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EP0832959B1 - Process for working up polyvinylchloride (PVC) - Google Patents

Process for working up polyvinylchloride (PVC) Download PDF

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Publication number
EP0832959B1
EP0832959B1 EP97112377A EP97112377A EP0832959B1 EP 0832959 B1 EP0832959 B1 EP 0832959B1 EP 97112377 A EP97112377 A EP 97112377A EP 97112377 A EP97112377 A EP 97112377A EP 0832959 B1 EP0832959 B1 EP 0832959B1
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EP
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Prior art keywords
pvc
process according
slag
slag bath
gas
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EP97112377A
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German (de)
French (fr)
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EP0832959A1 (en
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Siegmar Dr. Ing. Marschner
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Linde Engineering Dresden GmbH
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Linde KCA Dresden GmbH
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    • 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
    • C10J3/57—Gasification using molten salts or metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • 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
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • 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
    • C10J2300/00—Details of gasification processes
    • C10J2300/12—Heating the gasifier
    • C10J2300/1223—Heating the gasifier by burners

Definitions

  • the invention relates to a process for working up polyvinyl chloride (PVC) raw material decomposition.
  • PVC polyvinyl chloride
  • PVC polyvinyl chloride
  • PVC-based plastics One differentiates basically between hard PVC and soft PVC. While hard PVC only in small amounts Concentration of stabilizers, lubricants, color pigments and possibly fillers (e.g. Chalk) contains the plasticized PVC in high concentration plasticizers admixed (mainly esters of phthalic acid).
  • the Refurbishment of old PVC a number of by-products, their quantity and Composition essentially from the method used and from the Depending on the composition of the old PVC.
  • the old PVC becomes a tightly intermeshing Twin screw extruder at 300-400 ° C split off the HCI gas.
  • the the Split coke leaving extruder can then be fed to gasification or serves as a reducing agent in the metallurgical industry.
  • the HCl gas contains especially in the case of old PVC with a high proportion of soft PVC, large quantities of others volatile fission products, the separation of which is expensive. These fission products are in generally only usable for the generation of thermal energy.
  • old PVC are often In addition to other plastics, inorganic admixtures such as metal parts, Contains concrete residues or stones.
  • the steam obtained in the waste heat boiler is used to generate electricity and partly for heating the extractive distillation.
  • the plant needs extensive Facilities for waste gas purification, waste water purification and evaporation of the Calcium chloride solution.
  • waste gas purification, waste water purification and evaporation of the Calcium chloride solution In addition to lignite dust and sand as auxiliaries for PVC combustion are used for the removal of nitrogen oxides and ammonia and natural gas Dioxides from the flue gas are required.
  • the object of the present invention is to demonstrate a method which Splitting of old PVC into HCl gas and usable or landfillable products enables a single process step.
  • the object is achieved in that the PVC waste shredded to a grain size of a few millimeters is placed in a rotating, liquid slag bath and decomposed there with the addition of oxygen and water vapor and / or CO 2 at 1300-1500 ° C. to give a cracked gas and slag become.
  • the rotation of the slag bath is achieved by introducing the oxygen and the gasifying agent (water vapor and / or CO 2 ) tangentially.
  • the discarded old PVC is constantly mixed with hot, high-energy slag.
  • the HCI gas is split off spontaneously, the remaining organic components of the old PVC are partly converted to CO and H 2 with oxygen in part in the slag bath and partly in the gas space above.
  • the chalk contained in the old PVC is broken down into CO 2 and CaO in the slag bath.
  • CO 2 acts as a gasifying agent for organic components of the old PVC.
  • the CaO is one of the most important slag components.
  • the slag mainly contains SiO 2 . This is partly caused by silicate admixtures in the old PVC (e.g. concrete residues on floor coverings) and partly provided by mixed sand.
  • the other components of the slag are metals and their oxides that have been introduced with the old PVC.
  • a preliminary separation of the inorganic admixtures prior to processing is therefore not necessary for the process according to the invention; rather, inorganic admixtures with a small grain size are even desirable.
  • the splitting of the old PVC takes place in a liquid, rotating slag bath, which mainly consists of components from reconditioned old PVC and itself constantly renewed from the fed old PVC.
  • the excess slag flows over a centrally located overflow and drips into an underlying one Water bath where the slag is quenched and transformed into a glassy state becomes. In this form, the slag can be deposited without restrictions.
  • the gasification of old PVC with oxygen is exothermic in total, so that it can be autothermal.
  • the energy sources of the old PVC are the organic component of the chemically pure PVC (42% by weight), the plasticizers (20 to 100%, based on PVC) and other organic admixtures.
  • energy requires the elimination of the HCl gas, the splitting of the chalk into CO 2 and CaO, and the melting of the entered silicates and metals.
  • Gasification takes place in a temperature range of 1300-1500 ° C at a system pressure of up to 30 bar.
  • the slag bath temperature is regulated by the amount of oxygen entered per unit of old PVC and the ratio of oxygen to gasifying agent (water vapor or CO 2 ).
  • the slag temperature can also be raised by one or more additional burners in the gas space.
  • the additional burners also heat up the slag bath to the operating temperature during commissioning. For example, they are fed with natural gas during commissioning.
  • the fuel gas generated in the carburetor can be used in continuous operation.
  • the temperature can be increased by feeding oxygen into the gas space.
  • the cracked gas emerging from the gasifier mainly contains H 2 , CO, CO 2 , H 2 O and HCl.
  • the HCl is removed from the cracked gas by absorption in aqueous solution as concentrated hydrochloric acid.
  • the HCl-free gas can be used after the treatment in well-known cleaning stages as synthesis gas or as fuel gas.
  • the old PVC is either present as solid particles with the gasifier Grain sizes of less than or equal to 5 mm in diameter or at a temperature between 100 and 250 ° C, preferably between 140 to 200 ° C, heated and premelted abandoned in pasty form.
  • metal chlorides for example, can also be added to the slag bath Alkaline or alkaline earth chlorides, are supplied to them using energy Win HCI gas.
  • a particularly advantageous application of the method according to the invention is if it is used in conjunction with a plant for the production of PVC, because then the effort for storage and / or transportation of the usable Products of the method according to the invention are omitted entirely or partially.
  • the old PVC is available with a grain size of ⁇ 5 mm.
  • the old PVC gas ifies in the slag bath at 1380 ° C to 2485 m 3 (iN) / h gasification gas (stream 6) with the following composition regarding the main components: H 2 40.9 vol% CO 38.5% by volume CO 2 3.9% by volume H 2 O 10.4 vol .-% HCl 5.0 vol.% N 2 1.3 vol.%
  • slag bath gasifier can also be influenced by adding slag formers, chlorinated hydrocarbons and / or metal chlorides (stream 8) and by supplying oxygen to the gas space (stream 9) and / or the additional burner 10.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Processing Of Solid Wastes (AREA)

Description

Die Erfindung betrifft ein Verfahren zur Aufarbeitung von Polyvinylchlorid (PVC) durch rohstoffliche Zerlegung.The invention relates to a process for working up polyvinyl chloride (PVC) raw material decomposition.

PVC (Polyvinylchlorid) ist ein häufig verwendeter Kunststoff. Dabei wird in der Regel das PVC nicht in der chemisch reinen Form eingesetzt, sondern mit unterschiedlichen Beimengungen vermischt. Die große Vielfalt an Beimengungen in unterschiedlichen Konzentrationen ergeben die sehr weit gefächerte Palette von Anwendungseigenschaften der Kunststoffe auf PVC-Basis. Man unterscheidet grundsätzlich zwischen Hart-PVC und Weich-PVC. Während Hart-PVC nur in geringer Konzentration Stabilisatoren, Gleitmittel, Farbpigmente und eventuell Füllstoffe (z.B. Kreide) enthält, sind dem Weich-PVC in hoher Konzentration Weichmacher zugemischt (vorwiegend Ester der Phthalsäure).PVC (polyvinyl chloride) is a commonly used plastic. It usually does PVC is not used in the chemically pure form, but with different ones Admixtures mixed. The large variety of admixtures in different Concentrations result in the very wide range of Application properties of PVC-based plastics. One differentiates basically between hard PVC and soft PVC. While hard PVC only in small amounts Concentration of stabilizers, lubricants, color pigments and possibly fillers (e.g. Chalk) contains the plasticized PVC in high concentration plasticizers admixed (mainly esters of phthalic acid).

Zur Schonung der Ressourcen sowie der Deponiekapazität ist man bestrebt, Kunststoffabfälle zu Recyclaten aufzuarbeiten und danach erneut zu verwenden. Dieses werkstoffliche Recycling ist bei PVC wegen der großen Sortenvielfalt nur bedingt möglich. So lassen sich sortenrein gesammelte PVC-Abfälle aus Fensterprofilen nach einem Umschmelzen erneut zu Fensterprofilen verarbeiten. Das werkstoffliche Recycling von PVC-Gemischen führt dagegen nur zu minderwertigen Produkten. Gemischte PVC-Abfälle sind deshalb vorteilhaft nur durch rohstoffliches Recycling aufzuarbeiten. Unter rohstofflichem Recycling wird die Aufspaltung der Polymerketten in die monomeren Grundbausteine der Kunststoffe verstanden.To conserve resources and landfill capacity, efforts are made to Recycle plastic waste into recyclates and then reuse it. This material recycling is only with PVC because of the large variety conditionally possible. In this way, sorted PVC waste can be collected Process window profiles again after re-melting into window profiles. The Mechanical recycling of PVC mixtures, on the other hand, only leads to inferior ones Products. Mixed PVC waste is therefore only advantageous through raw materials Recycle recycling. Raw material recycling is the splitting of the polymer chains understood in the monomeric basic building blocks of plastics.

Auch das rohstoffliche Recycling von PVC ist im Vergleich zu anderen Kunststoffen schwierig. Während z.B. Polyolefine durch Wärmebehandlung in ihre monomeren Grundbausteine, die Olefine, zerfallen können, gelingt es nicht, das PVC wieder direkt in Vinylchlorid umzuwandeln. Vielmehr spaltet reines PVC, d.h. ohne Beimengungen von Stabilisatoren, Weichmachern, Füllstoffen, bei Temperaturen oberhalb 200 °C Chlorwasserstoff (HCl) ab. Als flüchtige Spaltprodukte entweichen außerdem aromatische Verbindungen, überwiegend Benzol (s. Knümann, Bockhorn; Chemie-Ingenieur-Technik 66 (1994), 1, 74-76). Nach der bei etwa 400 °C abgeschlossenen Abtrennung des HCI erfolgt bis etwa 500 °C die weitere Aufspaltung in vorwiegend aromatische Verbindungen und einen koksartigen Rückstand. The raw material recycling of PVC is also compared to other plastics difficult. While e.g. Polyolefins by heat treatment in their monomers The basic building blocks, the olefins, can decay, the PVC does not succeed again convert to vinyl chloride. Rather, pure PVC splits, i.e. without additives of stabilizers, plasticizers, fillers, at temperatures above 200 ° C Hydrogen chloride (HCl). Also escape as volatile fission products aromatic compounds, predominantly benzene (see Knümann, Bockhorn; chemical engineering technology 66: 1, 74-76 (1994). After completed at about 400 ° C Separation of the HCI takes place up to about 500 ° C. aromatic compounds and a coke-like residue.

Bei entsprechender Reinheit kann HCl-Gas zu erneuten Gewinnung von PVC verwendet werden über die Reaktionsschritte:

  • Oxichlorierung von Ethen zu 1,2-Dichlorethan (EDC) C2H4 + 2 HCl +0,5O2 ⇒ CICH2 - CH2Cl + H2O
  • Dehydrochlorierung von EDC zu Vinylchlorid ClCH2 - CH2Cl ⇒ H2C = CHCI + HCl
  • Polymerisation von Vinylchlorid zu PVC.
With appropriate purity, HCl gas can be used to recover PVC via the reaction steps:
  • Oxichlorination of ethene to 1,2-dichloroethane (EDC) C 2 H 4 + 2 HCl + 0.5O 2 ⇒ CICH 2 - CH 2 Cl + H 2 O
  • Dehydrochlorination of EDC to vinyl chloride ClCH 2 - CH 2 Cl ⇒ H 2 C = CHCI + HCl
  • Polymerization of vinyl chloride to PVC.

Damit ist der Chlorkreis für PVC geschlossen.This closes the chlorine circuit for PVC.

Neben dem HCI-Gas als Hauptprodukt der PVC-Spaltung entstehen bei der Aufarbeitung von Alt-PVC eine Reihe von Nebenprodukten, deren Menge und Zusammensetzung wesentlich vom verwendeten Verfahren und von der Zusammensetzung des Alt-PVC abhängen.In addition to the HCI gas as the main product of PVC splitting, the Refurbishment of old PVC a number of by-products, their quantity and Composition essentially from the method used and from the Depending on the composition of the old PVC.

Nach PCT/DE 94/01366 wird aus dem Alt-PVC in einem dichtkämmenden Doppelschnecken-Extruder bei 300-400 °C das HCI-Gas abgespalten. Der den Extruder verlassende Spaltkoks kann anschließend einer Vergasung zugeführt werden oder dient als Reduktionsmittel in der Hüttenindustrie. Das HCl-Gas enthält besonders bei Alt-PVC mit einem hohen Anteil an Weich-PVC noch große Mengen anderer flüchtiger Spaltprodukte, deren Abtrennung aufwendig ist. Diese Spaltprodukte sind in der Regel nur zur Erzeugung von thermischer Energie nutzbar. Im Alt-PVC sind oft neben anderen Kunststoffen auch anorganische Beimengungen wie Metallteile, Betonreste oder Steine enthalten. Zum Schutz der Extruder müssen diese anorganischen Beimengungen vor der Verarbeitung möglichst vollständig aussortiert werden. Die Aufarbeitung von Alt-PVC erfordert nach dieser Methode mehrere Verfahrensstufen. Bekannt ist ein Verfahren zur Verbrennung von Alt-PVC im Drehrohrofen bei Temperaturen bis zu 1000 °C (Datenbank PVC und Umwelt 9/93, AgPU Bonn). Um die Verbrennung sicher zu beherrschen, werden den geshredderten PVC-Abfällen Braunkohlenstaub und Sand zugemischt. Das HCl-Gas wird nach einer Abkühlung im Abhitzekessel aus dem Rauchgas durch Absorption im Wasser ausgewaschen. Die dabei entstehende ca. 20 %ige Salzsäure wird mittels Extraktivdestillation mit Calciumchloridlösung zu 100 %igem HCl-Gas aufgearbeitet. According to PCT / DE 94/01366, the old PVC becomes a tightly intermeshing Twin screw extruder at 300-400 ° C split off the HCI gas. The the Split coke leaving extruder can then be fed to gasification or serves as a reducing agent in the metallurgical industry. The HCl gas contains especially in the case of old PVC with a high proportion of soft PVC, large quantities of others volatile fission products, the separation of which is expensive. These fission products are in generally only usable for the generation of thermal energy. In old PVC are often In addition to other plastics, inorganic admixtures such as metal parts, Contains concrete residues or stones. To protect the extruders, they must be inorganic Additions are sorted out as completely as possible before processing become. The reprocessing of old PVC using this method requires several Procedural stages. A method for the combustion of waste PVC is known in the Rotary tube furnace at temperatures up to 1000 ° C (database PVC and environment 9/93, AgPU Bonn). In order to safely control the combustion, the shredder is shredded PVC waste mixed with brown coal dust and sand. The HCl gas is after a Cooling in the waste heat boiler from the flue gas by absorption in the water washed out. The approx. 20% hydrochloric acid that is formed is removed using Extractive distillation worked up with calcium chloride solution to 100% HCl gas.

Der im Abhitzekessel gewonnene Wasserdampf dient zur Stromerzeugung und teilweise zur Beheizung der Extraktivdestillation. Die Anlage benötigt umfangreiche Einrichtungen zur Abgasreinigung, Abwasserreinigung und die Eindampfung der Calciumchloridlösung. Neben Braunkohlenstaub und Sand als Hilfsstoffe für die PVC-Verbrennung werden Ammoniak und Erdgas für die Entfernung von Stickoxiden und Dioxiden aus dem Rauchgas benötigt.The steam obtained in the waste heat boiler is used to generate electricity and partly for heating the extractive distillation. The plant needs extensive Facilities for waste gas purification, waste water purification and evaporation of the Calcium chloride solution. In addition to lignite dust and sand as auxiliaries for PVC combustion are used for the removal of nitrogen oxides and ammonia and natural gas Dioxides from the flue gas are required.

Gegenüber der Verbrennung mit Luft hat die Vergasung von Alt-PVC unter Verwendung von Sauerstoff verfahrenstechnische und ökologische Vorteile:

  • a) Die Vergasung arbeitet mit Sauerstöffunterschuß. Die Hauptkomponenten im Vergasungsgas sind deshalb H2, CO und CH4. Der Schwefel setzt sich zu H2S um, welcher nach der HCl-Entfernung aus dem Vergasungsgas gleichfalls mit relativ geringem technologischen Aufwand entfernt werden kann. Das Vergasungsgas ist als Brenngas einsetzbar.
    Die Verbrennung arbeitet mit Sauerstoffüberschuß. Die Hauptkomponenten im Rauchgas sind deshalb CO2, H2O und NOX. Der Schwefel setzt sich zu SO2 um, welches mit vergleichsweise größerem technologischen Aufwand entfernt werden muß.
  • b) Die Vergasung erfolgt bei höherer Temperatur als die Verbrennung. Damit wird eine höhere Zerstörungseffizienz von organischen Schadstoffen erreicht, die Dioxin-Furan-Problematik wird sicher beherrscht, und es ist eine mineralische Einbindung von Schwermetallen in die Schlacke zu nicht eluierbaren Verbindungen möglich.
    Bei der Verbrennung bilden die in den Abfallstoffen enthaltenen Aschebildner einen Rückstand, der eine zusätzliche Verfahrensstufe der Aufschmelzung erfordert oder zur sicheren Ablagerung besondere Deponiemaßnahmen bedingt. In der aufwendigen Rauchgasreinigung können dioxinbelastete Filterstäube und Schwermetallschlämme anfallen.
  • c) Die auf Normzustand bezogene Brenngasmenge aus der Vergasung beträgt nur etwa 1/10 der Rauchgasmenge aus der Verbrennung. Beim gewöhnlich erhöhten Betriebsdruck der Vergasung von 5-30 bar liegt der Volumenstrom des Brenngases sogar unter 1 % des Volumenstromes vom Rauchgas. Dadurch werden die Apparate für die Gasreinigung vergleichsweise klein. Durch die höhere HCl-Konzentration im Brenngas kann eine höher konzentrierte Salzsäure am Ablauf der HCI-Absorption erzeugt werden, wodurch geringere Betriebskosten für die HCl-Destillation anfallen.
    • Compared to combustion with air, the gasification of waste PVC using oxygen has procedural and ecological advantages:
  • a) The gasification works with oxygen deficit. The main components in the gasification gas are therefore H 2 , CO and CH 4 . The sulfur converts to H 2 S, which can also be removed from the gasification gas with relatively little technological effort after HCl removal. The gasification gas can be used as fuel gas.
    The combustion works with an excess of oxygen. The main components in the flue gas are therefore CO 2 , H 2 O and NO X. The sulfur converts to SO 2 , which has to be removed with comparatively greater technological effort.
  • b) The gasification takes place at a higher temperature than the combustion. This achieves a higher destruction efficiency of organic pollutants, the dioxin-furan problem is safely mastered, and it is possible to mineralize heavy metals in the slag to form non-elutable compounds.
    During incineration, the ash formers contained in the waste materials form a residue, which requires an additional melting step or which requires special landfill measures for safe storage. Dioxin-contaminated filter dusts and heavy metal sludges can occur in the complex flue gas cleaning.
  • c) The amount of fuel gas from the gasification based on standard conditions is only about 1/10 of the amount of flue gas from the combustion. At the usually increased operating pressure of the gasification of 5-30 bar, the volume flow of the fuel gas is even less than 1% of the volume flow of the flue gas. This makes the gas cleaning apparatus comparatively small. Due to the higher HCl concentration in the fuel gas, a more concentrated hydrochloric acid can be generated at the end of the HCI absorption, which results in lower operating costs for the HCl distillation.

    • Die Verwendung der bekannten Vergasungstechnologien ist für die Aufarbeitung von Alt-PVC problematisch. Denn in Festbettvergasern bäckt das Alt-PVC zu einer zähen, in der Regel klebrigen Masse zusammen. Daher ist eine kontinuierliche Vergasung im Festbettvergaser nicht möglich. Eine denkbare Entsorgung von Alt-PVC durch einen Flugstromvergaser bedingt eine vorangehende Tieftemperaturvermahlung des Einsatzstoffes, die einerseits sehr aufwendig und andererseits außerordentlich kostenintensiv ist.The use of the known gasification technologies is for the processing of Old PVC is problematic. Because in fixed bed gasifiers, the old PVC bakes into a tough, usually sticky mass together. Therefore, a continuous gasification in the Fixed bed carburettor not possible. A conceivable disposal of old PVC by one Entrained-flow gasifier requires a previous low-temperature grinding of the Input material, which is very complex on the one hand and extraordinary on the other is expensive.

    Nach dem Catalyc Extractor Processing, CEP, von Molten Metal Technology gelingt die Spaltung von Alt-PVC wie auch anderer Abfälle im flüssigen Metallbad, vorwiegend einem Eisen-Nickelbad, bei Temperaturen von 1300 - 1800 °C in einem einzigen Verfahrensschritt. Man gewinnt das HCI-Gas mit fast 100 %iger Ausbeute. Nachteilig ist die Anreicherung des Eisen- und Nickelbades mit den vom Alt-PVC eingetragenen Schwermetallen, was eine zusätzliche Aufarbeitung der entstehenden Metall-Legierung erfordert.After Catalyc Extractor Processing, CEP, by Molten Metal Technology the splitting of old PVC as well as other waste in a liquid metal bath, mainly an iron-nickel bath, at temperatures from 1300 - 1800 ° C in one Procedural step. The HCI gas is obtained in almost 100% yield. Disadvantageous is the enrichment of the iron and nickel bath with those entered by the old PVC Heavy metals, which means an additional work-up of the resulting metal alloy required.

    Die Aufgabe der vorliegenden Erfindung ist es, ein Verfahren aufzuzeigen, das die Spaltung von Alt-PVC zu HCl-Gas und verwertbaren oder deponiefähigen Produkte in einem einzigen Verfahrensschritt ermöglicht.The object of the present invention is to demonstrate a method which Splitting of old PVC into HCl gas and usable or landfillable products enables a single process step.

    Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß die auf wenige Millimeter Korngröße geshredderten PVC-Abfälle in ein rotierendes, flüssiges Schlackenbad gegeben werden und dort unter Zusatz von Sauerstoff sowie Wasserdampf und/oder CO2 bei 1300 - 1500 °C zu einem Spaltgas und Schlacke zersetzt werden. Die Rotation des Schlackenbades wird durch ein tangentiales Einleiten des Sauerstoffes sowie des Vergasungsmittels (Wasserdampf und/oder CO2) erreicht. Durch die Rotation des Schlackenbades wird das aufgegebene Alt-PVC ständig mit heißer, energiereicher Schlacke vermischt. Die Abspaltung des HCI-Gases erfolgt spontan, die verbleibenden organischen Bestandteile des Alt-PVC werden zum Teil im Schlackenbad und zum anderen Teil im darüberliegenden Gasraum mit Sauerstoff überwiegend zu CO und H2 umgewandelt. The object is achieved in that the PVC waste shredded to a grain size of a few millimeters is placed in a rotating, liquid slag bath and decomposed there with the addition of oxygen and water vapor and / or CO 2 at 1300-1500 ° C. to give a cracked gas and slag become. The rotation of the slag bath is achieved by introducing the oxygen and the gasifying agent (water vapor and / or CO 2 ) tangentially. By rotating the slag bath, the discarded old PVC is constantly mixed with hot, high-energy slag. The HCI gas is split off spontaneously, the remaining organic components of the old PVC are partly converted to CO and H 2 with oxygen in part in the slag bath and partly in the gas space above.

    Die im Alt-PVC enthaltene Kreide wird im Schlackenbad zu CO2 und CaO aufgespalten. Das CO2 wirkt bei den herrschenden Temperaturen unter Bildung von CO als Vergasungsmittel für organische Bestandteile des Alt-PVC. Das CaO ist einer der wichtigsten Schlackenbestandteile. Neben CaO enthält die Schlacke hauptsächlich SiO2. Dieses wird zum Teil durch silikatische Beimengungen im Alt-PVC (z.B. Betonreste an Fußbodenbelägen) eingetragen, zum Teil durch beigemischten Sand bereitgestellt. Die übrigen Komponenten der Schlacke sind mit dem Alt-PVC eingetragene Metalle und ihre Oxide. Für das erfindungsgemäße Verfahren ist demnach eine Vorabtrennung der anorganischen Beimengungen vor der Verarbeitung nicht notwendig, vielmehr sind anorganische Beimengungen mit kleiner Korngröße sogar erwünscht.The chalk contained in the old PVC is broken down into CO 2 and CaO in the slag bath. At the prevailing temperatures, CO 2 acts as a gasifying agent for organic components of the old PVC. The CaO is one of the most important slag components. In addition to CaO, the slag mainly contains SiO 2 . This is partly caused by silicate admixtures in the old PVC (e.g. concrete residues on floor coverings) and partly provided by mixed sand. The other components of the slag are metals and their oxides that have been introduced with the old PVC. A preliminary separation of the inorganic admixtures prior to processing is therefore not necessary for the process according to the invention; rather, inorganic admixtures with a small grain size are even desirable.

    Die Spaltung des Alt-PVC erfolgt also in einem flüssigen, rotierenden Schlackenbad, welches überwiegend aus Bestandteilen von aufgearbeiteten Alt-PVC besteht und sich ständig aus dem zugespeisten Alt-PVC erneuert. Die überschüssige Schlacke fließt über einen zentral angeordneten Überlauf und tropft in ein darunterliegendes Wasserbad, wo die Schlacke abgeschreckt und in einen glasartigen Zustand überführt wird. In dieser Form ist die Schlacke ohne Einschränkungen deponierfähig.The splitting of the old PVC takes place in a liquid, rotating slag bath, which mainly consists of components from reconditioned old PVC and itself constantly renewed from the fed old PVC. The excess slag flows over a centrally located overflow and drips into an underlying one Water bath where the slag is quenched and transformed into a glassy state becomes. In this form, the slag can be deposited without restrictions.

    Die Vergasung von Alt-PVC mit Sauerstoff ist in der Summe exotherm, so daß sie autotherm verlaufen kann. Energieträger des Alt-PVC sind die organische Komponente des chemisch reinen PVC (42 %-Gewichtsanteil), die Weichmacher (20 bis 100 %, bezogen auf PVC) sowie andere organische Beimengungen. Neben der Aufheizung des Alt-PVC auf die Schlackenbadtemperatur benötigen Energie die Abspaltung des HCl-Gases, die Aufspaltung der Kreide zu CO2 und CaO sowie das Aufschmelzen von eingetragenen Silikaten und Metallen.The gasification of old PVC with oxygen is exothermic in total, so that it can be autothermal. The energy sources of the old PVC are the organic component of the chemically pure PVC (42% by weight), the plasticizers (20 to 100%, based on PVC) and other organic admixtures. In addition to heating the old PVC to the slag bath temperature, energy requires the elimination of the HCl gas, the splitting of the chalk into CO 2 and CaO, and the melting of the entered silicates and metals.

    Die Vergasung erfolgt in einem Temperaturbereich von 1300 -1500 °C bei einem Systemdruck von bis zu 30 bar. Die Schlackenbadtemperatur wird geregelt durch die pro Mengeneinheit Alt-PVC eingetragene Sauerstoffmenge sowie das Verhältnis von Sauerstoff zu Vergasungsmittel (Wasserdampf oder CO2). Weiterhin kann die Schlackentemperatur durch einen oder mehrere Zusatzbrenner im Gasraum angehoben werden. Die Zusatzbrenner übernehmen auch das Aufheizen des Schlackenbades auf die Betriebstemperatur während der Inbetriebnahme. Sie werden während der Inbetriebnahme beispielsweise mit Erdgas gespeist. Im Dauerbetrieb kann das im Vergaser erzeugte Brenngas verwendet werden. Außerdem kann die Temperatur durch zusätzliche Sauerstoffeinspeisung in den Gasraum erhöht werden. Gasification takes place in a temperature range of 1300-1500 ° C at a system pressure of up to 30 bar. The slag bath temperature is regulated by the amount of oxygen entered per unit of old PVC and the ratio of oxygen to gasifying agent (water vapor or CO 2 ). The slag temperature can also be raised by one or more additional burners in the gas space. The additional burners also heat up the slag bath to the operating temperature during commissioning. For example, they are fed with natural gas during commissioning. The fuel gas generated in the carburetor can be used in continuous operation. In addition, the temperature can be increased by feeding oxygen into the gas space.

    Das aus dem Vergaser austretende Spaltgas enthält hauptsächlich H2, CO, CO2, H2O und HCI. Nach einem Quench und einer Abhitzeverwertung wird das HCI durch Absorption in wäßriger Lösung als konzentrierte Salzsäure aus dem Spaltgas entfernt. Das HCl-freie Gas kann nach der Behandlung in allgemein bekannten Reinigungsstufen als Synthesegas oder als Brenngas eingesetzt werden.The cracked gas emerging from the gasifier mainly contains H 2 , CO, CO 2 , H 2 O and HCl. After a quench and waste heat recovery, the HCl is removed from the cracked gas by absorption in aqueous solution as concentrated hydrochloric acid. The HCl-free gas can be used after the treatment in well-known cleaning stages as synthesis gas or as fuel gas.

    Das Alt-PVC wird dem Vergaser erfindungsgemäß entweder als feste Partikel mit Korngrößen von kleiner gleich 5 mm Durchmesser oder auf eine Temperatur zwischen 100 und 250 °C, vorzugsweise zwischen 140 bis 200 °C, erwärmt und vorgeschmolzen in pastöser Form aufgegeben.According to the invention, the old PVC is either present as solid particles with the gasifier Grain sizes of less than or equal to 5 mm in diameter or at a temperature between 100 and 250 ° C, preferably between 140 to 200 ° C, heated and premelted abandoned in pasty form.

    Erfindungsgemäß ist es möglich, in das Schlackenbad auch andere feste oder flüssige chlorierte Kohlenwasserstoffe einzubringen, um aus diesen HCI-Gas zu gewinnen. Weiterhin können dem Schlackenbad erfindungsgemäß Metallchloride, beispielsweise Alkali- oder Erdalkalichloride, zugeführt werden, um aus ihnen unter Energieverbrauch HCI-Gas zu gewinnen.According to the invention, it is also possible to use other solid or liquid in the slag bath to introduce chlorinated hydrocarbons in order to extract HCI gas from them. According to the invention, metal chlorides, for example, can also be added to the slag bath Alkaline or alkaline earth chlorides, are supplied to them using energy Win HCI gas.

    Eine besonders vorteilhafte Anwendung des erfindungsgemäßen Verfahrens liegt vor, wenn es im Verbund mit einer Anlage zur Herstellung von PVC eingesetzt wird, weil dann der Aufwand für die Lagerung und/oder den Transport der verwertbaren Produkte des erfindungsgemäßen Verfahrens ganz oder teilweise entfällt.A particularly advantageous application of the method according to the invention is if it is used in conjunction with a plant for the production of PVC, because then the effort for storage and / or transportation of the usable Products of the method according to the invention are omitted entirely or partially.

    Im folgenden wird die Erfindung anhand eines Ausführungsbeispieles näher erläutert (s. Fig. 1):The invention is explained in more detail below using an exemplary embodiment (see Fig. 1):

    In den Schlackenbadvergaser 1 mit dem rotierenden Schlackenbad 2 werden 1000 kg/h Alt-PVC folgender Zusammensetzung aufgegeben (Strom 3): 52 Gew.-% PVC mit 67 Gew.-% Rein-PVC 22 Gew.-% Weichmacher 10 Gew.-% Kreide 1 Gew.-% Pigmente und Stabilisatoren 40 Gew.-% organische, brennbare Stoffe (chlorfrei, Mol-Verhältnis C:H = 1:2) 3 Gew.-% Silikate 5 Gew.-% Metalle (60 % Fe, 35 % Al, 5 % Schwermetalle) In the slag bath gasifier 1 with the rotating slag bath 2, 1000 kg / h of waste PVC of the following composition are fed (stream 3): 52 wt .-% PVC with 67% by weight pure PVC 22% by weight plasticizer 10% by weight of chalk 1% by weight of pigments and stabilizers 40% by weight organic, flammable substances (chlorine-free, molar ratio C: H = 1: 2) 3% by weight Silicates 5% by weight Metals (60% Fe, 35% Al, 5% heavy metals)

    Das Alt-PVC liegt in einer Kömung ≤ 5 mm vor.
    Durch Zufuhr von 760 kg/h Sauerstoff (93 %ig) und 315 kg/h Wasserdampf (Ströme 4 und 5) vergast das Alt-PVC im Schlackenbad bei 1380 °C zu 2485 m3 (i.N.)/h Vergasungsgas (Strom 6) mit folgender Zusammensetzung bezüglich der Hauptkomponenten: H2 40,9 Vol.-% CO 38,5 Vol.-% CO2 3,9 Vol.-% H2O 10,4 Vol.-% HCl 5,0 Vol.-% N2 1,3 Vol.-%     The old PVC is available with a grain size of ≤ 5 mm.
    By supplying 760 kg / h oxygen (93%) and 315 kg / h water vapor (streams 4 and 5), the old PVC gasifies in the slag bath at 1380 ° C to 2485 m 3 (iN) / h gasification gas (stream 6) with the following composition regarding the main components: H 2 40.9 vol% CO 38.5% by volume CO 2 3.9% by volume H 2 O 10.4 vol .-% HCl 5.0 vol.% N 2 1.3 vol.%

    Es werden 134 kg/h Schlacke neu gebildet. Mit einer Zusammensetzung von 22,4 % SiO2, 21,6 % CaO, 23,9 % Al2O3 und 28,4 % FeO tropft die neu gebildete Menge in das unter dem Vergaser angeordnete Wasserbad (Strom 7).
    Aus dem Vergasungsgas werden mit bekannten Methoden 202 kglh Chlorwasserstoff entfernt und nach entsprechenden Reinigunsstufen gasförmig zur Oxichlorierung gegeben.
    Die Fahrweise des Schlackenbadvergasers kann zusätzlich beeinflußt werden durch die Zugabe von Schlackenbildnern, Chlorkohlenwasserstoffen und/oder Metallchloriden (Strom 8) sowie durch Sauerstoffzufuhr in den Gasraum (Strom 9) und/oder den Zusatzbrenner 10.    134 kg / h of slag are newly formed. With a composition of 22.4% SiO 2 , 21.6% CaO, 23.9% Al 2 O 3 and 28.4% FeO, the newly formed amount drips into the water bath located under the gasifier (stream 7).
    202 kg / h of hydrogen chloride are removed from the gasification gas using known methods and, after corresponding purification stages, are added in gaseous form for oxychlorination.
    The mode of operation of the slag bath gasifier can also be influenced by adding slag formers, chlorinated hydrocarbons and / or metal chlorides (stream 8) and by supplying oxygen to the gas space (stream 9) and / or the additional burner 10.

    Claims (11)

    1. Process for reprocessing PVC by breakdown in raw materials in a gasification process with oxygen and steam and/or CO2 as gasifier, characterized in that the PVC is introduced into a rotating liquid slag bath, whereupon a gasification gas composed mainly of H2, CO, CO2, H2O and HCl, and also fresh slag, are formed from the PVC, the gasifier, and the oxygen, and the HCl is separated from the gasification gas (e.g. by absorption in water).
    2. Process according to Claim 1, characterized in that the slag bath is set in rotation by the ingress of oxygen and steam and/or CO2, the ingress of at least one of these materials taking place tangentially.
    3. Process according to Claim 1 or 2, characterized in that the gasification takes place at a temperature of from 1300 to 1500°C and at a pressure of from 1 to 30 bar.
    4. Process according to any of Claims 1 to 3, characterized in that the excess slag drops from the gasifier into a water bath, where it is converted into a glassy state.
    5. Process according to Claims 1 to 4, characterized in that supplementary burners have been installed in the gas space above the slag bath.
    6. Process according to Claims 1 to 5, characterized in that oxygen is also fed into the gas space above the slag bath.
    7. Process according to any of Claims 1 to 6, characterized in that sand and/or other slag-forming substances are also introduced into the slag bath.
    8. Process according to any of Claims 1 to 7, characterized in that when the PVC is introduced it is in the solid state with a particle size of not more than 5 millimetres or has been preheated to a temperature of from 100 to 250°C, preferably from 140 to 200°C and is in a paste-like or liquid state.
    9. Process according to any of Claims 1 to 8, characterized in that other chlorinated hydrocarbons are also introduced to the slag bath.
    10. Process according to any of Claims 1 to 9, characterized in that alkali metal chlorides, alkaline earth metal chlorides, and/or other metal chlorides, are also introduced to the slag bath.
    11. Use of the process according to any of Claims 1 to 10 in association with a plant for preparing PVC.
    EP97112377A 1996-07-22 1997-07-18 Process for working up polyvinylchloride (PVC) Expired - Lifetime EP0832959B1 (en)

    Applications Claiming Priority (2)

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    DE19629544A DE19629544C2 (en) 1996-07-22 1996-07-22 Process for the preparation of polyvinyl chloride (PVC) and use of the process
    DE19629544 1996-07-22

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    EP0832959B1 true EP0832959B1 (en) 2001-05-30

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    DE19735153C2 (en) * 1997-08-13 2003-10-16 Linde Kca Dresden Gmbh Process and device for gasifying waste materials
    DE19949142C1 (en) * 1999-10-12 2001-05-10 Thermoselect Ag Vaduz Process and device for the disposal and utilization of waste goods
    DE102012008457B4 (en) 2012-04-24 2016-11-03 Adam Handerek Reactor for gasifying and / or purifying, in particular for depolymerizing plastic material, and associated method

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    DE1040734B (en) * 1952-08-21 1958-10-09 Roman Rummel Process and device for the combustion or gasification of fuels
    FR2509634B1 (en) * 1981-07-20 1986-10-10 Cirta Ct Int Rech Tech Appliqu PROCESS FOR THE DESTRUCTION OF ORGANIC MATERIALS CONTAINING SULFUR AND / OR HALOGENS AND APPLICATIONS THEREOF
    US4447262A (en) * 1983-05-16 1984-05-08 Rockwell International Corporation Destruction of halogen-containing materials
    DE3434004C2 (en) * 1984-09-15 1987-03-26 Dornier System Gmbh, 7990 Friedrichshafen Process and device for waste gasification
    AT388176B (en) * 1987-07-30 1989-05-10 Voest Alpine Ag METHOD AND PLANT FOR THE PRODUCTION OF LIQUID RAW IRON OR STEEL PRE-PRODUCTS FROM LIQUID, IRON OXIDE-CONTAINING MATERIALS
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    DE19629544A1 (en) 1998-01-29
    DE59703659D1 (en) 2001-07-05
    DE19629544C2 (en) 1998-10-22

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