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EP1219324B1 - Method for elimination of halogenated and non halogenated waste - Google Patents

Method for elimination of halogenated and non halogenated waste Download PDF

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Publication number
EP1219324B1
EP1219324B1 EP02004190A EP02004190A EP1219324B1 EP 1219324 B1 EP1219324 B1 EP 1219324B1 EP 02004190 A EP02004190 A EP 02004190A EP 02004190 A EP02004190 A EP 02004190A EP 1219324 B1 EP1219324 B1 EP 1219324B1
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Prior art keywords
halogenated
carbon
process according
waste materials
waste
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EP02004190A
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German (de)
French (fr)
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EP1219324A3 (en
EP1219324A2 (en
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Guy Rollinger
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Pac Holding SA
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Pac Holding SA
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/34—Dehalogenation using reactive chemical agents able to degrade
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/04—Pesticides, e.g. insecticides, herbicides, fungicides or nematocides
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen

Definitions

  • the present invention relates to a method for disposing of halogenated and non-halogenated waste materials.
  • halogenated hydrocarbons such as those present in carbon tetrachloride, chloroform, methylene chloride, tetra- and trichlorethylene, tetrachloroethane, PCB, etc. but also in PVC or polyvinylidene chloride, are after use a more or less problematic toxic or hazardous waste it is too Dispose applies.
  • PCBs or TCDD / TCDF are not readily recyclable and must be disposed of in an environmentally sound manner.
  • the disposal takes place either by landfill or by burning on the high seas or in the countryside in high-temperature furnaces with an excess of air.
  • the US-A-4,435,379 describes a process for the decomposition of chlorinated hydrocarbons with metal oxides with the aim to convert all carbon atoms into carbon monoxide. It is important to provide elemental chlorine for the conversion of hydrogen groups in HCI. The total ratio of chlorine to hydrogen groups must be at least 1: 1 in order to produce metal chloride can.
  • the US-A-4,587,116 describes a similar process in which nitrogen-containing waste can be disposed of.
  • the heating also takes place from the outside and not from the inside out.
  • the US-A-4 451 907 discloses a method for eliminating chlorinated organic compounds.
  • the chlorinated organic compounds are vaporized in a molten salt furnace, and then fed to a reactor.
  • the chlorinated organic compounds are heated to 800 to 1200 ° C in the presence of alumina and reactive carbon, and thus decomposed.
  • Nitrogen is used as a carrier gas to pass the vaporized chlorinated organic compounds from the molten salt furnace to the reactor.
  • the EP 0 306 540 describes a process for the production of energy from substituted hydrocarbons, such as, for example, as CCl 4 , CHCl 3 , C 2 H 2 Cl 4 , PCB,
  • the waste material is thermally decomposed in an inductively heatable reactor in the presence of a heavily verhüttbaren metal oxide and an electrically conductive material, such as electrode coke or electrographite and in contact with water vapor at temperatures between 800 and 1100 ° C.
  • a proportion of the metal oxide which corresponds to the chlorine content of the waste converted into volatile metal chloride.
  • a portion of the released carbon is converted into carbon monoxide and the non-metal oxide reactive portion of the carbon is converted to water gas (CO + H 2 ) by a stoichiometric amount of steam.
  • the object of the present invention is to develop a method which allows various halogenated and non-halogenated waste to be disposed of in an environmentally sound manner.
  • This object is achieved by a method for disposing of carbonaceous, hydrogen-containing, halogenated and carbonaceous, hydrogen-containing, non-halogenated waste, in which the waste with TiO 2 , SiO 2 , CaO and / or Fe 2 O 3 or a mixture thereof to the exclusion of Oxygen at temperatures of 800 ° C to 1100 ° C are reacted and generated as a gaseous product consisting of carbon monoxide, methane and hydrogen synthesis gas from which any volatile metal halide compounds formed by cooling are deposited.
  • the method described here is used for environmentally neutral recycling of halogenated and non-halogenated waste.
  • the volume of waste used is largely reduced, so that the least possible residues remain and the largest possible amount of metals / metal compounds is obtained.
  • the aim is to achieve the most positive energy balance possible.
  • carbon dioxide is added as fluidizing gas.
  • the reactor can also be charged with carbon in the form of graphite and / or carbon.
  • metal oxide-containing wastes such as, for example, silicon-containing residues from the metalworking industry, filter dusts, fly ash, fly sands, dump heaps, galvanic sludges, slags, shale residues, etc.
  • Simple quartz sand which consists to about 98% of silicon dioxide (SiO 2 ), is the simplest possible material, which can be used for the implementation.
  • All the above-mentioned materials are characterized by the fact that they contain a relatively high content of halogenatable metal oxides (CaO, SiO 2 , TiO 2 , Fe 2 O 3, etc.).
  • solvents such as carbon tetrachloride, chloroform, methylene chloride, tetra- and trichlorethylene, tetrachloroethane, refrigerants or refrigerants, PCBs, pesticides, fungicides and herbicides, halogenated plastics such as e.g. Insert PVC.
  • a proportion of the metal oxide corresponding to the chlorine content of the waste materials is converted by the above-mentioned process into metal chloride.
  • metal chloride There arise ecologically and economically valuable metal chlorides with silicon and titanium tetrachloride (SiCl 4 , TiCl 4 ) are particularly preferred products.
  • Waste oils, lubricants, greases, paints, paints, tars, waxes, plastics, coolants and solvents, brake fluid or similar non-halogenated substances and materials must be disposed of.
  • thermodynamically preferably formed under these process parameters
  • Reaction or reaction products are primarily gaseous hydrogen (H 2 ) in addition to lower percentages of methane (CH 4 ).
  • the reactor can be brought to the required operating temperatures either by using electrical heating elements (eg heating half-shells) or by using induction heating.
  • the temperatures required for the reaction are in the range of 800 ° C to 1100 ° C.
  • the reaction itself takes place under exclusion of oxygen.
  • the fluidizing gas used is carbon dioxide (CO 2 ).
  • the halogenated compounds are decomposed by the high temperatures into their simplest constituents; in the case of chlorinated hydrocarbons, hydrogen chloride, hydrogen, alkanes and chlorine gas are formed.
  • the chlorine gas and the hydrogen chloride serve as chlorinating agents for the metal oxide-containing products or waste. Products of this chlorination reaction are the thermodynamically preferred metal chlorides.
  • the carbon dioxide (CO 2 ) used as fluidizing gas is completely converted to carbon monoxide (CO) by reaction with the carbon of the decomposed hydrocarbons and by an additional coal or graphite feed in the top of the reactor.
  • All generated halogenated metal compounds are initially in gaseous form. Depending on the starting material, by cooling to room temperature solid, i. crystalline metal compounds are obtained, or by condensation at low temperatures liquid metal compounds.
  • the purity of these compounds is 96% and may be e.g. by a fractional distillation, or rectification called, still be improved.
  • Fig. 1 a diagram of the plant for the disposal of halogenated waste.
  • FIG. 1 1 shows a feed line 1 for the halogenated waste, a feed line 2 for metal oxide products, and a line 3 for discharging unreacted materials 3.
  • a feed 4 blows a fluidizing gas (CO 2 ) into the fluidized bed reactor 5.
  • the reactor 5 is heated by means of a reactor heater 6 to a temperature between 800 ° C and 1100 ° C, so that it comes to the reaction between the halogenated waste and the metal oxide-containing materials in the reactor.
  • the products formed are separated in a solids separator 7 and the solid metal chlorides formed, esp. FeCl 3 are discharged via a line 8.
  • the remaining gases are purified by an activated carbon filter 9 and then compressed by a blower 10.
  • the gases are then cooled in a cooling tank 12, which has a coolant inlet 11 and a coolant discharge 13, so that the remaining metal chlorides are eliminated.
  • These are mainly SiCl 4 .
  • the gases are then fed to a condenser 15 and subjected to alkaline scrubbing in a gas scrubber column 16.
  • the column 16 has a circulating pump 17 for the washing liquid.
  • the remaining synthesis gas, a mixture of CO and H 2 is discharged via the line 18 in the upper part of the gas washing column 16.
  • the various feedstocks such as u.a. Oils, fats, PCBs, CFCs, solvents or the like are fed via a metering device, e.g. an eccentric screw pump, conveyed into the reaction zone. There, a first thermal cleavage of the feedstocks into short-chain hydrocarbons occurs abruptly. By the height of the reaction zone, the residence time of the feedstocks and the resulting fission products is determined.
  • halogenated feedstocks in particular chlorinated materials
  • a reaction between the calcium oxide and the halogen atoms of the feedstocks occurs.
  • reaction product is formed essentially calcium chloride (CaCl 2 ), which remains in the reactor as slag or melt.
  • reaction equation 1 takes into account all essential products which are formed during the disposal or utilization of a halogenated hydrocarbon. The individual products were thermodynamically calculated and experimentally proven.
  • carbon in the form of fine soot particles is also discharged from the reactor.
  • gravity separators such as e.g. a high performance cyclone.
  • the cleaned gases can still be passed through activated carbon filters. Should foreign components still be contained in the process gas, they can be removed either by specific condensation or by gas scrubbing.

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Processing Of Solid Wastes (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Silicon Compounds (AREA)

Abstract

Process for disposing halogenated and non-halogenated waste comprises reacting the waste with products containing metal oxide with exclusion of oxygen at 800-1100 degrees C.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Entsorgung von halogenierten und nicht halogenierten Abfallstoffen.The present invention relates to a method for disposing of halogenated and non-halogenated waste materials.

Substituierte, insbesondere halogenierte Kohlenwasserstoffe, wie sie beispielsweise im Tetrachlorkohlenstoff, Chloroform, Methylenchlorid, Tetra- und Trichloräthylen, Tetrachloräthan, PCB etc. aber auch im PVC oder Polyvinylidenchlorid vorliegen, sind nach Gebrauch ein mehr oder weniger problematischer Gift- oder Sondermüll, den es zu Entsorgen gilt.Substituted, in particular halogenated hydrocarbons, such as those present in carbon tetrachloride, chloroform, methylene chloride, tetra- and trichlorethylene, tetrachloroethane, PCB, etc. but also in PVC or polyvinylidene chloride, are after use a more or less problematic toxic or hazardous waste it is too Dispose applies.

Stark toxisch auf die Umwelt und den Menschen wirkende Stoffe, wie halogenierte Verbindungen, insbesondere polyhalogenierte Stoffe wie z.B. PCBs oder TCDD/TCDF (Dioxine/Furane) lassen sich nicht ohne weiteres wiederverwerten und müssen umweltgerecht entsorgt werden.Highly toxic to the environment and humans acting substances such as halogenated compounds, in particular polyhalogenated substances such. PCBs or TCDD / TCDF (dioxins / furans) are not readily recyclable and must be disposed of in an environmentally sound manner.

Die Entsorgung erfolgt entweder durch Deponierung oder durch Verbrennung auf hoher See oder auch auf dem Lande in Hochtemperaturöfen mit einem Überschuß an Luft.The disposal takes place either by landfill or by burning on the high seas or in the countryside in high-temperature furnaces with an excess of air.

Der Energiebedarf ist in vielen Fällen nicht unerheblich, da nicht nur die zu beseitigenden Stoffe verdampft und auf die erforderliche Zersetzungstemperatur erhitzt, sondern auch enorme Luftmengen aufgeheizt werden müssen. Dabei wird entweder, wie bei der Verbrennung auf hoher See, eine Verschmutzung der Atmosphäre und die Gefahr sauren Regens in Kauf genommen oder es werden äußertest kostspielige Anlagen zur Luftreinhaltung erforderlich.The energy requirement is not insignificant in many cases, since not only the substances to be removed evaporated and heated to the required decomposition temperature, but also enormous amounts of air must be heated. Here, either as in the case of combustion on the high seas, a pollution of the atmosphere and the risk of acid rain in purchasing accepted or extremely expensive air pollution control systems are required.

Aus der DE-A-33 13 889 sind ein Verfahren oder eine Vorrichtung zur Beseitigung von Gift und Sondermüll bekannt, bei welchem die giftigen Abfallstoffe mit einem elektrisch leitenden Stoff, insbesondere in Gestalt von Eisenpulver und/oder Koks vermischt und in einem Induktionsofen auf die Zersetzungstemperatur des zu beseitigenden Gift- und/oder Sondermülls gebracht wird.From the DE-A-33 13 889 are known a method or apparatus for the removal of poison and hazardous waste, in which the toxic waste with an electrically conductive material, in particular in the form of iron powder and / or coke mixed and in an induction furnace to the decomposition temperature of the poison and / or Special waste is brought.

Die US-A-4,435,379 beschreibt ein Verfahren zur Zersetzung von chlorierten Kohlenwasserstoffen mit Metalloxyden mit dem Ziel, alle Kohlenstoffatome in Kohlenoxyd zu überführen. Dabei kommt es darauf an, elementares Chlor zur Umwandlung von Wasserstoffgruppen in HCI bereitzustellen. Dabei muß das gesamte Verhältnis von Chlor zu Wasserstoffgruppen mindestens 1 : 1 betragen, um Metallchlorid herstellen zu können.The US-A-4,435,379 describes a process for the decomposition of chlorinated hydrocarbons with metal oxides with the aim to convert all carbon atoms into carbon monoxide. It is important to provide elemental chlorine for the conversion of hydrogen groups in HCI. The total ratio of chlorine to hydrogen groups must be at least 1: 1 in order to produce metal chloride can.

Die US-A-4,587,116 beschreibt ein ähnliches Verfahren, bei dem auch stickstoffhaltige Abfallstoffe entsorgt werden können. Die Erhitzung erfolgt ebenfalls von außen und nicht von innen heraus.The US-A-4,587,116 describes a similar process in which nitrogen-containing waste can be disposed of. The heating also takes place from the outside and not from the inside out.

Die US-A- 4 451 907 offenbart ein Verfahren zur Beseitigung von chlorierten organischen Verbindungen. Zunächst werden die chlorierten organischen Verbindungen in einem Salzschmelzenofen verdampft, und dann zu einem Reaktor geführt. In dem Reaktor werden die chlorierten, organischen Verbindungen auf 800 bis 1200°C erhitzt, dies in Anwesenheit von Aluminiumoxid und reaktivem Kohlenstoff, und folglich zersetzt. Stickstoff wird als Trägergas verwendet, um die verdampften chlorierten organischen Verbindungen vom Salzschmelzenofen zum Reaktor zu führen.The US-A-4 451 907 discloses a method for eliminating chlorinated organic compounds. First, the chlorinated organic compounds are vaporized in a molten salt furnace, and then fed to a reactor. In the reactor, the chlorinated organic compounds are heated to 800 to 1200 ° C in the presence of alumina and reactive carbon, and thus decomposed. Nitrogen is used as a carrier gas to pass the vaporized chlorinated organic compounds from the molten salt furnace to the reactor.

Die EP 0 306 540 beschreibt ein Verfahren zur Energiegewinnung aus substituierten Kohlenwasserstoffen, wie sie z.B. als CCl4, CHCl3, C2H2Cl4, PCB,The EP 0 306 540 describes a process for the production of energy from substituted hydrocarbons, such as, for example, as CCl 4 , CHCl 3 , C 2 H 2 Cl 4 , PCB,

PVC, Polyvinylidenchlorid etc. in reiner oder gebundener Form vorliegen. Der Abfallstoff wird dabei in einem induktiv beheizbaren Reaktor in Anwesenheit eines schwer verhüttbaren Metalloxides und eines elektrisch leitfähigen Materials, beispielsweise Elektrodenkoks oder Elektrographit sowie im Kontakt mit Wasserdampf bei Temperaturen zwischen 800 und 1.100°C thermisch zersetzt. Dabei wird ein Anteil des Metalloxids das dem Chlorgehalt der Abfallstoffe entspricht, in flüchtiges Metallchlorid umgesetzt. Ein Anteil des freiwerdenden Kohlenstoffs wird in Kohlenmonoxid umgesetzt und der nicht an dem Metalloxid reagierende Anteil des Kohlenstoffs wird mit Hilfe einer stöchiometrischen Menge Wasserdampf zu Wassergas (CO + H2) umgesetzt.PVC, polyvinylidene chloride etc. in pure or bound form. The waste material is thermally decomposed in an inductively heatable reactor in the presence of a heavily verhüttbaren metal oxide and an electrically conductive material, such as electrode coke or electrographite and in contact with water vapor at temperatures between 800 and 1100 ° C. In this case, a proportion of the metal oxide which corresponds to the chlorine content of the waste, converted into volatile metal chloride. A portion of the released carbon is converted into carbon monoxide and the non-metal oxide reactive portion of the carbon is converted to water gas (CO + H 2 ) by a stoichiometric amount of steam.

Aufgabe der vorliegenden Erfindung ist es, ein Verfahren zu entwickeln, das es erlaubt, verschiedene halogenierte und nicht halogenierte Abfallstoffe umweltgerecht zu entsorgen.The object of the present invention is to develop a method which allows various halogenated and non-halogenated waste to be disposed of in an environmentally sound manner.

Diese Aufgabe wird erfindungsgemäß durch ein Verfahren zur Entsorgung kohlenstoffhaltiger, wasserstoffhaltiger, halogenierter und kohlenstoffhaltiger, wasserstoffhaltiger, nicht halogenierter Abfallstoffe gelöst, bei dem die Abfallstoffe mit TiO2, SiO2, CaO und/oder Fe2O3 oder eine Mischung daraus unter Ausschluß von Sauerstoff bei Temperaturen von 800°C bis 1100 °C umgesetzt werden und als gasförmiges Produkt ein aus Kohlenmonoxid, Methan und Wasserstoff bestehendes Synthesegas erzeugt wird aus welchem eventuell gebildete flüchtige Metallhalogenverbindungen durch Kühlung abgeschieden werden..This object is achieved by a method for disposing of carbonaceous, hydrogen-containing, halogenated and carbonaceous, hydrogen-containing, non-halogenated waste, in which the waste with TiO 2 , SiO 2 , CaO and / or Fe 2 O 3 or a mixture thereof to the exclusion of Oxygen at temperatures of 800 ° C to 1100 ° C are reacted and generated as a gaseous product consisting of carbon monoxide, methane and hydrogen synthesis gas from which any volatile metal halide compounds formed by cooling are deposited.

Das hier beschriebene Verfahren dient zur umweltneutralen Wiederverwertung von halogenierten und nicht halogenierten Abfallstoffen.The method described here is used for environmentally neutral recycling of halogenated and non-halogenated waste.

Das Volumen der eingesetzten Abfälle wird weitgehend verringert, so daß möglichst wenig Rückstände zurückbleiben und eine möglichst große Menge von Metallen/Metallverbindungen gewonnen wird. Bei der Umsetzung wird eine möglichst positive Energiebilanz angestrebt.The volume of waste used is largely reduced, so that the least possible residues remain and the largest possible amount of metals / metal compounds is obtained. The aim is to achieve the most positive energy balance possible.

In einer vorteilhaften Ausführung des Verfahrens wird Kohlendioxid als Fluidisierungsgas zugesetzt.In an advantageous embodiment of the method, carbon dioxide is added as fluidizing gas.

Weiterhin kann der Reaktor auch mit Kohlenstoff in Form von Graphit und/oder Kohle beaufschlagt werden.Furthermore, the reactor can also be charged with carbon in the form of graphite and / or carbon.

Als Reaktionspartner können auch verschiedene metalloxidhaltige Abfallstoffe, wie z.B. siliziumhaltige Rückstände aus der metallverarbeitenden Industrie, Filterstäube, Flugaschen, Flugsande, Haldenberge, Galvanikschlämme, Schlacken, Schieferreste etc. dienen. Einfacher Quarzsand, der zu etwa 98% aus Siliziumdioxid (SiO2) besteht, ist das denkbar einfachste Material, was zur Umsetzung eingesetzt werden kann.Other suitable metal oxide-containing wastes, such as, for example, silicon-containing residues from the metalworking industry, filter dusts, fly ash, fly sands, dump heaps, galvanic sludges, slags, shale residues, etc., can also serve as reactants. Simple quartz sand, which consists to about 98% of silicon dioxide (SiO 2 ), is the simplest possible material, which can be used for the implementation.

Alle obengenannten Materialien zeichnen sich dadurch aus, daß sie einen relativ hohen Gehalt an halogenierbaren Metalloxiden (CaO, SiO2, TiO2, Fe2O3 etc.) enthalten.All the above-mentioned materials are characterized by the fact that they contain a relatively high content of halogenatable metal oxides (CaO, SiO 2 , TiO 2 , Fe 2 O 3, etc.).

Daraus ergibt sich der Vorteil, daß für bisher mit wirtschaftlichen Mitteln nicht verhüttbare Metalloxide enthaltende Stoffe nunmehr eine nutzbringende Anwendung finden.This results in the advantage that now find a useful application for substances containing hitherto non-smokable metal oxides containing substances.

Man kann als halogenierte Abfallstoffe Lösungsmittel wie z.B.: Tetrachlorkohlenstoff, Chloroform, Methylenchlorid, Tetra- und Trichloräthylen, Tetrachloräthan, Kühl- oder Kältemittel, PCB, Pestizide, Fungizide und Herbizide, halogenierte Kunststoffe wie z.B. PVC einsetzen.As halogenated waste, solvents such as carbon tetrachloride, chloroform, methylene chloride, tetra- and trichlorethylene, tetrachloroethane, refrigerants or refrigerants, PCBs, pesticides, fungicides and herbicides, halogenated plastics such as e.g. Insert PVC.

Ein Anteil des Metalloxids das dem Chlorgehalt der Abfallstoffe entspricht, wird durch das o.g. Verfahren in Metallchlorid umgesetzt. Es entstehen ökologisch und ökonomisch wertvolle Metallchloride wobei Silizium- und Titantetrachlorid (SiCl4, TiCl4) besonders bevorzugte Produkte darstellen.A proportion of the metal oxide corresponding to the chlorine content of the waste materials is converted by the above-mentioned process into metal chloride. There arise ecologically and economically valuable metal chlorides with silicon and titanium tetrachloride (SiCl 4 , TiCl 4 ) are particularly preferred products.

Es können auch u.a. Altöle, Schmierstoffe, Fette, Lacke, Farben, Teere, Wachse, Kunststoffe, Kühl- und Lösungsmittel, Bremsflüssigkeit oder ähnliche nicht halogenierte Stoffe und Materialien entsorgt werden.It can also u.a. Waste oils, lubricants, greases, paints, paints, tars, waxes, plastics, coolants and solvents, brake fluid or similar non-halogenated substances and materials must be disposed of.

Die unter diesen Prozeßparametern thermodynamisch bevorzugt gebildetenThe thermodynamically preferably formed under these process parameters

Reaktions- bzw. Umsetzungsprodukte sind primär gasförmig anfallender Wasserstoff (H2) neben prozentual geringeren Voluminen an Methan (CH4).Reaction or reaction products are primarily gaseous hydrogen (H 2 ) in addition to lower percentages of methane (CH 4 ).

Die Bildung umweltgefährdender bzw. umweltbelastender, gasförmiger Stoffe wie Kohlenmonoxid (CO), sowie das als sog. Treibhausgas bekannte Kohlendioxid (CO2) ist, bei den bevorzugten Reaktionsbedingungen, vernachlässigbar gering. Erst bei Temperaturen oberhalb der 1100°C kann durch chemische Zersetzungsprozesse CO bzw. CO2 gebildet werden.
Die Umsetzung erfolgt in einem Wirbelbettreaktor. Dieser kann entweder aus speziellen Keramiken, Siliziumcarbid (SiC) oder spezial legierten Stählen gebaut sein.The formation of environmentally hazardous or polluting, gaseous substances such as carbon monoxide (CO), and the so-called greenhouse gas known carbon dioxide (CO 2 ) is, under the preferred reaction conditions, negligible. Only at temperatures above 1100 ° C can CO or CO 2 be formed by chemical decomposition processes.
The reaction takes place in a fluidized bed reactor. This can either be made of special ceramics, silicon carbide (SiC) or special alloyed steels.

Der Reaktor kann entweder durch Verwendung von elektrischen Heizelementen (z.B. Heizhalbschalen) oder durch Verwendung einer Induktionsheizung auf die notwendigen Betriebstemperaturen gebracht werden. Die zur Umsetzung notwendigen Temperaturen liegen im Bereich von 800°C bis 1100°C. Die Reaktion selbst erfolgt unter Sauerstoffabschluß. Als Fluidisierungsgas wird Kohlendioxid (CO2) eingesetzt.The reactor can be brought to the required operating temperatures either by using electrical heating elements (eg heating half-shells) or by using induction heating. The temperatures required for the reaction are in the range of 800 ° C to 1100 ° C. The reaction itself takes place under exclusion of oxygen. The fluidizing gas used is carbon dioxide (CO 2 ).

Die halogenierten Verbindungen werden durch die hohen Temperaturen in ihre einfachsten Bestandteile zerlegt, im Falle von chlorierte Kohlenwasserstoffe werden Chlorwasserstoff, Wasserstoff, Alkane und Chlorgas gebildet. Das Chlorgas und der Chlorwasserstoff dienen als Chlorierungsmittel für die metalloxidhaltigen Produkte bzw. Abfälle. Produkte dieser Chlorierungsreaktion sind die thermodynamisch bevorzugten Metallchloride.The halogenated compounds are decomposed by the high temperatures into their simplest constituents; in the case of chlorinated hydrocarbons, hydrogen chloride, hydrogen, alkanes and chlorine gas are formed. The chlorine gas and the hydrogen chloride serve as chlorinating agents for the metal oxide-containing products or waste. Products of this chlorination reaction are the thermodynamically preferred metal chlorides.

Neben den Chloriden wird Wasserstoff und Kohlenmonoxid gebildet, welches als Synthesegas entweder zu Gewinnung von elektrischer Energie oder für andere chemische Synthesen, so z.B. die Methanol-Synthese, eingesetzt werden kann.

        2 H2 + CO ⊗ CH3OH

In addition to the chlorides, hydrogen and carbon monoxide are formed, which can be used as synthesis gas either for the production of electrical energy or for other chemical syntheses, such as methanol synthesis.

2 H 2 + CO ⊗ CH 3 OH

Reaktionsgleichung 1Reaction equation 1

Das als Fluidisierungsgas eingesetzte Kohlendioxid (CO2) wird durch Reaktion mit dem Kohlenstoff der zersetzten Kohlenwasserstoffe und durch eine zusätzliche Kohle- oder Graphitschüttung im Kopf des Reaktors vollständig zu Kohlenmonoxid (CO) umgesetzt.The carbon dioxide (CO 2 ) used as fluidizing gas is completely converted to carbon monoxide (CO) by reaction with the carbon of the decomposed hydrocarbons and by an additional coal or graphite feed in the top of the reactor.

Man spricht in diesem Zusammenhang von der sog. BOUDOUARD-Reaktion:

        CO2 + C 2 CO

One speaks in this context of the so-called BOUDOUARD reaction:

CO 2 + C 2 CO

Reaktionsgleichung 2Reaction equation 2

Die Bildung umweltschädigender Verbindungen wie Dioxine, Furane oder z.B. Phosgen (COCl2) ist bei den vorherrschenden Reaktionsbedingungen extrem unwahrscheinlich.The formation of environmentally harmful compounds such as dioxins, furans or, for example, phosgene (COCl 2 ) is extremely unlikely under the prevailing reaction conditions.

Alle erzeugten halogenierten Metallverbindungen liegen zunächst gasförmig vor. Je nach Ausgangsmaterial können durch Kühlung auf Raumtemperatur feste, d.h. kristalline Metallverbindungen gewonnen werden, oder aber durch Kondensation bei tiefen Temperaturen flüssige Metallverbindungen.All generated halogenated metal compounds are initially in gaseous form. Depending on the starting material, by cooling to room temperature solid, i. crystalline metal compounds are obtained, or by condensation at low temperatures liquid metal compounds.

Der Reinheitsgrad dieser Verbindungen liegt bei 96% und kann z.B. durch eine fraktionierende Destillation, oder Rektifikation genannt, noch verbessert werden.The purity of these compounds is 96% and may be e.g. by a fractional distillation, or rectification called, still be improved.

Im folgenden werden nun verschiedene Ausgestaltungen der Erfindung anhand der beiliegenden Figuren beschrieben. Es zeigt:In the following, various embodiments of the invention will now be described with reference to the accompanying drawings. It shows:

Fig. 1: ein Schema der Anlage zur Entsorgung von halogenierten Abfallstoffen. Fig. 1 : a diagram of the plant for the disposal of halogenated waste.

Auf dem schematischen Fließbild des Verfahrens wie in Fig. 1 abgebildet, sieht man eine Zuleitung 1 für die halogenierten Abfallstoffe, eine Zuleitung 2 für metalloxidhaltige Produkte, sowie eine Leitung 3 zum Austragen von nicht umgesetzten Materialien 3. Über eine Zufuhr 4 wird ein Fluidisierungsgas (CO2) in den Wirbelbettreaktor 5 eingeblasen.On the schematic flow diagram of the method as in Fig. 1 1 shows a feed line 1 for the halogenated waste, a feed line 2 for metal oxide products, and a line 3 for discharging unreacted materials 3. A feed 4 blows a fluidizing gas (CO 2 ) into the fluidized bed reactor 5.

Der Reaktor 5 wird mittels einer Reaktorheizung 6 auf eine Temperatur zwischen 800°C und 1100°C aufgewärmt, so daß es zur Reaktion zwischen den halogenierten Abfällen und den metalloxidhaltigen Stoffen im Reaktor kommt. Die gebildeten Produkte werden in einem Feststoffabscheider 7 getrennt und die gebildeten festen Metallchloride, insbes. FeCl3, werden über eine Leitung 8 ausgetragen. Die restlichen Gase werden durch einen Aktivkohlefilter 9 gereinigt und anschließend durch ein Gebläse 10 verdichtet. Die Gase werden dann in einem Kühlbehälter 12, der einen Kühlmitteleintrag 11 und einen Kühlmittelaustrag 13 aufweist, abgekühlt, so daß die verbliebenen Metallchloride ausgeschieden werden . Es handelt sich hier hauptsächlich um SiCl4.The reactor 5 is heated by means of a reactor heater 6 to a temperature between 800 ° C and 1100 ° C, so that it comes to the reaction between the halogenated waste and the metal oxide-containing materials in the reactor. The products formed are separated in a solids separator 7 and the solid metal chlorides formed, esp. FeCl 3 are discharged via a line 8. The remaining gases are purified by an activated carbon filter 9 and then compressed by a blower 10. The gases are then cooled in a cooling tank 12, which has a coolant inlet 11 and a coolant discharge 13, so that the remaining metal chlorides are eliminated. These are mainly SiCl 4 .

Die Gase werden anschließend einem Kondensator 15 zugeführt und in einer Gaswaschkolonne 16 einer alkalischen Gaswäsche unterzogen. Die Kolonne 16 verfügt über eine Umwälzpumpe 17 für die Waschflüssigkeit. Das verbleibende Synthesegas, ein Gemisch aus CO und H2, wird über die Leitung 18 im oberen Teil der Gaswaschkolonne 16 ausgetragen.The gases are then fed to a condenser 15 and subjected to alkaline scrubbing in a gas scrubber column 16. The column 16 has a circulating pump 17 for the washing liquid. The remaining synthesis gas, a mixture of CO and H 2 , is discharged via the line 18 in the upper part of the gas washing column 16.

Anwendungsbeispiel 1 : Entsorgung von Kohlenwasserstoff- (KW) oder halogenkohlenwasserstoffhaltigen (HKW) Abfällen in Gegenwart von CalciumoxidUse Example 1: Disposal of hydrocarbon (HC) or halogenated hydrocarbon (HKW) wastes in the presence of calcium oxide

Die verschiedenen Einsatzmaterialien, wie u.a. Öle, Fette, PCB, FCKW, Lösungsmittel oder dgl., werden über eine Dosiereinrichtung, z.B. eine Exzenterschneckenpumpe, in die Reaktionszone gefördert. Dort erfolgt schlagartig eine erste thermische Spaltung der Einsatzmaterialienin kurzkettige Kohlenwasserstoffe. Durch die Höhe der Reaktionszone wird die Verweilzeit der Einsatzmaterialien bzw. die der entstandenen Spaltprodukte bestimmt.The various feedstocks, such as u.a. Oils, fats, PCBs, CFCs, solvents or the like are fed via a metering device, e.g. an eccentric screw pump, conveyed into the reaction zone. There, a first thermal cleavage of the feedstocks into short-chain hydrocarbons occurs abruptly. By the height of the reaction zone, the residence time of the feedstocks and the resulting fission products is determined.

In der Regel erfolgt eine nahezu quantitative Aufspaltung zu im wesentlichen Wasserstoff und Methan, wobei das Volumenverhältnis Wasserstoff zu Methan deutlich auf der Seite des Wasserstoffs liegt. Da der Schmelzpunkt von Calciumoxid (CaO) bei rund 2500°C liegt, ist mit keinen größeren Mengen synthetisierter Calciumverbindungen zu rechnen.In general, a nearly quantitative decomposition to essentially hydrogen and methane, wherein the volume ratio of hydrogen to methane is clearly on the side of the hydrogen. Since the melting point of calcium oxide (CaO) is around 2500 ° C, no large amounts of synthesized calcium compounds can be expected.

Werden hingegen halogenierte Einsatzmaterialien insbes. chlorierte Materialien zur Reaktion gebracht, dann tritt eine Reaktion zwischen dem Calciumoxid und den Halogenatomen der Einsatzmaterialien ein.If, on the other hand, halogenated feedstocks, in particular chlorinated materials, are reacted, then a reaction between the calcium oxide and the halogen atoms of the feedstocks occurs.

Als Reaktionsprodukt wird im wesentlichen Calciumchlorid (CaCl2) gebildet, welches im Reaktor als Schlacke bzw. Schmelze verbleibt. Die folgende Reaktionsgleichung (Reaktionsgleichung 1) berücksichtigt alle wesentlichen Produkte, die bei der Entsorgung bzw. Verwertung eines halogenierten Kohlenwasserstoffs gebildet werden. Die einzelnen Produkte wurden thermodynamisch berechnet und experimentell belegt.

Figure imgb0001
The reaction product is formed essentially calcium chloride (CaCl 2 ), which remains in the reactor as slag or melt. The following reaction equation (reaction equation 1) takes into account all essential products which are formed during the disposal or utilization of a halogenated hydrocarbon. The individual products were thermodynamically calculated and experimentally proven.
Figure imgb0001

Reaktionsgleichungreaction equation

Neben dieser Reaktion wird auch noch Kohlenstoff in Form von feinen Rußpartikeln aus dem Reaktor ausgetragen.In addition to this reaction, carbon in the form of fine soot particles is also discharged from the reactor.

Die Abtrennung von den übrigen gasförmigen Bestandteilen Wasserstoff und Methan, bzw. Wasserstoff und Kohlenmonoxid (CO), erfolgt durch Schwerkraftseparatoren, wie z.B. ein Hochleistungszyklon.The separation from the other gaseous constituents hydrogen and methane, or hydrogen and carbon monoxide (CO), takes place by means of gravity separators, such as e.g. a high performance cyclone.

Die so gesäuberten Gase können sicherheitshalber noch durch Aktivkohlefilter geleitet werden. Sollten immer noch Fremdbestandteile im Prozeßgas enthalten sein, so können diese entweder durch gezielte Kondensation oder durch eine Gaswäsche entfernt werden.As a precaution, the cleaned gases can still be passed through activated carbon filters. Should foreign components still be contained in the process gas, they can be removed either by specific condensation or by gas scrubbing.

Schlußendlich bleibt i.d.R. nur ein aus Kohlenmonoxid, Methan und Wasserstoff bestehendes Synthesegas übrig, welches für vielseitige techn. Anwendungen, so z.B. der Energiegewinnung oder der Nutzung für chemische Synthesen (Methanolsynthese), eingesetzt werden kann.Finally, i.d.R. only a synonymous of carbon monoxide, methane and hydrogen synthesis gas left, which for versatile techn. Applications, e.g. Energy production or use for chemical synthesis (methanol synthesis), can be used.

Claims (7)

  1. A process for disposing of halogenated and non-halogenated hydrogen-containing and carbon-containing waste materials, characterized in that the waste materials are reacted with TiO2, SiO2, CaO and/or Fe2O3 or a mixture thereof with exclusion of oxygen at temperatures from 800°C to 1,100°C and a synthesis gas consisting of carbon monoxide, methane and hydrogen is produced as a gaseous product, from which are separated optionally formed volatile metal halogen compounds by cooling
  2. The process according to claim 1, characterized in that carbon dioxide is added during the process
  3. The process according to any of the preceding claims, characterized in that carbon is added during the process
  4. The process according to claim 3, characterized in that graphite and/or coal is used as carbon
  5. The process according to any of the preceding claims, characterized in that solvents such as for example carbon tetrachloride, chloroform, methylene chloride, tetra- and tri-chloroethylene, tetrachloro-ethane, coolants or refrigerants, PCBs, pesticides, fungicides and herbicides, halogenated plastics such as PVC, are used as halogenated waste materials
  6. The process according to any of the preceding claims, characterized in that a portion of the metal oxide which corresponds to the chlorine content of the waste materials, is converted into a metal chloride
  7. The process according to any of claims 1 to 6, characterized in that spent oils, lubricants, fats, paints, dyes, tars, waxes, plastics, coolants and solvents, brake fluid or similar non-halogenated substances or materials are used as non-halogenated waste materials.
EP02004190A 1997-07-23 1998-07-20 Method for elimination of halogenated and non halogenated waste Expired - Lifetime EP1219324B1 (en)

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LU90109A LU90109B1 (en) 1997-07-23 1997-07-23 Process for disposing (non)-halogenated waste e.g. carbon tetra:chloride - comprises reacting waste with products containing metal oxide with exclusion of oxygen
LU90109 1997-07-23
LU90191A LU90191A7 (en) 1997-07-23 1997-12-24 Process for the disposal of halogenated and non-halogenated waste materials
LU90191 1997-12-24
EP98940244A EP0999878B1 (en) 1997-07-23 1998-07-20 Method for eliminating halogenated and non halogenated waste

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CN104147745B (en) * 2014-08-22 2017-02-15 上海化工研究院 Method for removing volatile halocarbons in environment through chemical conversion
RU2667566C1 (en) * 2017-09-04 2018-09-21 Федеральное государственное бюджетное образовательное учреждение высшего образования "Ярославский государственный технический университет" ФГБОУВО "ЯГТУ" Method of preparation of galvanic sludge for its utilization
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US4541907A (en) * 1984-04-16 1985-09-17 Aluminum Company Of America Process for decomposing chlorinated hydrocarbon compounds
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