solution can be pre-heated with the aid of the heat exchanger before introduction into the depolymerization reactor, which in turn increases the efficiency of the energy input.
    The invention will be described below with reference to a preferred embodiment shown in the drawing. Embodiment, to which it should not be limited, however, explained in more detail.
    The single drawing figure shows schematically the construction of the method according to the invention or of the device according to the invention.
    In the single drawing figure it is apparent that pre-sorted plastic material, which consists in particular of polyolefins, preferably polyethylene and / or polypropylene, and optionally polystyrene, is fed to an extruder provided as an entry device or degassing and melting device 2. In the extruder 2, the plastic material 8 is compacted, degassed and melted. The exiting from the extruder 2 plastic melt is not fed directly to a depolymerization reactor 3, but introduced into a supply circuit line 4. In addition, a portion of the plastic melt located in the reactor 3 is withdrawn via the supply circuit line 4 with the aid of a pump 5 above a reactor tap resulting in the lower part of the reactor 3.
    By introducing solvent 6 into the supply circuit line 4, the solvent 6 is thus admixed with the plastic melt withdrawn from the reactor 3 and with the plastic melt supplied via the extruder 2. Before admixing the solvent 6 to the plastic melt, the solvent 6 is fed to a solvent introduction device 6 ', in which the solvent 6 is preheated to about 200 ° C. to 300 ° C., in particular about 250 ° C.
    By the supply of the solvent 6 in the supply line 4 via the solvent introduction device 6 ', which in particular not shown nozzles for at least one metering pump controlled injection of solvent 6 in the plastic melt, thus, the viscosity of Kunststoffschtne! ze, which is introduced into the Depolymerisarionsreaktor 3 can be reduced. Preferably, to achieve a homogeneous solution preheated heavy oil (HFO) is added. Preferably, a heavy oil with an EI-NECS (European Inventory of Existing Commercial Chemical Substances) number or CAS (Chemical Abstracts Service) number selected from the following Table 1 or a mixture of various of these heavy oils is admixed. EINECS number CAS number 269-783-6 68333-27-7 295-990-6 92201-59-7 265-064-6 64741-62-4 269-782-0 68333-26-6 265-063- 064741-61-3 269-784-1 68333-28-8 274-684-6 70592-77-7 9 270-984-6 68512-62-9 274-683-0 70592-76-6 265-058 -3 64741-57-7 265-189-6 64742-86-5 265-162-9 64742-59-2 273-263-4 68955-27-1 274-685-1 70592-78-8 285-555 -9 85117-03-9 292-658-2 90669-76-4 270-796-4 68478-17-1 270-983-0 68512-61-8 271-763-7 68607-30-7 272-184 -2 68783-08-4 269-777-3 68333-22-2 265-045-2 64741-45-3 265-181-2 64742-78-5 265-193-8 64742-90-1 308-733 -0 98219-64-8 271-013-9 68513-69-9 292-657-7 90669-75-3 273-272-3 68955-36-2 270-792-2 68478-13-7 265-069 -3 64741-67-9 265-081-9 64741-80-6 265-082-4 64741-81-7 265-076-1 64741-75-9 309-863-0 101316-57-8 298-754 -0 93821-66-0 295-396-7 92045-14-2 272-187-9 68783-13-1 271-384-7 68553-00-4 270-675-6 68476-33-5 270-674 -0 63476-32-4 265-057-8 64741-56-6 265-188-0 64742-85-4 295-51 8-9 92062-05-0 302-656-6 94114-22-4 309-712-9 100684-39-7 10 309-713-4 100684-40-0 265-043-1 64741-43-1 272 -341-5 68814-87-9 272-817-2 68915-96-8 296-468-0 92704-36-4 309-695-8 100684-24-0 265-060-4 64741-59-9 265 -062-5 64741-60-2 269-781-5 68333-25-5 271-260-2 68527-18-4 285-505-6 85116-53-6 295-411-7 92045-29-9 308 -278-8 97926-59-5 309-865-1 101316-59-0 309-939-3 101631-14-5 307-662-2 97675-88-2 265-049-4 64741-49-7 265 -059-9 64741-58-8 265-190-1 64742-87-6 295-407-5 92045-24-4 295-408-0 92045-26-6 295-409-6 92045-27-7 307 -750-0 97722-01-5 309-693-7 100684-22-8 309-694-2 100684-23-9 265-092-9 64741-90-8 265-112-6 64742-12-7 265 -129-9 64742-29-6 265-148-2 64742-46-7 265-182-8 64742-79-6 265-183-3 64742-80-9 270-719-4 68477-29-2 270 -721-5 68477-30-5 292-454-3 - 292-615-8 90640-93-0 309-667-5 100683-97-4 309-668-0 100683-98-5 309-669-6 100683-99-6 11 ι · ♦ «< * ·· * 270-671-4 68476-30-2 270-676-1 684 76-36-6 270-673-5 68476-31-3
    Table 1
    Tests have shown that by admixing such a solvent, the viscosity of the solution introduced into the depolymerization reactor 3 is significantly reduced compared to the pure plastic melt.
    Example 1:
    Pure polypropylene granules and solvent (" Quenched Sump Oil " (GSO), EINECs No. 265-064-6) were mixed at 0% by weight, 50% by weight, 70% by weight, and 100% by weight. % produced. Under nitrogen atmosphere, the mixtures were heated and maintained for a short time (a few minutes) to a preferred process temperature of the depolymerization of about 360-390 ° C, on the one hand to take into account the process conditions, on the other hand to achieve the fullest possible homogenization of the samples. The dynamic viscosity was then measured at the respective measurement temperatures using a cylinder rheometer (type: Bohlin Visco 88 Viscometer) with different rotational speeds in the middle adjustment range of the cylinder.
    The following values could be determined for the mixtures constant and almost independent of the shear rate (at medium speeds) (the viscosity of the pure solvent could not be determined, since the viscosity was outside the measuring range):
    Addition rates Solvent L% J Measurement temperature [° Cj 0 (= pure plastic melt) 50 7 0 100 180 1,9 0, 17 0, 03 n. B. 200 0.6 0, 12 0, 02 n. B. 220 0.46 0, 09 0.02 n. B. 240 0.37 0.0 6 0.01 n. B. 12 * · · · · «* v ·« ·· * · · ·
    Table 2: Viscosities of the mixtures [Pa * s]
    The addition of a solvent and the resulting reduction in viscosity also advantageously results in higher turbulences in the depolymerization reactor 3, which in particular improves the heat input to the molecules of the plastic material. In addition, thus, the drop in the temperature gradient can be reduced along the reactor radius, which in turn has a lower risk of overheating in the outer edge region of the reactor 3 in the vicinity of a jacket-shaped heater 3 'of the reactor and the risk of coking of the plastic material can be reduced.
    In addition, in order to make the heat input more efficient for the purpose of depolymerization, a heat exchanger 5 'is additionally provided in the supply circuit line 4, via which the plastic melt solution is heated before it is introduced into the depolymerization reactor 3.
    In the depolymerization reactor 3, the plastic material is then depolymerized in a temperature range of about 350 ° C to 450 ° C and at substantially atmospheric pressure. This results in a vaporous product, which is withdrawn via a Entnahmelei-tong 7 overhead from the reactor 3. D.ie required heat to achieve the endothermic cracking reactions for the purpose of depolymerization takes place on the one hand on the heater 3 'of the depolymerization reactor 3 and on the other hand via the heat exchanger 5', before the Kunststoffschmel ze / heavy oil mixture or the solution of the supply circuit 4 in the Depolymer.i sat.i onreaktor 3 is introduced.
    In addition, the remaining residue in the reactor 3 in the bottom of the reactor in a Fij trationskre.i.slauf lei device 8 is pumped by means of a pump 9. The unreacted KunstStoffreste and coke formed during the depolymerization are in this case removed by means of filters 10 from the bottom product, which in turn is partially recycled to the depolymerization reactor 3. This plastic material conveyed in the filtration circuit discharge 8 can also be heated in a heat exchanger not shown in detail before being returned to the reactor 3. A particularly heavy-boiling part is hereby branched off from the filtration circuit line 8 as a by-product 11.
    The withdrawn at the top of the reactor 3 via the removal line 7 gaseous product mixture is fed to a downstream separation column 12. The product mixture is distilled off here in the separation column 12 into three product streams. In this case, the separation essentially takes place in a gas stream 13, liquefied petroleum gas (LPG), i. Propane, butane and mixtures thereof, and a naphtha-containing product 14 and gas-oil-like products 15.
    With the help of the addition of the solvent 6 in the plastic melt can thus be operated in an economically viable manner, a comparatively large depolymerization reactor with a sales volume of well over 6,000 tons per year, preferably over 100,000 tons per year, due to the viscosity reduction of the plastic melt not only An improved heat input into the plastic material can take place, but also the energy expenditure for the operation of the pumps 5, 9 of the lines 4, 8 of the supply and filter circuit can be reduced. In addition, can advantageously be dispensed with a stirring device in the reactor and thus the energy consumption can be further reduced.
    权利要求:
    Claims (20)
    [1]
    1. A process for the depolymerization of plastic material (1), in particular waste or waste plastics, wherein the plastic material (1) is melted and degassed to a plastic melt before it is fed to a Depolymerisationsreaktor (3}, characterized in that the A solvent (6) is added to the plastic melt, so that the viscosity of the plastic melt solution fed to the depolymerization reactor (3) is reduced compared to the viscosity of the plastic melt.
    [2]
    2. The method according to claim 1, characterized in that a part of the in the depolymerization reactor (3) located plastic melt f pumped and fed back into the depolymerization reactor (3) via a supply circuit.
    [3]
    3. The method according to claim 2, characterized in that continuously plastic melt is pumped out of the depolymerization reactor (3) and recycled to the depolymerization reactor (3).
    [4]
    4. The method according to claim 2 or 3, characterized in that the solvent (6) introduced into the supply circuit, preferably injected, is.
    [5]
    5. The method according to any one of claims 2 to 4, characterized in that the polymer melt to be depolymerized is introduced via the supply circuit in the depolymerization reactor.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that as a solvent (6) one, preferably to about at least. ] 50 ° C, in particular heated to substantially 200 ° C to 300 ° C, obtained from crude oil fraction is added.
    [7]
    7. The method according to any one of claims 1 to 6, characterized in that as solvent (6) a heavy oil is added. 15 • · ·
    [8]
    8. The method according to any one of claims 1 to 7, characterized in that the solvent (6), preferably the heavy oil, a boiling end > 300 ° C, preferably > 350 ° C, has.
    [9]
    9. The method according to any one of claims 1 to 8, characterized in that a heavy oil with a content of aromatic hydrocarbons of at least 25% is used as the solvent (6).
    [10]
    10. The method according to any one of claims 1 to 9, characterized in that a heavy oil is mixed, which in the EI-NECS classification no. 265-xxx-x or no. 270-xxx-x, where x is an arbitrary Represents a wildcard, in particular a heavy oil selected from a group comprising the following EINECs numbers: 265-064-6, 265-058-3, 265-189-6, 265-045-2, 265-193-8, 265-081- 9, 270-675-6, 265-060-4, or a mixture thereof.
    [11]
    11. The method according to any one of claims 1 to 9, characterized in that the viscosity of the plastic melt solution at a temperature of substantially 180 ° C to 24 0 ° C over the plastic melt without solvent by at least 30%, preferably by at least 50% , in particular by at least 80% is reduced.
    [12]
    12. The method according to any one of claims 1 to 11, characterized in that as plastic material (1) polyolefins, in particular polyethylene and polypropylene, or polystyrene are used or is.
    [13]
    13. The method according to any one of claims 1 to 12, characterized in that the plastic material (1) in the Depolymerisati onsreaktor at about 300 ° C to 500 ° C, preferably 350 ° C to 450 ° C, depolymerized.
    [14]
    14. The method according to any one of claims 1 to 13, characterized in that the depolymerized plastic material (1) in an upper portion of the depolymerization reactor (3) vapor-16 is withdrawn.
    [15]
    15. The method according to any one of claims 1 to 14, characterized in that the vaporous, depolymerized plastic material is separated into a plurality of products, preferably a gas stream (13), liquid gas and naphtha (14), and a gasölähnliches product (15).
    [16]
    16. The method according to any one of claims 1 to 15, characterized in that the plastic melt solution is heated prior to introduction into the depolymerization reactor (3).
    [17]
    17. A device for depolymerization of Kunststoffmateriai (1) in particular waste or waste plastics, with a degassing or melting device (2), with which the plastic material (1) is transferred to a plastic melt, and a Depolymerization reactor (3), characterized in that a solvent introduction device is provided, via which a solvent (6) is added to the plastic melt, so that the viscosity of the plastic melt solution supplied to the depolymerization reactor (3) is reduced compared to the viscosity of the plastic melt.
    [18]
    18. The apparatus according to claim 17, characterized in that to the depolymerization reactor (3) a supply circuit line (4) is connected, via which a part of the depolymerization polymer in Depo (3) located plastic melt is pumped and in the depolymerization reactor (3) is recycled.
    [19]
    19. The apparatus according to claim 18, characterized in that the degassing or Schme1zvorriohtung (2) and the solvent introduction Vor-richtur.g (6 ') is connected to the supply circuit line (4).
    [20]
    20. Device according to claim 18 or 19, characterized in that a heat exchanger (5 ') is connected to the supply circuit line (4).
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    引用文献:
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    法律状态:
    优先权:
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