EP0692009B1 - Procede de traitement de matieres plastiques usees ou de dechets de matieres plastiques - Google Patents

Procede de traitement de matieres plastiques usees ou de dechets de matieres plastiques Download PDF

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Publication number
EP0692009B1
EP0692009B1 EP94913053A EP94913053A EP0692009B1 EP 0692009 B1 EP0692009 B1 EP 0692009B1 EP 94913053 A EP94913053 A EP 94913053A EP 94913053 A EP94913053 A EP 94913053A EP 0692009 B1 EP0692009 B1 EP 0692009B1
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Prior art keywords
phase
depolymerization
process according
condensate
subjected
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German (de)
English (en)
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EP0692009A1 (fr
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Rolf Holighaus
Klaus Niemann
Martin Rupp
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Der Gruene Punkt Duales System Deutschland AG
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Veba Oel AG
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    • 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
    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/005—Coking (in order to produce liquid products mainly)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
    • 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
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • 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

Definitions

  • the invention relates to a method for processing old or waste plastics for the purpose of obtaining chemical raw materials and liquid fuel components.
  • the invention is based on a process for the hydrotreatment of carbon-containing material, in which polymers, in particular polymer wastes in comminuted or dissolved form, are added to a high-boiling oil and this mixture is hydrogenated in the presence of hydrogen in order to obtain fuel components and chemical raw materials (cf. DD 254 207 A1).
  • a process for converting used tires, rubber and / or other plastics into liquid, gaseous and solid products by depolymerizing treatment in a solvent under elevated pressure and elevated temperature has been described in DE-A-25 30 229.
  • no harmful substances such as SO 2 , soot or the like should enter the atmosphere in this process.
  • hydrogen tires were added to a hydrogenation reactor under hydrogenation at a hydrogen pressure of 150 bar and a temperature of 450 ° C. in the presence of substances catalyzing the cleavage and hydrogenation reactions.
  • DE-A-2 205 001 describes a process for the thermal treatment of waste and rubber, in which the waste is split at temperatures from 250 to 450 ° C. in the presence of an auxiliary phase which is liquid at the reaction temperature.
  • a method is also known in which polymer waste, in particular waste rubber, is dissolved in the residue products of petroleum processing. The resulting mixture is then coked to coke. Here there are gaseous and liquid products. The latter are suitable as fuel components when processed accordingly, cf. DD 0 144 171.
  • the polymer concentration in the hydrogenation feed is, for example, between 0.01 and 20% by weight according to the process according to DD 254 207.
  • the joint hydrogenating treatment of heavy oils with dissolved and / or suspended polymers is limited to hydrogenation processes in which the hydrogenation is carried out in tubular reactors with or without a suspended catalyst. If reactors were operated with fixedly arranged catalysts, the use of polymers was only possible to a limited extent, in particular if polymers were added which already depolymerize in the heating phase up to approximately 420 ° C. before the reactor enters.
  • Another task is to relieve or better utilize complex and capital-intensive process steps such as smoldering, gasification or bottom phase hydrogenation with regard to the required throughput quantities.
  • the invention consists in a process for processing waste or waste plastics for the purpose of obtaining chemical raw materials and liquid fuel components by depolymerizing the starting materials without adding hydrogen to a pumpable and a volatile phase, separating the volatile phase into a gas phase and a condensate which is subjected to the standard refinery procedures is, wherein the pumpable phase remaining after separation of the volatile phase is subjected to a bottom phase hydrogenation, gasification, smoldering or a combination of these process steps.
  • the resulting gaseous depolymerization products gas
  • the resulting condensable depolymerization products condensate
  • the pumpable, viscous depolymerization products containing, bottom phase depolymerized product
  • the process parameters are preferably selected so that the highest possible proportion of the so-called condensate is formed.
  • the plastics to be used in the present process are e.g. B. Mixed fractions from waste collections, including by Duale System Kunststoff GmbH (DSD). In these mixed fractions z. B. contain polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymer blends such as ABS and polycondensates. Plastic production waste, commercial packaging waste made of plastic, residual, mixed and pure fractions from the plastic processing industry can also be used, the chemical composition of this plastic waste not being critical for the suitability for use in the present process. Suitable insert products are also elastomers, technical rubber articles or used tires in a suitable pre-shredded form.
  • the used plastics or waste plastics come from molded parts, laminates, composite materials, foils or synthetic fibers, for example.
  • halogen-containing plastics are chlorinated polyethylene (PEC), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), chloroprene rubber, to name just a few important representatives.
  • sulfur-containing plastics such as polysulfones or rubbers cross-linked with sulfur bridges, such as in old tires, are produced in large quantities and, if the appropriate equipment for pre-shredding and pre-sorting in plastic and metal components is used for depolymerization and further processing to obtain chemical raw materials or fuel components accessible.
  • thermoplastics this also includes thermosets and polyadducts and products based on cellulose such as cellulose and paper.
  • the products made from this include semi-finished products, individual parts, components, packaging, storage and transport containers and consumer goods.
  • the semi-finished products also include boards and boards (printed circuit boards) as well as laminated boards, some of which may still contain metal coatings and which, like the other products to be used, have been pre-shredded to particle or piece sizes of 0.5 to 50 mm, possibly of metal or glass. or ceramic components can be separated using suitable classification processes.
  • the old and waste plastics mentioned generally also contain inorganic secondary components such as pigments, glass fibers, fillers such as titanium or zinc oxide, flame retardants, pigment-containing printing inks, carbon black and also metals such as. B. metallic aluminum.
  • inorganic secondary components such as pigments, glass fibers, fillers such as titanium or zinc oxide, flame retardants, pigment-containing printing inks, carbon black and also metals such as. B. metallic aluminum.
  • the old and waste plastics mentioned, the z. B. from the collections of the DSD in mixtures or batches of different compositions can contain up to 10, possibly up to 20 wt .-% of inorganic minor components.
  • These plastic mixtures are usually used in shredded or preconditioned form z. B. used as granules or chips or the like in the present process:
  • the individual product streams in particular the condensate, can subsequently be processed in the course of further processing in the sense of raw material recycling, eg. B. used as raw materials for olefin production in ethylene plants.
  • An advantage of the process according to the invention is that inorganic secondary constituents of the old or waste plastics are concentrated in the sump phase, while the condensate not containing these constituents can be processed further by less complex processes.
  • by optimally setting the process parameters temperature and residence time it can be achieved that, on the one hand, a relatively high proportion of condensate is formed and, on the other hand, the viscous depolymerizate of the bottom phase remains pumpable under the process conditions.
  • a useful approximation is that an increase in temperature by 10 ° C. with an average residence time increases the yield of the products passing into the volatile phase by more than 50%.
  • the residence time dependency for two typical temperatures is shown in FIG. 3.
  • Typical of the present process is a condensate yield of about 50% by weight and more based on the total amount of the plastics used in the depolymerization. This advantageously considerably relieves the cost-intensive process stages of pressure gasification, bottom phase hydrogenation and smoldering (pyrolysis).
  • the preferred temperature range for the depolymerization for the process according to the invention is 150 to 470 ° C. A range from 250 to 450 ° C. is particularly suitable.
  • the residence time can be 0.1 to 20 hours. A range from 1 to 10 h has proven to be generally sufficient.
  • the pressure is in the invention Procedure a less critical size. So it may be preferable to carry out the process under negative pressure, e.g. B. if volatile components have to be deducted for procedural reasons. Relatively high pressures are also practicable, however, they require more equipment. In general, the pressure should be in the range from 0.01 to 300 bar, in particular 0.1 to 100 bar.
  • the method can preferably be good at normal pressure or slightly above z. B.
  • the depolymerization can preferably be carried out with the addition of a catalyst, for example a Lewis acid such as aluminum chloride, a radical-forming substance such as a peroxide or a metal compound, for example a zeolite impregnated with a heavy metal salt solution.
  • a catalyst for example a Lewis acid such as aluminum chloride, a radical-forming substance such as a peroxide or a metal compound, for example a zeolite impregnated with a heavy metal salt solution.
  • the depolymerization can take place under turbulent flow conditions, e.g. B. by mechanical stirrer, but also by pumping around the reactor contents.
  • inventions of the process consist of depolymerization under inert gas, ie gas which is essentially inert towards the starting materials and depolymerization products, e.g. B. N 2 , CO 2 , CO or hydrocarbons.
  • inert gas ie gas which is essentially inert towards the starting materials and depolymerization products, e.g. B. N 2 , CO 2 , CO or hydrocarbons.
  • stripping gases and stripping vapors such as nitrogen, water vapor or hydrocarbon gases.
  • Suitable liquid auxiliary phases or solvents or solvent mixtures are, for example, used organic solvents, that is to say waste solvents, incorrect production batches of organic liquids, waste oils or fractions from petroleum refining, for example vacuum residues.
  • the depolymerization can be carried out in a conventional reactor, e.g. B. a stirred tank reactor with external circulation, which is designed for the corresponding process parameters, such as pressure and temperature, and whose container material is resistant to the acidic components that may arise, such as hydrogen chloride.
  • a conventional reactor e.g. B. a stirred tank reactor with external circulation, which is designed for the corresponding process parameters, such as pressure and temperature, and whose container material is resistant to the acidic components that may arise, such as hydrogen chloride.
  • suitable "unit operations" methods can be considered, such as those used for the so-called visbreaking of heavy crude oils or of residual oils from mineral oil processing. Possibly. they must be adapted according to the requirements of the method according to the invention.
  • This process stage is advantageously designed for continuous operation, i. H. the plastic is continuously introduced into the liquid phase of the depolymerization reactor and the depolymerizate and top product are continuously removed.
  • the equipment required for depolymerization is comparatively low. This applies in particular if the process is carried out in the vicinity of normal pressure, ie in the range from 0.2 to 2 bar. In comparison to hydrogenating pretreatments, the expenditure on equipment is also significantly lower. With optimal depolymerization process control, the subsequent process steps can be relieved by up to 50% and more. At the same time, a large proportion of condensable hydrocarbons is deliberately produced in the depolymerization, which can be worked up to valuable products by known and comparatively inexpensive processes.
  • the depolymerizate is easy to handle, since it remains pumpable and, in this form, is a good starting material for the subsequent process stages.
  • the depolymerized material and the condensate are worked up separately from one another.
  • the condensable depolymerization products are preferably subjected to a hydrogenating refining on fixed granular catalyst.
  • the condensate can be subjected to conventional hydrotreating using commercially available nickel / molybdenum or cobalt / molybdenum contacts at hydrogen partial pressures of 10 to 250 bar and temperatures of 200 to 430 ° C.
  • a guard bed for trapping entrained ash components or coke-forming components is expediently connected upstream.
  • the contact is arranged on solid trays as usual and the direction of flow of the condensate can be provided from the tray towards the top of the hydrotreating column or in the opposite direction.
  • acidic components such as hydrogen halide, hydrogen sulfide and. The like.
  • the feeding of water, alkali compounds and possibly corrosion inhibitors into the condensation part of appropriate separators is expedient.
  • the condensable depolymerization products or the condensate can also be subjected to hydrogenating refining on a moving catalyst or in a flowing catalyst bed.
  • the condensate obtained during the depolymerization is, for example, an excellent starting material for a steam cracker after it has passed through the hydrotreater.
  • the Z. B. liquid product obtained in the hydrotreater is processed as synthetic crude oil (syncrude) in conventional refinery structures for the production of fuel components or as a chemical raw material, for example for ethylene production in ethylene plants.
  • gaseous components obtained during hydrotreating are suitable, for example, to be added to the products used for steam reforming.
  • At least a partial stream of the depolymerizate is subjected to pressure gasification.
  • all entrained-flow carburettors (Texaco, Shell, Prenflo), fixed bed carburettors (Lurgi, Espag) and Ziwi carburettors are suitable as devices for pressure gasification.
  • Processes for the thermal decomposition of hydrocarbons with oxygen are particularly suitable, as are carried out in processes of oil gasification by partial oxidation of the hydrocarbons as a flame reaction in a combustion chamber. The reactions are autothermal - not catalytic.
  • the crude gas which essentially consists of CO and H 2 and is produced in the pressure gasification, can be worked up to synthesis gas or used to generate hydrogen.
  • At least a partial stream of the depolymerizate is fed to a bottom phase hydrogenation.
  • the bottom phase hydrogenation is particularly preferred when a high proportion of liquid hydrocarbons is to be obtained from the depolymerizate.
  • the bottom phase hydrogenation of the pumpable liquid-viscous depolymerizate is carried out, for example, in such a way that any petroleum-derived vacuum residue is mixed in and hydrogenation gas is added after compression to 300 bar.
  • the reaction material passes through heat exchangers connected in series, in which the heat exchange with product streams takes place, for example, a hot separator top product.
  • the reaction mixture which has been preheated to typically 400 ° C., is further heated to the desired reaction temperature and then fed to the reactor or a reactor cascade in which the bottom phase hydrogenation takes place.
  • the gaseous components at reaction temperature are separated from liquid and solid components under process pressure.
  • the latter also contain the inorganic minor components.
  • the heavier oil components are separated from the gaseous fraction in a separator, which can be fed to an atmospheric distillation after expansion.
  • the process gases are first removed from the uncondensed portion, which are worked up in a gas scrubber and recycled as recycle gas.
  • the remaining amount of the hot separator product is, for example, freed from the process water after further cooling and fed to an atmospheric column for further processing.
  • the bottom draw of the hot separator can expediently be expanded in two stages and subjected to vacuum distillation to remove residual oil.
  • the thickened residue which also contains the inorganic secondary constituents, can be fed to the gasification device in liquid or solid form for the purpose of generating synthesis gas.
  • the residues obtained in the bottom phase hydrogenation (hot separator residue) and the smoldering coke obtained when the depolymerizate smells, each containing the inorganic secondary constituents, can be utilized by a further thermal process step, the residues obtained there containing the inorganic secondary constituents e.g. B. can be further processed for the purpose of metal recovery.
  • the light and medium oil fractions obtained from the bottom phase hydrogenation can be used in refinery structures as valuable raw materials for the production of fuels or plastic precursors such as olefins or aromatics. If these products from the bottom phase hydrogenation should not be stable in storage, they can be subjected to the hydrotreating treatment provided for condensate or condensable components in the present process.
  • a preferred embodiment of the process according to the invention consists in that the pumpable viscous depolymerizate, after separating off the gaseous and condensable depolymerization products as a liquid product, is each divided into a partial gasification which is to be pressurized and also a partial stream to be fed to a bottom phase hydrogenation.
  • the division of the pumpable viscous depolymerizate according to the invention into one partial pressure gasification and one partial phase hydrogenation and possibly pyrolysis feed in connection with the separate processing of the condensable components in a hydrotreating step leads to one significantly improved plant utilization.
  • Devices such as those developed for the pressure gasification of solid fuels or for the thermal decomposition of hydrocarbons with oxygen or in plants for the sump phase hydrogenation of carbon-containing materials under high pressure are very capital-intensive plant parts, the throughput capacity of which is optimally used when it is used by Feed materials are relieved, as previously separated in the present process as a condensate stream and subjected to a separate workup in a hydrotreater under comparatively mild process conditions.
  • Another preferred option of the present method is to subject at least a partial stream of the depolymerization to a smoldering process to obtain smoldering gas, smoldering tar and smoldering coke.
  • the gaseous hydrogen chloride gas or condensable in the form of an aqueous solution during depolymerization can be used separately in the sense of material recycling. Remaining fractions which are not components of the gaseous depolymerization products which can be condensed as a liquid product yield and which u. a. chlorine-organic as well as sulfur- and nitrogen-containing compounds can be freed from the heteroatoms chlorine, sulfur, nitrogen or oxygen in the course of the bottom phase hydrogenation or the residue processing integrated into the same, which are separated off as hydrogen compounds.
  • the gaseous depolymerization products if appropriate freed from acidic components such as hydrogen halides, can preferably be fed to the hydrogen feed gas or the hydrogen cycle gas of the bottom phase hydrogenation.
  • the combination of depolymerization, hydrogenating treatment of the preferred distillate components, bottom phase hydrogenation, gasification (partial oxidation) and / or smoldering of the depolymerizate of the bottom phase means that the latter treatment stages, which are technologically particularly complex and complex but tolerate inorganic ingredients, can be relieved in terms of capacity.
  • the method according to the invention offers a high material recycling potential of the plastics used.
  • a flow chart for the system configuration according to FIG. 1 is given as follows in the sense of an exemplary embodiment for the specified feed products.
  • the appropriately comminuted, possibly washed and dried waste plastic is continuously fed to the depolymerization reactor 1, which is provided with heating, stirring, pressure-maintaining devices, associated inlet and outlet valves and measuring and control devices for checking the level.
  • 25.0% by weight of the bottom phase hydrogenation 3 and 25.0% by weight of the gasification device 4 are fed in from the depolymerizate.
  • 25.0% by weight of vacuum residue are fed to the bottom phase hydrogenation 3 as a recycle stream.
  • the reaction product of the gasification device consists in a typical procedure of 24.0% by weight of a synthesis gas and approximately 1.0% by weight of an ash-containing soot.
  • the product stream of the depolymerizate from reactor 1 can be partly fed to pyrolysis or smoldering plant 5 for the production of pyrolysis coke, smoldering tar and smoldering gas.
  • the pyrolysis coke is fed to the gasification device, the smoldering tar and the smoldering gas of the bottom phase hydrogenation.
  • the inorganic secondary constituents enriched in the depolymerizate are further concentrated in the subsequent workup. If the depolymerizate is fed to gasification, the inorganic secondary components are subsequently found in the discharged slag. In the case of the bottom phase hydrogenation, they are contained in the hydrogenation residue and in the smoldering in the smoked coke. If the hydrogenation residue and / or the smoked coke are also fed to the gasification, all of the inorganic secondary constituents entered in the process according to the invention leave the processing stage as gasification slag.
  • the old or waste plastic enters the silo 1 and from there into the reactor 2 via the conveying device 16.
  • the reactor contents are heated by means of a circulation system consisting of a circulation pump 4 and a furnace 3.
  • a stream is withdrawn from the circulation via the suspension pump 5, which flow into the insert container 6
  • Vacuum residue supplied via line 14 is mixed and then fed to further processing via high pressure pump 7.
  • the gases and condensable components formed in reactor 2 are passed through condenser 8 and separated. After passing through hydrochloric acid washer 9, the cleaned gases 10 are passed on for further use.
  • the acid components previously contained are removed after washing as aqueous hydrochloric acid 12.
  • the condensate separated in condenser 8 is fed from there for further use.
  • the plastic mixture was depolymerized in the reactor at temperatures between 360 ° C and 420 ° C. Four fractions were formed, the quantity distribution depending on the reactor temperature is shown in the following table:
  • the depolymerized material stream (III) was drawn off continuously and fed to a bottom phase hydrogenation plant together with petroleum-derived vacuum residue for further cleavage.
  • the viscosity of the depolymerizate was 200 mPas at 175 ° C.
  • the hydrocarbon condensates (stream II) were condensed in a separate plant and sent for further processing in a hydrotreater.
  • the gaseous hydrogen chloride (stream IV) was taken up with water and released as 30% aqueous hydrochloric acid.
  • the hydrocarbon gases (stream 1) were fed to the bottom phase hydrogenation plant for conditioning.
  • Condensate from a depolymerization plant which was obtained at a temperature between 400 and 420 ° C from a plastic mixture (DSD house collection), was freed of HCI by washing with ammoniacal solution. It then had a Cl content of 400 ppm.
  • This pretreated condensate was subjected to a catalytic dechlorination process in a continuously operating apparatus.
  • the condensate was first compressed to 50 bar and then subjected to hydrogen, so that a gas / condensate ratio of 1000 l / kg was maintained.
  • the mixture was heated and reacted in a fixed bed reactor over a NiMo catalyst. After leaving the reactor, the reaction mixture was quenched with ammoniacal water so that the HCl formed completely passed into the aqueous phase. Before the reaction mixture was let down, a gas / liquid phase separation was carried out so that the gas and liquid phases could be released separately. After relaxation, the liquid phase was broken down into an aqueous and an organic phase.
  • the organic phase which represented more than 90% by weight of the condensate used, showed the following Cl contents [ppm] depending on the chosen reaction conditions: Temperature [° C] WHSV [kg oil / kg cat./h] 0.5 1 2nd 370 - ⁇ 1 3rd 390 3rd ⁇ 1 ⁇ 1 410 ⁇ 1 ⁇ 1

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Processing Of Solid Wastes (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Claims (10)

  1. Procédé de traitement de matières plastiques usées et de déchets en vue d'obtenir des matières premières pour la chimie et des composants de carburant liquides par dépolymérisation des matières à mettre en oeuvre sans addition d'hydrogène en une phase pompable ainsi qu'une phase liquide, séparation de la phase volatile en une phase gazeuse et un condensat, qui est soumis à des procédures standard usuelles en raffinerie, tandis que la phase restant pompable après la séparation de la phase volatile est soumise à une hydrogénation de bas de colonne, une gazéification, une distillation lente ou une combinaison de ces étapes de procédé.
  2. Procédé selon la revendication 1,
    caractérisé en ce que
    la dépolymérisation est exécutée à une pression de 0,01 à 300 bars, de préférence de 0,1 à 100 bars, en particulier de 0,2 à 2 bars, à une température de 150 à 470°C, de préférence de 250 à 450°C et à un temps de permanence de 0,1 à 10 heures, de préférence de 0,5 à 5 heures et trois courants partiels sont extraits en des quantités de :
    1) 15 à 85,0 % en poids d'un dépolarisant, de
    2) 10,0 à 80,0 % en poids d'un condensat ainsi que de
    3) 5,0 à 20 % en poids d'un mélange gazeux, respectivement par rapport au mélange de matières plastiques mis en oeuvre.
  3. Procédé selon les revendications 1 et 2,
    caractérisé en ce que
    la dépolymérisation est réalisée par addition d'un catalyseur.
  4. Procédé selon au moins une des revendications précédentes,
    caractérisé en ce que
    la dépolymérisation est réalisée dans des conditions d'écoulement turbulentes.
  5. Procédé selon au moins une des revendications précédentes,
    caractérisé en ce que
    la dépolymérisation est exécutée sous gaz inerte.
  6. Procédé selon au moins une des revendications précédentes,
    caractérisé en ce que
    la dépolymérisation est réalisée par mise en oeuvre de moyens de stripage comme l'azote, la vapeur d'eau, des gaz contenant des hydrocarbures ou d'autres à bas point d'ébullition.
  7. Procédé selon au moins une des revendications précédentes,
    caractérisé en ce qu'
    aux matières plastiques usées ou de déchet est ajoutée une phase auxiliaire liquide.
  8. Procédé selon au moins une des revendications précédentes,
    caractérisé en ce que
    le condensat est soumis à un raffinage hydrogénant sur un catalyseur à lit fixe.
  9. Procédé selon au moins une des revendications précédentes,
    caractérisé en ce que
    le condensat est soumis à un raffinage hydrogénant sur un catalyseur en mouvement ou sur un lit de catalyseur ondulé.
  10. Procédé selon au moins une des revendications précédentes,
    caractérisé en ce que
    les produits de dépolymérisation gazeux sont amenés à l'hydrogénation de bas de colonne par insertion d'un lavage destiné à éliminer des composants acides comme du gaz hydrochlorique.
EP94913053A 1993-04-03 1994-03-25 Procede de traitement de matieres plastiques usees ou de dechets de matieres plastiques Expired - Lifetime EP0692009B1 (fr)

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DE4311034 1993-04-03
DE4311034A DE4311034A1 (de) 1993-04-03 1993-04-03 Verfahren zur Gewinnung von Chemierohstoffen und Kraftstoffkomponenten aus Alt- oder Abfallkunststoff
PCT/EP1994/000954 WO1994022979A1 (fr) 1993-04-03 1994-03-25 Procede de traitement de matieres plastiques usees ou de dechets de matieres plastiques

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CN1049237C (zh) 2000-02-09
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FI954685A (fi) 1995-10-02
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HU218853B (hu) 2001-02-28
NO953758L (no) 1995-09-22
BG62572B1 (bg) 2000-02-29
PL310893A1 (en) 1996-01-08
BG100108A (bg) 1996-07-31
SK280953B6 (sk) 2000-10-09
JP2003129066A (ja) 2003-05-08
JPH08508520A (ja) 1996-09-10
UA39203C2 (uk) 2001-06-15
FI954685A0 (fi) 1995-10-02
EP0692009A1 (fr) 1996-01-17
KR970706371A (ko) 1997-11-03
DE4435238A1 (de) 1996-04-11
ATE153692T1 (de) 1997-06-15
DE59402926D1 (de) 1997-07-03
UA48954C2 (uk) 2002-09-16
US5849964A (en) 1998-12-15
SK121695A3 (en) 1996-05-08
ES2104375T3 (es) 1997-10-01
PL178639B1 (pl) 2000-05-31
CZ292837B6 (cs) 2003-12-17
DK0692009T3 (da) 1997-07-14
CZ254695A3 (en) 1996-03-13
WO1994022979A1 (fr) 1994-10-13
HU9502874D0 (en) 1995-11-28
KR960701970A (ko) 1996-03-28
NZ265043A (en) 1997-06-24
CN1120347A (zh) 1996-04-10
GR3024422T3 (en) 1997-11-28
CA2158032A1 (fr) 1994-10-13
NO953758D0 (no) 1995-09-22
AU681652B2 (en) 1997-09-04
AU6536194A (en) 1994-10-24
KR100390236B1 (ko) 2003-10-04

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