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EP0639631A1 - Process for preparing syngas - Google Patents

Process for preparing syngas Download PDF

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Publication number
EP0639631A1
EP0639631A1 EP94112796A EP94112796A EP0639631A1 EP 0639631 A1 EP0639631 A1 EP 0639631A1 EP 94112796 A EP94112796 A EP 94112796A EP 94112796 A EP94112796 A EP 94112796A EP 0639631 A1 EP0639631 A1 EP 0639631A1
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EP
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Prior art keywords
liquid
products
waste
gas
plastic waste
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EP94112796A
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German (de)
French (fr)
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EP0639631B1 (en
Inventor
Ulrich Gerhardus
Horst Dr. Hanke
Josef Hibbel
Norbert Leder
Klaus Poloszyk
Heinz Scheve
Volkmar Schmidt
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Celanese Sales Germany GmbH
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Hoechst 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
    • 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
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels

Definitions

  • the invention relates to a process for converting plastic waste into synthesis gas, which can be used as a raw material for chemical synthesis.
  • Plastic waste can only be disposed of by incineration without special precautionary measures if it is ensured that no pollutants are released into the environment. This requirement is only given in exceptional cases, because they often contain chlorine-containing, but also sulfur- or nitrogen-containing components, as well as heavy metals, which lead to undesired combustion products during combustion. Dust removal and flue gas scrubbing, if necessary special combustion devices, are then indispensable. Conveying and dosing problems can also occur if the waste contains non-flammable and non-melting foreign substances. In addition, economic reasons speak against burning high-quality finishing products of petrochemical raw materials such as their raw materials, namely petroleum and petroleum products.
  • a gasoline-kerosene mixture is obtained by degrading polyethylene at 400 to 450 ° C (CA Vol. 76, 1972, 158024 q). This process can also be carried out in the presence of nickel catalysts (Chem. Ind. XXIII, 1971, 630).
  • the splitting of carbon-containing organic waste Synthetic or predominantly synthetic origin takes place according to the process of EP-A-291 698 under hydrogenating conditions and results predominantly in hydrocarbon fractions in the gasoline and medium oil (diesel oil) boiling range.
  • Waste from plastic and rubber are split thermally at 250 to 450 ° C in the presence of an auxiliary phase which is liquid at the reaction temperature by the process described in DE-C-2 205 001. Over 90% liquid hydrocarbons are formed and soot is only produced in minor amounts.
  • a primary goal of thermal processing is the conversion of plastics into liquid fuels that can be easily conveyed and dosed and distributed homogeneously in the combustion air to ensure smoke-free and soot-free combustion.
  • Prior use of the hydrocarbons e.g. as a solvent, extraction or cleaning agent is not excluded.
  • a decisive disadvantage of the known methods is the need to degrade the plastics to a large extent while maintaining the appropriate temperatures and residence times.
  • they require a complex separation of the solids often contained in the plastics, such as inorganic or organic pigments, opacifiers and fillers.
  • the invention has for its object to convert plastic waste into technically usable raw materials.
  • solids incorporated into the plastics are to be concentrated in the preparation process and are free of organic constituents, so that they can be disposed of in an environmentally friendly manner.
  • This object is achieved by a process for producing synthesis gas from plastic waste. It is characterized in that the waste is thermally split predominantly into liquid products and the liquid split products are converted into synthesis gas by partial oxidation.
  • plastic waste in the sense of the new process is very broad. It includes uniform substances and mixtures of substances of whatever origin and composition.
  • the waste is derived from thermoplastic or thermosetting plastics based on their thermal behavior.
  • the plastic waste includes used plastics that were used for packaging purposes or as materials, e.g. in the construction, electrical or textile industry, in machine and vehicle construction, or were processed into articles for everyday use, such as household and sports equipment or toys.
  • Plastic waste is also faulty batches and unusable residues and residues from production and processing. Plastic waste can therefore briefly be called plastic material that cannot be regenerated or used for other economic purposes. According to the new procedure, waste e.g.
  • plastics polyolefins, vinyl resins such as polyvinyl chloride, polyvinyl acetate and polyvinyl alcohol, furthermore polystyrenes, polycarbonates, polymethylene oxides, polyacrylates, polyurethanes, polyamides, polyester resins and hardened epoxy resins.
  • the process is particularly easy to carry out with thermoplastics.
  • the feed material from which coarse impurities such as metals, glass and ceramic materials have been mechanically separated, becomes thermally low molecular weight Dismantled fragments.
  • all known processes are suitable for this process step, which preferably result in liquid decomposition products and / or soot only in a minor amount.
  • the polymeric compounds can be cleaved in the presence or absence of hydrogen. Subsequent hydrogenation of the cleavage products is also possible; However, it is not absolutely necessary in any sub-step of the thermal pretreatment of the waste to work under hydrogenating conditions. The choice of the process suitable for the thermal degradation of the plastics therefore largely depends on the respective circumstances.
  • the depolymerization of plastic waste not only leads to easily metered and homogeneous, liquid products. In particular, it also results in dechlorination of the chlorine-containing plastics that are often present in the plastic waste.
  • the halogen is split off as hydrogen chloride, which is washed out from the gaseous degradation products in a known manner.
  • the liquid fission products only contain chlorine in small amounts that can be tolerated in the subsequent gasification.
  • auxiliary phase which is liquid at the reaction temperature has proven to be particularly suitable (cf. DE-C-2 205 001).
  • This auxiliary phase is used in particular to transfer the heat to the feed materials in the cracking reactor. In addition, it promotes thermal degradation by allowing the starting materials to swell in a gel-like manner in many cases.
  • auxiliary phase such substances are used with success that the waste products used and the Dissolve cleavage products at least partially at the given reaction temperature. Natural or artificial waxy hydrocarbons, polyglycols and in particular the liquid degradation products of the plastic waste itself have proven successful.
  • the breakdown of the waste to be processed is promoted by mechanically crushing it before thermal decomposition. In addition, it can be accelerated by adding suitable catalysts. In this way, waste containing predominantly polyolefins can easily be broken down into low-molecular fragments in the presence of manganese, vanadium, copper, chromium, molybdenum or tungsten compounds at elevated temperatures.
  • the catalytically active metals can already be present in the plastics in the form of the additives, so that their addition is unnecessary.
  • the fission products boil in the area of crude gasoline (naphtha) and middle distillates and also have the viscosity of these petroleum fractions. They can therefore be pumped using conventional devices.
  • Hydrocarbons generated during the splitting partly leave the reactor as vapors in a mixture with hydrogen chloride and small amounts of other fission gases such as carbon monoxide, hydrogen, nitrogen and ammonia. They are obtained from the gaseous mixture by partial condensation as an ash-free condensate. It is a for further processing, e.g. on naphtha, suitable raw material.
  • the gas phase containing hydrogen chloride can e.g. be converted into about 30% hydrochloric acid.
  • the remaining part of the fission product which contains all of the ash, is discharged in liquid form and converted into synthesis gas either alone or in a mixture with other raw materials, eg naphtha, with steam and oxygen.
  • This reaction can also be carried out by known methods. Processes that allow problem-free separation of the ashes and their extraction without external admixtures are particularly suitable.
  • the solution to this problem requires the highest possible carbon conversion in the reactor in order to avoid the discharge of soot together with the ash.
  • special cooling devices must be provided for the raw gas that carries liquid ash. Direct cooling with water in a quench cooler or a system consisting of a radiation cooler and a convection cooler has proven its worth. The cooling stage is followed by water washes, in which the last ash residues are removed.
  • the ashes can be stored in landfills or processed into metals.
  • the gasification itself takes place at temperatures between 1100 and 1500 ° C and a pressure of 1 to 10 MPa.
  • the raw gas leaving the gasification reactor at a temperature of 1300 to 1500 ° C. contains, in addition to soot, metals and / or metal compounds in the stated amount in liquid form. It is first pre-cooled in a radiation cooler to 500 to 1000 ° C, a temperature range in which the metallic contaminants solidify without substantial contact with the cooler wall. Some of the solid particles settle in the water sump of the radiation cooler and are discharged from there. For further cooling to 150 to 300 ° C, preferably 260 to 280 ° C, the remaining portion of fine metal particles and soot particles containing raw gas is passed into a convection cooler.
  • the carbon monoxide / hydrogen mixture obtained by gasification of the depolymerized plastic waste can be used directly as a starting material for chemical reactions, for example for oxosynthesis.
  • the C / H ratio of their fission products is lower than that of heavy fuel oils, the common raw material for synthesis gas production.
  • the CO / H2 ratio of 1: 1 required for certain applications (eg in the oxo process) is therefore not always achieved.
  • a hydrogen-rich fraction can be separated from the solid-free raw gas in a membrane system, which is burned or worked up by conversion to pure hydrogen.
  • the gas mixture as a whole can also be converted into hydrogen by conversion.
  • the figure shows the new process in the form of a block diagram.
  • Plastic waste is broken down thermally in the depolymerization stage at temperatures which, depending on the process, are in the range of 200 to 500 ° C to liquid products, the flowability of which corresponds roughly to that of heavy heating oils at the same temperature.
  • the depolymerization is accompanied by the elimination of hydrogen chloride from chlorine-containing plastics, the hydrogen chloride is washed out with water from the reaction product and in a known manner, e.g. to 30% crude acid, worked up. In special cases, the hydrogen chloride can also be neutralized in an alkaline wash.
  • the splitting is followed by gasification, i.e. the partial oxidation of the depolymerized waste with oxygen in the presence of water vapor.
  • hydrogen can also be obtained from the raw gas.
  • it is converted, the resulting CO2 / H2 mixture is fed into a chemical wash and separated into CO2 and H2 in a pressure swing absorption stage.
  • Returned packaging material made of plastic with a content of 2.5% by weight of water and 3.3% by weight of chlorine is suspended in a liquid auxiliary phase, which was obtained by thermal splitting of plastic waste, and to separate the water at about 130 ° C. heated.
  • the plastic suspension is then transferred to the cleavage reactor, in which the feed material is depolymerized at about 350 ° C. and has a residence time of about 4 hours. Gaseous fission products are cooled to about 30 ° C and fed to an appropriate absorption system for the separation of hydrogen chloride.
  • the liquid depolymerizate has the following composition.
  • N 0.4% by weight
  • Part of the liquid fission product is used as an auxiliary phase (suspension medium) for the thermal fission of further plastic waste, the rest is partially oxidized to water gas.
  • the depolymerizate is reacted with oxygen and water vapor in a known manner at about 1400 ° C. and a pressure of 4 MPa.
  • 400 kg of depolymerized material 325 Nm3 of oxygen and 110 kg of steam are required.
  • the raw gas contains 43.8 vol .-% CO, 48.6 vol .-% H2 and 6.6 vol .-% CO2; the CO / H2 ratio is about 0.9.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Processing Of Solid Wastes (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Plastic wastes are thermally cracked to give predominantly liquid products and the cracking products are converted into synthesis gas by partial oxidation.

Description

Die Erfindung betrifft ein Verfahren zur Umwandlung von Kunststoffabfällen in Synthesegas, das als Rohstoff für chemische Synthesen verwendet werden kann.The invention relates to a process for converting plastic waste into synthesis gas, which can be used as a raw material for chemical synthesis.

Eines der drängendsten Umweltprobleme, dem sich die Fachweit gegenübersieht, ist die Beseitigung von Abfällen, darunter auch solchen aus Kunststoff. Die bisher vielfach geübte Lagerung derartiger Materialien in Mischung mit anderen Abfällen in Deponien hat sich als fragwürdig erwiesen, weil sie die langfristige Einwirkung auf Grundwasser und Boden nicht berücksichtigte. Durch Lagerung in Sonderdeponien bemüht man sich, solchen Umweltbelastungen vorzubeugen, weil aber entsprechende Abladestätten nur in begrenztem Umfang zur Verfügung stehen, wird die Lösung der Aufgabe, die Abfälle umweltneutral zu beseitigen, tatsächlich nur in die Zukunft verschoben.One of the most pressing environmental problems faced by experts in the field is the disposal of waste, including plastic waste. The previously widely practiced storage of such materials in a mixture with other waste in landfills has proven questionable because it did not take into account the long-term effects on groundwater and soil. By storing them in special landfills, efforts are made to prevent such environmental pollution, but because the corresponding unloading sites are only available to a limited extent, the solution to the task of disposing of the waste in an environmentally neutral manner is actually only postponed to the future.

Daher hat man sich in letzter Zeit vielfach bemüht, Verfahren zur Aufarbeitung der genannten Abfälle zu entwickeln. Sie haben nicht allein die Schonung der Umwelt zum Ziel, sondern häufig auch die Gewinnung verwertbarer Produkte aus den ihrer eigentlichen Bestimmung nicht mehr unmittelbar zuzuführenden Stoffe.Therefore, efforts have recently been made many times to develop processes for processing the waste mentioned. Their goal is not only the protection of the environment, but often also the recovery of usable products from the substances that are no longer to be directly used for their intended purpose.

Die Aufarbeitung gebrauchter oder nicht typgerechter Kunststoffe zum wiederverwertbaren Ursprungsmaterial scheitert in den meisten Fällen daran, daß Abfälle Kunststoffe verschiedener stofflicher Zusammensetzung enthalten. Es ist leicht einzusehen, daß sich solche Gemische im allgemeinen nicht zu einem Ursprungswerkstoff aufarbeiten lassen. Die Trennung der Gemische in Anteile gleicher stofflicher Beschaffenheit scheitert an der Schwierigkeit, die einzelnen Komponenten zu identifizieren. Aber auch aus Abfällen identischer Kunststoffe kann nur ausnahmsweise das Ausgangsmaterial in ursprünglicher Qualität wiedergewonnen werden, weil durch die erforderlichen chemischen und/oder physikalischen Behandlungsschritte die molekulare Struktur der Polymerisate und damit ihre ursprünglichen Eigenschaften verändert werden.In most cases, the processing of used or non-type-appropriate plastics into recyclable original material fails because waste contains plastics of different material compositions. It is easy to see that such mixtures generally cannot be processed into an original material. The separation of the mixtures into parts of the same material nature fails due to the difficulty in identifying the individual components. But even from waste of identical plastics, the original material can only be recovered in its original quality in exceptional cases because the chemical and / or physical treatment steps required change the molecular structure of the polymers and thus their original properties.

Durch Verbrennen können Kunststoffabfälle nur dann ohne besondere Vorsichtsmaßnahmen entsorgt werden, wenn sichergestellt ist, daß hierbei keine Schadstoffe in die Umwelt gelangen. Diese Voraussetzung ist nur in Ausnahmefällen gegeben, denn häufig enthalten sie chlorhaltige, aber auch schwefel- oder stickstoffhaltige Bestandteile sowie Schwermetalle, die bei der Verbrennung zu unerwünschten Verbrennungsprodukten führen. Entstaubung und Rauchgaswäsche, gegebenenfalls spezielle Verbrennungsvorrichtungen, sind dann unerläßlich. Förder- und Dosierungsprobleme können zusätzlich dann auftreten, wenn die Abfälle nicht brennbare und nicht schmelzende Fremdstoffe enthält. Überdies sprechen wirtschaftliche Gründe dagegen, hochwertige Veredlungsprodukte petrochemischer Rohstoffe wie deren Rohstoffe, nämlich Erdöl und Erdölprodukte, zu verbrennen.Plastic waste can only be disposed of by incineration without special precautionary measures if it is ensured that no pollutants are released into the environment. This requirement is only given in exceptional cases, because they often contain chlorine-containing, but also sulfur- or nitrogen-containing components, as well as heavy metals, which lead to undesired combustion products during combustion. Dust removal and flue gas scrubbing, if necessary special combustion devices, are then indispensable. Conveying and dosing problems can also occur if the waste contains non-flammable and non-melting foreign substances. In addition, economic reasons speak against burning high-quality finishing products of petrochemical raw materials such as their raw materials, namely petroleum and petroleum products.

Statt sie zu verbrennen, hat man nicht mehr verwertbare Kunststoffe auch thermisch gespalten. Die hierzu entwickelten Verfahren sind vielgestaltig. So erhält man durch Abbau von Polyethylen bei 400 bis 450°C ein Gasolin-Kerosin-Gemisch (C.A. Vol. 76, 1972, 158024 q). Dieser Prozeß kann auch in Gegenwart von Nickelkatalysatoren durchgeführt werden (Chem. Ind. XXIII, 1971, 630). Die Spaltung Kohlenstoff enthaltender organischer Abfälle synthetischen oder überwiegend synthetischen Ursprungs erfolgt nach dem Verfahren der EP-A-291 698 unter hydrierenden Bedingungen und ergibt überwiegend Kohlenwasserstofffraktionen im Benzin und Mittelöl-(Dieselöl)Siedebereich. Abfälle aus Kunststoff und Kautschuk werden nach dem in der DE-C-2 205 001 beschriebenen Prozeß thermisch bei 250 bis 450°C in Gegenwart einer bei der Reaktionstemperatur flüssigen Hilfsphase gespalten. Es entstehen über 90 % flüssige Kohlenwasserstoffe und nur in untergeordneten Mengen Ruß.Instead of burning them, plastics that are no longer usable have also been thermally split. The processes developed for this are varied. A gasoline-kerosene mixture is obtained by degrading polyethylene at 400 to 450 ° C (CA Vol. 76, 1972, 158024 q). This process can also be carried out in the presence of nickel catalysts (Chem. Ind. XXIII, 1971, 630). The splitting of carbon-containing organic waste Synthetic or predominantly synthetic origin takes place according to the process of EP-A-291 698 under hydrogenating conditions and results predominantly in hydrocarbon fractions in the gasoline and medium oil (diesel oil) boiling range. Waste from plastic and rubber are split thermally at 250 to 450 ° C in the presence of an auxiliary phase which is liquid at the reaction temperature by the process described in DE-C-2 205 001. Over 90% liquid hydrocarbons are formed and soot is only produced in minor amounts.

Ein vordergründiges Ziel der thermischen Aufbereitung ist die Umwandlung der Kunststoffe in flüssige Brennstoffe, die leicht gefördert und dosiert und in der Verbrennungsluft homogen verteilt werden können, um eine rauch- und rußfreie Verbrennung sicherzustellen. Eine vorherige Verwendung der Kohlenwasserstoffe z.B. als Lösungs-, Extraktions- oder Reinigungsmittel ist dabei nicht ausgeschlossen.A primary goal of thermal processing is the conversion of plastics into liquid fuels that can be easily conveyed and dosed and distributed homogeneously in the combustion air to ensure smoke-free and soot-free combustion. Prior use of the hydrocarbons e.g. as a solvent, extraction or cleaning agent is not excluded.

Ein entscheidender Nachteil der bekannten Verfahren ist das Erfordernis, die Kunststoffe unter Einhaltung entsprechender Temperaturen und Verweilzeiten sehr weitgehend abzubauen. Überdies erfordern sie eine aufwendige Abtrennung der in den Kunststoffen oftmals enthaltenen Feststoffe wie anorganische oder organische Pigmente, Trübungsmittel und Füllstoffe.A decisive disadvantage of the known methods is the need to degrade the plastics to a large extent while maintaining the appropriate temperatures and residence times. In addition, they require a complex separation of the solids often contained in the plastics, such as inorganic or organic pigments, opacifiers and fillers.

Der Erfindung liegt die Aufgabe zugrunde, Kunststoffabfälle in technisch verwertbare Rohstoffe umzuwandeln. Hierbei sollen in die Kunststoffe eingearbeitete Feststoffe im Aufbereitungsprozeß konzentriert und frei von organischen Bestandteilen anfallen, so daß sie umweltschonend entsorgt werden können.The invention has for its object to convert plastic waste into technically usable raw materials. Here, solids incorporated into the plastics are to be concentrated in the preparation process and are free of organic constituents, so that they can be disposed of in an environmentally friendly manner.

Diese Aufgabe wird gelöst durch ein Verfahren zur Herstellung von Synthesegas aus Kunststoffabfällen. Es ist dadurch gekennzeichnet, daß die Abfälle thermisch überwiegend zu flüssigen Produkten gespalten und die flüssigen Spaltprodukte durch partielle Oxidation in Synthesegas überführt werden.This object is achieved by a process for producing synthesis gas from plastic waste. It is characterized in that the waste is thermally split predominantly into liquid products and the liquid split products are converted into synthesis gas by partial oxidation.

Der Begriff Kunststoffabfälle im Sinne des neuen Verfahrens ist sehr weit zu fassen. Er schließt einheitliche Stoffe und Stoffgemische gleich welcher Herkunft und Zusammensetzung ein. Nach ihrem thermischen Verhalten leiten sich die Abfälle von thermoplastischen oder duroplastischen Kunststoffen her. Zu den Kunststoffabfällen zahlen gebrauchte Kunststoffe, die zu Verpackungszwecken dienten oder als Werkstoffe, z.B. in der Bau-, Elektro- oder Textilindustrie, im Maschinen- und Fahrzeugbau, verwendet wurden oder zu Artikeln des täglichen Bedarfs, wie Haushalts- und Sportgeräte oder Spielzeug verarbeitet worden waren. Kunststoffabfälle sind auch Fehlchargen und nicht verwertbare Reste und Rückstände aus Produktion und Verarbeitung. Als Kunststoffabfälle kann man daher kurz Kunststoffmaterial bezeichnen, das sich nicht regenerieren oder einer anderen wirtschaftlichen Verwertung zuführen läßt. Nach dem neuen Verfahren lassen sich Abfälle z.B. folgender Kunststoffe verarbeiten: Polyolefine, Vinylharze wie Polyvinylchlorid, Polyvinylacetat und Polyvinylalkohol, ferner Polystyrole, Polycarbonate, Polymethylenoxide, Polyacrylate, Polyurethane, Polyamide, Polyesterharze sowie gehärtete Epoxidharze. Besonders einfach ist das Verfahren mit thermoplastischen Kunststoffen durchzuführen.The term plastic waste in the sense of the new process is very broad. It includes uniform substances and mixtures of substances of whatever origin and composition. The waste is derived from thermoplastic or thermosetting plastics based on their thermal behavior. The plastic waste includes used plastics that were used for packaging purposes or as materials, e.g. in the construction, electrical or textile industry, in machine and vehicle construction, or were processed into articles for everyday use, such as household and sports equipment or toys. Plastic waste is also faulty batches and unusable residues and residues from production and processing. Plastic waste can therefore briefly be called plastic material that cannot be regenerated or used for other economic purposes. According to the new procedure, waste e.g. Process the following plastics: polyolefins, vinyl resins such as polyvinyl chloride, polyvinyl acetate and polyvinyl alcohol, furthermore polystyrenes, polycarbonates, polymethylene oxides, polyacrylates, polyurethanes, polyamides, polyester resins and hardened epoxy resins. The process is particularly easy to carry out with thermoplastics.

Erfindungsgemäß wird das Einsatzmaterial, aus dem grobe Verunreinigungen wie Metalle, Glas und keramische Werkstoffe mechanisch abgetrennt wurden, thermisch zu niedermolekularen Bruchstücken abgebaut. Grundsätzlich sind für diesen Verfahrensschritt alle bekannten Prozesse geeignet, die bevorzugt flüssige und nur in untergeordneter Menge gasförmige Zersetzungsprodukte und/oder Ruß ergeben. Die Spaltung der polymeren Verbindungen kann in Gegenwart oder Abwesenheit von Wasserstoff erfolgen. Ebenso ist eine nachträgliche Hydrierung der Spaltprodukte möglich; es ist jedoch in keinem Teilschritt der thermischen Vorbehandlung der Abfälle zwingend erforderlich, unter hydrierenden Bedingungen zu arbeiten. Die Wahl des für den thermischen Abbau der Kunststoffe geeigneten Verfahrens hängt daher weitgehend von den jeweiligen Gegebenheiten ab.According to the invention, the feed material, from which coarse impurities such as metals, glass and ceramic materials have been mechanically separated, becomes thermally low molecular weight Dismantled fragments. In principle, all known processes are suitable for this process step, which preferably result in liquid decomposition products and / or soot only in a minor amount. The polymeric compounds can be cleaved in the presence or absence of hydrogen. Subsequent hydrogenation of the cleavage products is also possible; However, it is not absolutely necessary in any sub-step of the thermal pretreatment of the waste to work under hydrogenating conditions. The choice of the process suitable for the thermal degradation of the plastics therefore largely depends on the respective circumstances.

Die Depolymerisation der Kunststoffabfälle führt nicht nur zu gut dosierbaren und homogenen, flüssigen Produkten. Sie hat insbesondere auch eine Entchlorierung der in den Kunststoffabfällen vielfach vorhandenen, Chlor enthaltenden Kunststoffe zur Folge. Das Halogen wird als Chlorwasserstoff abgespalten, der aus den gasförmigen Abbauprodukten in bekannter Weise ausgewaschen wird. Die flüssigen Spaltprodukte enthalten Chlor nur noch in geringen Mengen, die bei der anschließenden Vergasung tolerierbar sind.The depolymerization of plastic waste not only leads to easily metered and homogeneous, liquid products. In particular, it also results in dechlorination of the chlorine-containing plastics that are often present in the plastic waste. The halogen is split off as hydrogen chloride, which is washed out from the gaseous degradation products in a known manner. The liquid fission products only contain chlorine in small amounts that can be tolerated in the subsequent gasification.

Als besonders geeignet hat sich die thermische Aufbereitung der Kunststoffabfälle bei Temperaturen zwischen 250 und 450°C unter Verwendung einer, bei der Reaktionstemperatur flüssigen Hilfsphase erwiesen (vgl. DE-C-2 205 001). Diese Hilfsphase dient insbesondere zur Übertragung der Wärme auf die Einsatzstoffe im Spaltreaktor. Darüber hinaus fördert sie den thermischen Abbau dadurch, daß sie die Einsatzstoffe in vielen Fällen gelartig aufquellen läßt. Als Hilfsphase werden mit Erfolg solche Stoffe angewandt, die die eingesetzten Abfallprodukte und die Spaltprodukte bei der gegebenen Reaktionstemperatur zumindest teilweise lösen. Bewährt haben sich natürliche oder künstliche wachsartige Kohlenwasserstoffe, ferner Polyglykole und insbesondere die flüssigen Abbauprodukte der Kunststoffabfälle selbst.Thermal processing of the plastic waste at temperatures between 250 and 450 ° C. using an auxiliary phase which is liquid at the reaction temperature has proven to be particularly suitable (cf. DE-C-2 205 001). This auxiliary phase is used in particular to transfer the heat to the feed materials in the cracking reactor. In addition, it promotes thermal degradation by allowing the starting materials to swell in a gel-like manner in many cases. As an auxiliary phase, such substances are used with success that the waste products used and the Dissolve cleavage products at least partially at the given reaction temperature. Natural or artificial waxy hydrocarbons, polyglycols and in particular the liquid degradation products of the plastic waste itself have proven successful.

Der Abbau der aufzubereitenden Abfälle wird dadurch gefördert, daß man sie vor der thermischen Spaltung mechanisch zerkleinert. Überdies kann er durch Zusatz geeigneter Katalysatoren beschleunigt werden. So lassen sich Abfälle, die vorwiegend Polyolefine enthalten, in Gegenwart von Mangan-, Vanadin-, Kupfer-, Chrom-, Molybdän- oder Wolframverbindungen bei erhöhter Temperatur leicht in niedermolekulare Bruchstücke aufspalten. Die katalytisch wirksamen Metalle können in den Kunststoffen bereits in Form der Zuschlagstoffe vorliegen, so daß sich ihr Zusatz erübrigt.The breakdown of the waste to be processed is promoted by mechanically crushing it before thermal decomposition. In addition, it can be accelerated by adding suitable catalysts. In this way, waste containing predominantly polyolefins can easily be broken down into low-molecular fragments in the presence of manganese, vanadium, copper, chromium, molybdenum or tungsten compounds at elevated temperatures. The catalytically active metals can already be present in the plastics in the form of the additives, so that their addition is unnecessary.

Die Umwandlung der hochmolekularen Einsatzstoffe erfolgt in herkömmlichen Reaktoren, z.B. in geschlossenen, mit einer Heizvorrichtung versehenen Rührkesseln. Üblicherweise arbeitet man in einer Stufe. Insbesondere wenn sich bei der Aufarbeitung von Abfällen aggressive Gase entwickeln, empfiehlt es sich, den Spaltprozeß zwei- oder mehrstufig durchzuführen, wobei die Spaltung in den einzelnen Stufen im allgemeinen nicht bei gleicher Temperatur, sondern mit von Stufe zu Stufe ansteigenden Temperaturen betrieben wird. So hat es sich bei Einsatz Chlor enthaltender Polymerer als zweckmäßig erwiesen, wasserfeuchte Kunststoffe zunächst bei mäßiger Temperatur, die noch nicht zur HCl-Abspaltung führt, zu trocknen, um eine korrosive Beanspruchung der Reaktorwerkstoffe durch wäßrigen Chlorwasserstoff zu vermeiden. Erst nach der Trocknung wird die Temperatur soweit gesteigert, daß sich als Folge der Spaltung der Polymerisate Chlorwasserstoff bildet. Die Entchlorierung kann in einer zusätzlichen Stufe durch weitere Erhöhung der Temperatur und der Verweilzeit vervollständigt werden. Der stufenweise thermische Abbau Chlor enthaltender polymerer Substanzen ermöglicht es, durch Wahl der Reaktionstemperatur, die aggressive Gase entwickelnden Spaltprodukte bevorzugt in der ersten Spaltstufe anzureichern, so daß bei der nachfolgenden Abtrennung der für die Umwelt schädlichen Gase nur ein Teil der Spaltprodukte einer Reinigungsvorrichtung zugeführt werden müssen. Hervorzuheben ist jedoch, daß selbst Kunststoffabfälle, die Chlor in einer Größenordnung von etwa 5 Gew.-% enthalten, nach dem erfindungsgemäßen Verfahren in flüssige Spaltprodukte umgewandelt werden können, deren Chlorgehalt nur wenige 100 ppm beträgt.The conversion of the high molecular weight feedstocks takes place in conventional reactors, for example in closed stirred tanks equipped with a heating device. Usually you work in one stage. In particular if aggressive gases develop during the processing of waste, it is advisable to carry out the splitting process in two or more stages, the splitting in the individual stages generally not being carried out at the same temperature, but rather with temperatures increasing from stage to stage. Thus, when using chlorine-containing polymers, it has proven to be expedient to first dry water-moist plastics at a moderate temperature which does not yet lead to the elimination of HCl in order to avoid corrosive stress on the reactor materials by aqueous hydrogen chloride. Only after drying does the temperature increase to such an extent that hydrogen chloride is formed as a result of the cleavage of the polymers forms. The dechlorination can be completed in an additional step by further increasing the temperature and the residence time. The gradual thermal degradation of chlorine-containing polymeric substances makes it possible, through the choice of the reaction temperature, to enrich the fission products which develop aggressive gases, preferably in the first fission stage, so that during the subsequent separation of the gases which are harmful to the environment, only some of the fission products have to be fed to a cleaning device . It should be emphasized, however, that even plastic wastes containing chlorine in the order of about 5% by weight can be converted into liquid fission products with a chlorine content of only a few 100 ppm by the process according to the invention.

Die Spaltprodukte sieden im Bereich des Rohbenzins (Naphtha) und der Mitteldestillate und besitzen auch die Viskosität dieser Erdölfraktionen. Sie lassen sich daher mit üblichen Vorrichtungen pumpen.The fission products boil in the area of crude gasoline (naphtha) and middle distillates and also have the viscosity of these petroleum fractions. They can therefore be pumped using conventional devices.

Bei der Spaltung entstandene Kohlenwasserstoffe verlassen den Reaktor zum Teil als Dämpfe in Mischung mit Chlorwasserstoff und geringen Mengen anderer Spaltgase wie Kohlenmonoxid, Wasserstoff, Stickstoff und Ammoniak. Sie werden aus dem gasförmigen Gemisch durch partielle Kondensation als aschefreies Kondensat gewonnen. Es ist ein für die weitere Aufarbeitung, z.B. auf Naphtha, geeigneter Rohstoff. Die chlorwasserstoffhaltige Gasphase kann z.B. in etwa 30 %ige Salzsäure überführt werden.Hydrocarbons generated during the splitting partly leave the reactor as vapors in a mixture with hydrogen chloride and small amounts of other fission gases such as carbon monoxide, hydrogen, nitrogen and ammonia. They are obtained from the gaseous mixture by partial condensation as an ash-free condensate. It is a for further processing, e.g. on naphtha, suitable raw material. The gas phase containing hydrogen chloride can e.g. be converted into about 30% hydrochloric acid.

Der restliche Anteil des Spaltproduktes, der die gesamte Asche enthält, wird flüssig ausgetragen und allein oder in Mischung mit anderen Rohstoffen, z.B. Naphtha, mit Wasserdampf und Sauerstoff zu Synthesegas umgesetzt.The remaining part of the fission product, which contains all of the ash, is discharged in liquid form and converted into synthesis gas either alone or in a mixture with other raw materials, eg naphtha, with steam and oxygen.

Diese Reaktion kann ebenfalls nach bekannten Verfahren erfolgen. Geeignet sind insbesondere Prozesse, die eine problemblose Abtrennung der Asche und ihre Gewinnung ohne fremde Beimischungen erlaubt. Die Lösung dieser Aufgabe erfordert einen möglichst hohen Kohlenstoffumsatz im Reaktor, um den Austrag von Ruß zusammen mit der Asche zu vermeiden. Ferner sind für das Rohgas, das flüssige Asche mitführt, besondere Kühlvorrichtungen vorzusehen. Bewährt hat sich die unmittelbare Kühlung mit Wasser in einem Quenchkühler oder einem aus Strahlungskühler und Konvektionskühler bestehenden System. Der Kühlstufe schließen sich Wasserwäschen an, in der letzte Aschereste entfernt werden. Die Asche kann in Deponien gelagert oder zu Metallen aufgearbeitet werden.This reaction can also be carried out by known methods. Processes that allow problem-free separation of the ashes and their extraction without external admixtures are particularly suitable. The solution to this problem requires the highest possible carbon conversion in the reactor in order to avoid the discharge of soot together with the ash. Furthermore, special cooling devices must be provided for the raw gas that carries liquid ash. Direct cooling with water in a quench cooler or a system consisting of a radiation cooler and a convection cooler has proven its worth. The cooling stage is followed by water washes, in which the last ash residues are removed. The ashes can be stored in landfills or processed into metals.

Ein Verfahren, das insbesondere hinsichtlich der Schadstoffvermeidung den vorstehend skizzierten Ansprüchen genügt, ist z.B. in der EP-A-0 515 950 beschrieben. Es ist dadurch charakterisiert, daß man das Einsatzmaterial unter Bedingungen oxidiert, die zur Bildung von etwa 0,1 bis etwa 0,3 Gew.-% Ruß, bezogen auf den in Form von Kohlenwasserstoffen eingesetzten Kohlenstoff, führen. Diese Arbeitsweise läßt sich mit Erfolg auch auf die Umwandlung der Spaltprodukte von Kunststoffabfällen in Kohlenmonoxid-Wasserstoff-Gemische anwenden. In diesem Fall ist der Kohlenstoffgehalt der depolymerisierten Kunststoffe Bezugsgröße für den Rußanteil. Seine Höhe wird dabei in bekannter Weise über die zugeführte Sauerstoffmenge eingestellt, überdies kann sich der Einsatz eines speziell gestalteten Brenners empfehlen (vgl. z.B. EP-B-0 095 103). Die Vergasung selbst erfolgt bei Temperaturen zwischen 1100 und 1500°C und einem Druck von 1 bis 10 MPa. Das den Vergasungsreaktor mit einer Temperatur von 1300 bis 1500°C verlassende Rohgas enthält neben Ruß in der angegebenen Menge Metalle und/oder Metallverbindungen in flüssiger Form. Es wird zunächst in einem Strahlungskühler auf 500 bis 1000°C vorgekühlt, ein Temperaturbereich, in dem die metallischen Verunreinigungen ohne wesentlichen Kontakt mit der Kühlerwandung erstarren. Die festen Partikel setzen sich zum Teil im Wassersumpf des Strahlungskühlers ab und werden von dort ausgetragen. Zur weiteren Abkühlung auf 150 bis 300°C, vorzugsweise 260 bis 280°C, leitet man das noch restliche Anteile feiner Metallpartikel und Rußteilchen enthaltende Rohgas in einen Konvektionskühler. Weil die vom Gas mitgeführten Verunreinigungen bereits im Strahlungskühler erstarrt sind, beeinträchtigen sie die Wirksamkeit des Konvektionskühlers durch Verlegung der Strömungswege und Ablagerungen auf den Austauschflächen nicht. Die nahezu restlose Abscheidung der Feststoffe erfolgt durch Waschen des Gases mit Wasser. Dieser Teilschritt des Verfahrens wird zweckmäßigerweise mit Hilfe von Naßabscheidern des Standes der Technik z.B. mit Wasser berieselte Füllkörpertürmen, die gegebenenfalls auch in Verbindung mit Venturiwäschern angewandt werden können, durchgeführt. Aus dem Waschwasser wird die Asche durch mechanische Abtrennung, z.B. Filtration, gewonnen.A method which, in particular with regard to the avoidance of pollutants, meets the claims outlined above is described, for example, in EP-A-0 515 950. It is characterized in that the feed is oxidized under conditions which lead to the formation of about 0.1 to about 0.3% by weight of carbon black, based on the carbon used in the form of hydrocarbons. This procedure can also be successfully applied to the conversion of the fission products of plastic waste into carbon monoxide-hydrogen mixtures. In this case, the carbon content of the depolymerized plastics is the reference value for the soot content. Its height is adjusted in a known manner via the amount of oxygen supplied, moreover the use of a specially designed burner can be recommended (cf. for example EP-B-0 095 103). The gasification itself takes place at temperatures between 1100 and 1500 ° C and a pressure of 1 to 10 MPa. The raw gas leaving the gasification reactor at a temperature of 1300 to 1500 ° C. contains, in addition to soot, metals and / or metal compounds in the stated amount in liquid form. It is first pre-cooled in a radiation cooler to 500 to 1000 ° C, a temperature range in which the metallic contaminants solidify without substantial contact with the cooler wall. Some of the solid particles settle in the water sump of the radiation cooler and are discharged from there. For further cooling to 150 to 300 ° C, preferably 260 to 280 ° C, the remaining portion of fine metal particles and soot particles containing raw gas is passed into a convection cooler. Because the contaminants carried by the gas have already solidified in the radiation cooler, they do not impair the effectiveness of the convection cooler by laying the flow paths and deposits on the exchange surfaces. The almost complete separation of the solids takes place by washing the gas with water. This sub-step of the method is expediently carried out with the aid of wet separators of the prior art, for example packed towers sprinkled with water, which can optionally also be used in connection with venturi scrubbers. The ashes are extracted from the washing water by mechanical separation, eg filtration.

Das durch Vergasung der depolymerisierten Kunststoffabfälle erhaltene Kohlenmonoxid-/Wasserstoffgemisch kann unmittelbar als Ausgangsstoff für chemische Reaktionen, z.B. für die Oxosynthese, eingesetzt werden. Entsprechend der Zusammensetzung von Kunststoffabfällen ist das C/H-Verhältnis ihrer Spaltprodukte niedriger als das schwerer Heizöle, dem üblichen Rohstoff für die Synthesegasgewinnung. Das für bestimmte Anwendungen (z.B. im Oxoprozeß) benötigte CO/H₂-Verhältnis von 1 : 1 wird daher nicht immer erreicht. Um den Wasserstoffanteil zu vermindern, kann aus dem feststofffreien Rohgas in einer Membrananlage eine wasserstoffreiche Fraktion abgetrennt werden, die verbrannt oder durch Konvertierung zu reinem Wasserstoff aufgearbeitet wird. Selbstverständlich läßt sich aber auch das Gasgemisch insgesamt durch Konvertierung in Wasserstoff überführen.The carbon monoxide / hydrogen mixture obtained by gasification of the depolymerized plastic waste can be used directly as a starting material for chemical reactions, for example for oxosynthesis. Depending on the composition of plastic waste, the C / H ratio of their fission products is lower than that of heavy fuel oils, the common raw material for synthesis gas production. The CO / H₂ ratio of 1: 1 required for certain applications (eg in the oxo process) is therefore not always achieved. In order to reduce the hydrogen content, a hydrogen-rich fraction can be separated from the solid-free raw gas in a membrane system, which is burned or worked up by conversion to pure hydrogen. Of course, the gas mixture as a whole can also be converted into hydrogen by conversion.

In der Abbildung ist das neue Verfahren in Form eines Blockschemas dargestellt. Kunststoffabfälle werden in der Depolymerisationsstufe thermisch bei Temperaturen, die, abhängig vom Verfahren, im Bereich von 200 bis 500°C liegen, zu flüssigen Produkten abgebaut, deren Fließfähigkeit etwa der schwerer Heizöle bei gleicher Temperatur entsprechen. Die Depolymerisation wird von der Abspaltung von Chlorwasserstoff aus chlorhaltigen Kunststoffen begleitet, der Chlorwasserstoff wird mit Wasser aus dem Reaktionsprodukt ausgewaschen und in bekannter Weise, z.B. zu 30 %iger Rohsäure, aufgearbeitet. In Sonderfällen kann der Chlorwasserstoff auch in einer alkalischen Wäsche neutralisiert werden. Der Spaltung schließt sich die Vergasung, d.h. die partielle Oxidation der depolymerisierten Abfälle mit Sauerstoff in Gegenwart von Wasserdampf, an. Im Spaltprodukt in geringer Konzentration verbleibende Chlor-Kohlenstoff-Verbindungen beeinträchtigen diesen Verfahrensschritt nicht. Das bei der Vergasung resultierende CO/H₂-Gemisch wird zur Entfernung von Feststoffen und HCl mit Wasser, dem gegebenenfalls alkalische Reagenzien, wie Alkalicarbonat oder -hydroxid, zugesetzt wurde, gewaschen. Zur Herstellung von Synthesegas mit einem bestimmten, von der Zusammensetzung des Rohgases abweichenden CO/H₂-Verhältnisses wird das Rohgas über ein Membranfilter geführt.The figure shows the new process in the form of a block diagram. Plastic waste is broken down thermally in the depolymerization stage at temperatures which, depending on the process, are in the range of 200 to 500 ° C to liquid products, the flowability of which corresponds roughly to that of heavy heating oils at the same temperature. The depolymerization is accompanied by the elimination of hydrogen chloride from chlorine-containing plastics, the hydrogen chloride is washed out with water from the reaction product and in a known manner, e.g. to 30% crude acid, worked up. In special cases, the hydrogen chloride can also be neutralized in an alkaline wash. The splitting is followed by gasification, i.e. the partial oxidation of the depolymerized waste with oxygen in the presence of water vapor. Chlorine-carbon compounds remaining in a low concentration in the cleavage product do not impair this process step. The resulting CO / H₂ mixture in the gasification is washed to remove solids and HCl with water, optionally with alkaline reagents, such as alkali carbonate or hydroxide, added. To produce synthesis gas with a certain CO / H₂ ratio which differs from the composition of the raw gas, the raw gas is passed through a membrane filter.

Statt Synthesegas kann aus dem Rohgas auch Wasserstoff gewonnen werden. Hierzu wird es konvertiert, das resultierende CO₂/H₂-Gemisch einer chemischen Wäsche zugeführt und in einer Druckwechsel-Absorptionsstufe in CO₂ und H₂ aufgetrennt.Instead of synthesis gas, hydrogen can also be obtained from the raw gas. For this purpose, it is converted, the resulting CO₂ / H₂ mixture is fed into a chemical wash and separated into CO₂ and H₂ in a pressure swing absorption stage.

Beispielexample

Zurückgeführtes Verpackungsmaterial aus Kunststoff mit einem Gehalt von 2,5 Gew.-% Wasser und 3,3 Gew.-% Chlor wird in einer flüssigen Hilfsphase, die durch thermische Spaltung von Kunststoffabfällen erhalten wurde, suspendiert und zur Abtrennung des Wassers auf etwa 130°C erhitzt. Darauf überführt man die Kunststoffsuspension in den Spaltreaktor, in dem die Depolymerisation des Einsatzmaterials bei etwa 350°C und einer Verweilzeit von etwa 4 h erfolgt. Gasförmige Spaltprodukte werden auf etwa 30°C abgekühlt und zur Abtrennung von Chlorwasserstoff einer entsprechenden Absorptionanlage zugeführt. Das flüssige Depolymerisat hat folgende Zusammensetzung. C = 84,3 Gew.-% H = 12,0 Gew.-% N = 0,4 Gew.-% S = 1,3 Gew.-% Asche = 2,0 Gew.-% Returned packaging material made of plastic with a content of 2.5% by weight of water and 3.3% by weight of chlorine is suspended in a liquid auxiliary phase, which was obtained by thermal splitting of plastic waste, and to separate the water at about 130 ° C. heated. The plastic suspension is then transferred to the cleavage reactor, in which the feed material is depolymerized at about 350 ° C. and has a residence time of about 4 hours. Gaseous fission products are cooled to about 30 ° C and fed to an appropriate absorption system for the separation of hydrogen chloride. The liquid depolymerizate has the following composition. C. = 84.3% by weight H = 12.0% by weight N = 0.4% by weight S = 1.3% by weight ash = 2.0% by weight

Es enthält 300 mg Cl/l, hat eine Dichte von 920 kg/m³ und eine Viskosität von 404 mPa . s (bei 90°C).It contains 300 mg Cl / l, has a density of 920 kg / m³ and a viscosity of 404 mPa. s (at 90 ° C).

Ein Teil des flüssigen Spaltproduktes wird als Hilfsphase (Suspensionsmittel) für die thermische Spaltung weiterer Kunststoffabfälle verwendet, der Rest partiell zu Wassergas oxidiert. Hierzu setzt man das Depolymerisat bei etwa 1400°C und einem Druck von 4 MPa in bekannter Weise mit Sauerstoff und Wasserdampf um. Zur Erzeugung von 1000 Nm² CO/H₂-Gemisch benötigt man 400 kg Depolymerisat, 325 Nm³ Sauerstoff und 110 kg Dampf. Das Rohgas enthält 43,8 Vol.-% CO, 48,6 Vol.-% H₂ und 6,6 Vol.-% CO₂; das CO/H₂-Verhältnis ist etwa 0,9.Part of the liquid fission product is used as an auxiliary phase (suspension medium) for the thermal fission of further plastic waste, the rest is partially oxidized to water gas. For this purpose, the depolymerizate is reacted with oxygen and water vapor in a known manner at about 1400 ° C. and a pressure of 4 MPa. To generate 1000 Nm² of CO / H₂ mixture, 400 kg of depolymerized material, 325 Nm³ of oxygen and 110 kg of steam are required. The raw gas contains 43.8 vol .-% CO, 48.6 vol .-% H₂ and 6.6 vol .-% CO₂; the CO / H₂ ratio is about 0.9.

Claims (11)

Verfahren zur Herstellung von Synthesegas aus Kunststoffabfällen, dadurch gekennzeichnet, daß die Abfälle thermisch überwiegend zu flüssigen Produkten gespalten und die flüssigen Spaltprodukte durch partielle Oxidation in Synthesegas überführt werden.A process for the production of synthesis gas from plastic waste, characterized in that the waste is mainly thermally split into liquid products and the liquid split products are converted into synthesis gas by partial oxidation. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die thermische Spaltung bei Temperaturen zwischen 250 und 450°C unter Verwendung einer bei der Reaktionstemperatur flüssigen Hilfsphase erfolgt.Process according to Claim 1, characterized in that the thermal cleavage takes place at temperatures between 250 and 450 ° C using an auxiliary phase which is liquid at the reaction temperature. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die flüssige Hilfsphase aus den flüssigen Abbauprodukten der Kunststoffabfälle besteht.A method according to claim 2, characterized in that the liquid auxiliary phase consists of the liquid degradation products of the plastic waste. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die thermische Spaltung in Gegenwart von Katalysatoren erfolgt.Method according to one or more of claims 1 to 3, characterized in that the thermal cleavage takes place in the presence of catalysts. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß insbesondere, wenn chlorhaltige Kunststoffabfälle vorhanden sind, die thermische Spaltung in zwei oder mehr Stufen durchgeführt wird, wobei die Temperatur von Stufe zu Stufe ansteigt und durch Wahl der Temperatur die Hauptmenge des als Spaltprodukt anfallenden Chlorwasserstoffs in der ersten Stufe gebildet wird.Method according to one or more of claims 1 to 4, characterized in that, in particular if chlorine-containing plastic waste is present, the thermal cleavage is carried out in two or more stages, the temperature increasing from stage to stage and the majority of the is formed as a cleavage product of hydrogen chloride in the first stage. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die partielle Oxidation der flüssigen Spaltprodukte bei Temperaturen zwischen 1100 und 1500°C und einem Druck von 1 bis 10 MPa erfolgt.Method according to one or more of claims 1 to 5, characterized in that the partial oxidation of the liquid fission products takes place at temperatures between 1100 and 1500 ° C and a pressure of 1 to 10 MPa. Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die partielle Oxidation über die zugesetzte Sauerstoffmenge so geführt wird, daß etwa 0,1 bis etwa 0,3 Gew.-% Ruß, bezogen auf die flüssigen Spaltprodukte, gebildet werden.Method according to one or more of claims 1 to 6, characterized in that the partial oxidation over the amount of oxygen added is carried out in such a way that about 0.1 to about 0.3% by weight of soot, based on the liquid fission products, is formed . Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das den Vergasungsreaktor verlassende Rohgas zunächst in einem Strahlungskühler auf 500 bis 1000°C und darauf in einem Konvektionskühler auf 150 bis 300°C gekühlt wird.Method according to one or more of claims 1 to 7, characterized in that the raw gas leaving the gasification reactor is first cooled to 500 to 1000 ° C in a radiation cooler and then to 150 to 300 ° C in a convection cooler. Verfahren nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das gekühlte Gas mit Wasser gewaschen und darauf die im Waschwasser suspendierte Asche abgetrennt wird.Method according to one or more of claims 1 to 8, characterized in that the cooled gas is washed with water and then the ash suspended in the washing water is separated off. Verfahren nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das gereinigte Gas zur Einstellung eines gewünschten CO/H₂-Verhältnisses einer Membranfilteranlage zugeführt wird.Method according to one or more of claims 1 to 9, characterized in that the cleaned gas is fed to a membrane filter system in order to set a desired CO / H₂ ratio. Verfahren nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das gereinigte Gas einer Konvertierungsanlage zugeführt wird.Method according to one or more of claims 1 to 9, characterized in that the cleaned gas is fed to a conversion system.
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JP2534461B2 (en) 1996-09-18
KR950005959A (en) 1995-03-20
CA2130019C (en) 1999-10-19
ES2141788T3 (en) 2000-04-01
TW310333B (en) 1997-07-11
US5457250A (en) 1995-10-10
EP0639631B1 (en) 1999-11-24
DE59408948D1 (en) 1999-12-30
JPH07197041A (en) 1995-08-01
KR100308464B1 (en) 2001-12-01
DE4328188C2 (en) 1996-04-18
DE4328188A1 (en) 1995-02-23
BR9403282A (en) 1995-04-11
ATE186940T1 (en) 1999-12-15

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