EP1219324A2 - Method for elimination of halogenated and non halogenated waste - Google Patents
Method for elimination of halogenated and non halogenated waste Download PDFInfo
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- EP1219324A2 EP1219324A2 EP02004190A EP02004190A EP1219324A2 EP 1219324 A2 EP1219324 A2 EP 1219324A2 EP 02004190 A EP02004190 A EP 02004190A EP 02004190 A EP02004190 A EP 02004190A EP 1219324 A2 EP1219324 A2 EP 1219324A2
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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
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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
- A62D3/34—Dehalogenation using reactive chemical agents able to degrade
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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
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/04—Pesticides, e.g. insecticides, herbicides, fungicides or nematocides
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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
- 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 the disposal of halogenated and non-halogenated waste.
- halogenated hydrocarbons such as for example in carbon tetrachloride, chloroform, methylene chloride, tetra- and Trichlorethylene, tetrachloroethane, PCB etc. but also in PVC or Polyvinylidene chloride are more or less after use problematic toxic or special waste that needs to be disposed of.
- halogenated substances Compounds, especially polyhalogenated substances such as e.g. PCBs or TCDD / TCDF (dioxins / furans) cannot be easily recycled and must be disposed of in an environmentally friendly manner.
- DE-A-33 13 889 describes a method or an apparatus for Removal of poison and hazardous waste known, in which the toxic Waste materials with an electrically conductive substance, in particular in the form of Iron powder and / or coke mixed and placed in an induction furnace Decomposition temperature of the toxic and / or special waste to be disposed of brought.
- US-A-4,435,379 describes a process for the decomposition of chlorinated Hydrocarbons with metal oxides with the aim of all carbon atoms in To transfer carbon oxide. It is important to use elemental chlorine To provide conversion of hydrogen groups to HCI. The must total ratio of chlorine to hydrogen groups is at least 1: 1, to be able to produce metal chloride.
- US-A-4,587,116 describes a similar process in which nitrogenous waste can be disposed of. The heating takes place also from the outside and not from the inside.
- US-A-4 451 907 discloses a process for the removal of chlorinated organic compounds. First, the chlorinated organic Compounds evaporated in a molten salt furnace, and then to one Reactor led. The chlorinated, organic Compounds heated to 800 to 1200 ° C, in the presence of aluminum oxide and reactive carbon, and consequently decomposes. Nitrogen is used as a carrier gas used to evaporate the chlorinated organic compounds Lead the molten salt furnace to the reactor.
- EP 0 306 540 describes a process for the production of energy from substituted hydrocarbons, such as those used as CCl 4 , CHCl 3 , C 2 H 2 Cl 4 , PCB,
- PVC, polyvinylidene chloride, etc. are present in pure or bound form.
- the waste material is thermally decomposed in an inductively heatable reactor in the presence of a metal oxide which is difficult to smelt and an electrically conductive material, for example electrode coke or electrographite, and in contact with water vapor at temperatures between 800 and 1,100 ° C.
- a proportion of the metal oxide that corresponds to the chlorine content of the waste materials is converted into volatile metal chloride.
- a portion of the released carbon is converted into carbon monoxide and the portion of the carbon that does not react with the metal oxide is converted into water gas (CO + H 2 ) with the aid of a stoichiometric amount of water vapor.
- the object of the present invention is to develop a method that allowed various halogenated and non-halogenated waste materials to dispose of in an environmentally friendly manner.
- This object is achieved according to the invention by a process for the disposal of halogenated non-halogenated waste materials, in which the halogenated and non-halogenated waste materials are mixed with TiO 2 , SiO 2 , CaO and / or Fe 2 O 3 or a mixture thereof with the exclusion of oxygen at temperatures of 800 ° C to 1100 ° C can be implemented.
- the procedure described here is for environmentally neutral recycling of halogenated and non-halogenated waste materials.
- carbon dioxide is used as Fluidizing gas added.
- the reactor can also use carbon in the form of graphite and / or Coal are charged.
- Various metal oxide-containing waste materials such as silicon-containing residues from the metalworking industry, filter dusts, fly ash, flying sands, pile of heaps, electroplating sludge, slag, slate residues etc. can also serve as reaction partners.
- Simple quartz sand which consists of approximately 98% silicon dioxide (SiO 2 ), is the simplest possible material that can be used for the implementation.
- halogenatable metal oxides CaO, SiO 2 , TiO 2 , Fe 2 O 3 etc.
- Halogenated waste materials can be solvents such as: Carbon tetrachloride, chloroform, methylene chloride, tetra- and trichlorethylene, Tetrachloroethane, coolants or refrigerants, PCB, pesticides, fungicides and herbicides, halogenated plastics such as Use PVC.
- solvents such as: Carbon tetrachloride, chloroform, methylene chloride, tetra- and trichlorethylene, Tetrachloroethane, coolants or refrigerants, PCB, pesticides, fungicides and herbicides, halogenated plastics such as Use PVC.
- a proportion of the metal oxide that corresponds to the chlorine content of the waste materials is converted into metal chloride by the above-mentioned process.
- Ecologically and economically valuable metal chlorides are formed, with silicon and titanium tetrachloride (SiCl 4 , TiCl 4 ) being particularly preferred products.
- Used oils, lubricants, greases, varnishes, paints, tars, waxes, No plastics, coolants and solvents, brake fluid or the like halogenated substances and materials are disposed of.
- thermodynamically preferred formed under these process parameters are:
- 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 necessary operating temperatures either by using electrical heating elements (eg heating half-shells) or by using induction heating.
- the temperatures required for the implementation are in the range of 800 ° C to 1100 ° C.
- the reaction itself takes place with the exclusion of oxygen.
- Carbon dioxide (CO 2 ) is used as the fluidizing gas.
- the halogenated compounds are in their high temperatures the simplest components are broken down 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 bed of carbon or graphite in the head of the reactor.
- All halogenated metal compounds produced are initially in gaseous form. Depending on the starting material, solid cooling, i.e. crystalline metal compounds can be obtained, or by condensation metal compounds liquid at low temperatures.
- the purity of these compounds is 96% and can 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.
- the reactor 5 is heated by means of a reactor heater 6 to a temperature between 800 ° C and 1100 ° C, so that there is a reaction between the halogenated waste and the metal oxide-containing substances in the reactor.
- the products formed are separated in a solids separator 7 and the solid metal chlorides, in particular FeCl 3 , are discharged via a line 8.
- the remaining gases are cleaned by an activated carbon filter 9 and then compressed by a blower 10.
- the gases are then cooled in a cooling container 12, which has a coolant inlet 11 and a coolant outlet 13, so that the remaining metal chlorides are eliminated. It is mainly SiCl 4 .
- the gases are then fed to a condenser 15 and subjected to an alkaline gas scrubbing in a gas scrubbing column 16.
- the column 16 has a circulation pump 17 for the washing liquid.
- the remaining synthesis gas, a mixture of CO and H 2 is discharged via line 18 in the upper part of the gas scrubbing column 16.
- Application example 1 Disposal of hydrocarbon (KW) or halogenated hydrocarbon (HKW) wastes in the presence of calcium oxide
- the various feed materials such as Oils, fats, PCBs, CFCs, Solvents or the like are dispensed via a metering device, e.g. a Eccentric screw pump, conveyed into the reaction zone. Done there suddenly a first thermal splitting of the feed materials into short-chain Hydrocarbons. The residence time of the Input materials or the resulting fission products determined.
- a metering device e.g. a Eccentric screw pump
- halogenated feedstocks especially chlorinated materials reacted
- a reaction occurs between the calcium oxide and the halogen atoms of the feed materials.
- reaction equation 1 takes into account all essential products that are formed during the disposal or recycling of a halogenated hydrocarbon. The individual products were calculated thermodynamically and verified experimentally.
- carbon is also in the form of fine Soot particles discharged from the reactor.
- Gravity separators e.g. a high performance cyclone.
- the gases cleaned in this way can still be filtered using activated carbon filters be directed. Should still contain foreign matter in the process gas , these can either be through targeted condensation or through a Gas scrubbing can be removed.
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Abstract
Verfahren zur Entsorgung halogenierter und nicht halogenierter Abfallstoffe wobei
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.
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Entsorgung von halogenierten und nicht halogenierten Abfallstoffen.The present invention relates to a method for the disposal of halogenated and non-halogenated waste.
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, especially halogenated hydrocarbons such as for example in carbon tetrachloride, chloroform, methylene chloride, tetra- and Trichlorethylene, tetrachloroethane, PCB etc. but also in PVC or Polyvinylidene chloride are more or less after use problematic toxic or special waste that needs to be disposed of.
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.Substances that are highly toxic to the environment and humans, such as halogenated substances Compounds, especially polyhalogenated substances such as e.g. PCBs or TCDD / TCDF (dioxins / furans) cannot be easily recycled and must be disposed of in an environmentally friendly 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.Disposal takes place either by landfill or by incineration high seas or in the country in high temperature furnaces with one Excess 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 that eliminating substances evaporated and to the required decomposition temperature heated, but also enormous amounts of air have to be heated. Doing so either, as with combustion at sea, pollution of the The atmosphere and the risk of acid rain are accepted Extremely expensive air pollution control systems 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. DE-A-33 13 889 describes a method or an apparatus for Removal of poison and hazardous waste known, in which the toxic Waste materials with an electrically conductive substance, in particular in the form of Iron powder and / or coke mixed and placed in an induction furnace Decomposition temperature of the toxic and / or special waste to be disposed of 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.US-A-4,435,379 describes a process for the decomposition of chlorinated Hydrocarbons with metal oxides with the aim of all carbon atoms in To transfer carbon oxide. It is important to use elemental chlorine To provide conversion of hydrogen groups to HCI. The must total ratio of chlorine to hydrogen groups is at least 1: 1, to be able to produce metal chloride.
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.US-A-4,587,116 describes a similar process in which nitrogenous waste can be disposed of. The heating takes place also from the outside and not from the inside.
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.US-A-4 451 907 discloses a process for the removal of chlorinated organic compounds. First, the chlorinated organic Compounds evaporated in a molten salt furnace, and then to one Reactor led. The chlorinated, organic Compounds heated to 800 to 1200 ° C, in the presence of aluminum oxide and reactive carbon, and consequently decomposes. Nitrogen is used as a carrier gas used to evaporate the chlorinated organic compounds Lead 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,EP 0 306 540 describes a process for the production of energy from substituted hydrocarbons, such as those used 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. are present in pure or bound form. The waste material is thermally decomposed in an inductively heatable reactor in the presence of a metal oxide which is difficult to smelt and an electrically conductive material, for example electrode coke or electrographite, and in contact with water vapor at temperatures between 800 and 1,100 ° C. A proportion of the metal oxide that corresponds to the chlorine content of the waste materials is converted into volatile metal chloride. A portion of the released carbon is converted into carbon monoxide and the portion of the carbon that does not react with the metal oxide is converted into water gas (CO + H 2 ) with the aid of a stoichiometric amount of water vapor.
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 that allowed various halogenated and non-halogenated waste materials to dispose of in an environmentally friendly manner.
Diese Aufgabe wird erfindungsgemäß durch ein Verfahren zur Entsorgung halogenierter nicht halogenierter Abfallstoffe gelöst, bei dem die halogenierten und nicht halogenierten 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.This object is achieved according to the invention by a process for the disposal of halogenated non-halogenated waste materials, in which the halogenated and non-halogenated waste materials are mixed with TiO 2 , SiO 2 , CaO and / or Fe 2 O 3 or a mixture thereof with the exclusion of oxygen at temperatures of 800 ° C to 1100 ° C can be implemented.
Das hier beschriebene Verfahren dient zur umweltneutralen Wiederverwertung von halogenierten und nicht halogenierten Abfallstoffen.The procedure described here is for environmentally neutral recycling of halogenated and non-halogenated waste materials.
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 as little residue as possible and as much as possible of Metals / metal compounds is obtained. When implementing a aiming for a positive energy balance.
In einer bevorzugten Ausführung des Verfahrens werden kohlenstoffhaltige, halogenierte Abfallstoffe umgesetzt.In a preferred embodiment of the method, carbon-containing, halogenated waste materials implemented.
In einer vorteilhaften Ausführung des Verfahrens wird Kohlendioxid als Fluidisierungsgas zugesetzt.In an advantageous embodiment of the method, carbon dioxide is used as Fluidizing gas added.
Weiterhin kann der Reaktor auch mit Kohlenstoff in Form von Graphit und/oder Kohle beaufschlagt werden.Furthermore, the reactor can also use carbon in the form of graphite and / or Coal are charged.
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. Various metal oxide-containing waste materials, such as silicon-containing residues from the metalworking industry, filter dusts, fly ash, flying sands, pile of heaps, electroplating sludge, slag, slate residues etc. can also serve as reaction partners. Simple quartz sand, which consists of approximately 98% silicon dioxide (SiO 2 ), is the simplest possible material that 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 of the above materials are distinguished 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 has the advantage that for so far not with economic means substances containing smeltable metal oxides are now useful Find application.
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.Halogenated waste materials can be solvents such as: Carbon tetrachloride, chloroform, methylene chloride, tetra- and trichlorethylene, Tetrachloroethane, coolants or refrigerants, PCB, pesticides, fungicides and herbicides, halogenated plastics such as Use 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 that corresponds to the chlorine content of the waste materials is converted into metal chloride by the above-mentioned process. Ecologically and economically valuable metal chlorides are formed, with silicon and titanium tetrachloride (SiCl 4 , TiCl 4 ) being 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.Among other things, Used oils, lubricants, greases, varnishes, paints, tars, waxes, No plastics, coolants and solvents, brake fluid or the like halogenated substances and materials are disposed of.
Die unter diesen Prozeßparametern thermodynamisch bevorzugt gebildetenThe thermodynamically preferred formed under these process parameters
Reaktions- bzw. Umsetzungsprodukte sind primär gasförmig anfallender Wasserstoff (H2) neben prozentual geringeren Voluminen an Methan (CH4).The 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 carbon dioxide (CO 2 ) known as so-called greenhouse gas, is negligible under the preferred reaction conditions. Only at temperatures above 1100 ° C can CO or CO 2 be formed by chemical decomposition processes.
The implementation takes place in a fluidized bed reactor. This can either be made of special ceramics, silicon carbide (SiC) or specially 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 necessary operating temperatures either by using electrical heating elements (eg heating half-shells) or by using induction heating. The temperatures required for the implementation are in the range of 800 ° C to 1100 ° C. The reaction itself takes place with the exclusion of oxygen. Carbon dioxide (CO 2 ) is used as the fluidizing gas.
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 in their high temperatures the simplest components are broken down 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.
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 bed of carbon or graphite in the head of the reactor.
Man spricht in diesem Zusammenhang von der sog. BOUDOUARD-Reaktion:
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 halogenated metal compounds produced are initially in gaseous form. Depending on the starting material, solid cooling, i.e. crystalline metal compounds can be obtained, or by condensation metal compounds liquid at low temperatures.
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 can 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:Various configurations of the invention will now be described below of the accompanying figures. 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.1 shows a feed line 1 for the halogenated waste materials, a feed line 2 for products containing metal oxide, and a line 3 for discharging unreacted materials 3. A fluidization gas ( CO 2 ) blown into the fluidized
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
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
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 feed materials, such as Oils, fats, PCBs, CFCs, Solvents or the like are dispensed via a metering device, e.g. a Eccentric screw pump, conveyed into the reaction zone. Done there suddenly a first thermal splitting of the feed materials into short-chain Hydrocarbons. The residence time of the Input materials or the resulting fission products 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.As a rule, there is an almost quantitative split up to essentially Hydrogen and methane, the volume ratio of hydrogen to methane is clearly on the side of hydrogen. Since the melting point of Calcium oxide (CaO) is around 2500 ° C, with no large amounts synthesized calcium compounds.
Werden hingegen halogenierte Einsatzmaterialien insbes. chlorierte Materialien zur Reaktion gebracht, dann tritt eine Reaktion zwischen dem Calciumoxid und den Halogenatomen der Einsatzmaterialien ein.In contrast, halogenated feedstocks, especially chlorinated materials reacted, then a reaction occurs between the calcium oxide and the halogen atoms of the feed materials.
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.
Neben dieser Reaktion wird auch noch Kohlenstoff in Form von feinen Rußpartikeln aus dem Reaktor ausgetragen. In addition to this reaction, carbon is also in the form of fine Soot particles 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 components hydrogen and Methane, or hydrogen and carbon monoxide (CO), takes place through Gravity separators, 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.For safety reasons, the gases cleaned in this way can still be filtered using activated carbon filters be directed. Should still contain foreign matter in the process gas , these can either be through targeted condensation or through a Gas scrubbing can be removed.
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.In the end, usually only one made of carbon monoxide, methane and hydrogen existing synthesis gas left, which for versatile techn. Applications, so e.g. energy generation or use for chemical synthesis (Methanol synthesis) can be used.
Claims (8)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 | ||
| LU90191 | 1997-12-24 | ||
| LU90191A LU90191A7 (en) | 1997-07-23 | 1997-12-24 | Process for the disposal of halogenated and non-halogenated waste materials |
| EP98940244A EP0999878B1 (en) | 1997-07-23 | 1998-07-20 | Method for eliminating halogenated and non halogenated waste |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98940244A Division EP0999878B1 (en) | 1997-07-23 | 1998-07-20 | Method for eliminating halogenated and non halogenated waste |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1219324A2 true EP1219324A2 (en) | 2002-07-03 |
| EP1219324A3 EP1219324A3 (en) | 2004-04-07 |
| EP1219324B1 EP1219324B1 (en) | 2009-12-23 |
Family
ID=26640365
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02004190A Expired - Lifetime EP1219324B1 (en) | 1997-07-23 | 1998-07-20 | Method for elimination of halogenated and non halogenated waste |
| EP98940244A Expired - Lifetime EP0999878B1 (en) | 1997-07-23 | 1998-07-20 | Method for eliminating halogenated and non halogenated waste |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98940244A Expired - Lifetime EP0999878B1 (en) | 1997-07-23 | 1998-07-20 | Method for eliminating halogenated and non halogenated waste |
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|---|---|
| US (1) | US6645449B2 (en) |
| EP (2) | EP1219324B1 (en) |
| JP (1) | JP4208412B2 (en) |
| CN (1) | CN1198669C (en) |
| AT (2) | ATE452689T1 (en) |
| AU (1) | AU747426B2 (en) |
| BR (1) | BR9810858A (en) |
| CA (1) | CA2295907C (en) |
| DE (2) | DE59803209D1 (en) |
| DK (2) | DK0999878T3 (en) |
| ES (2) | ES2172185T3 (en) |
| HK (1) | HK1047900B (en) |
| LU (1) | LU90191A7 (en) |
| PT (2) | PT999878E (en) |
| RU (1) | RU2200601C2 (en) |
| WO (1) | WO1999004861A1 (en) |
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| RU2178115C2 (en) * | 2000-01-12 | 2002-01-10 | Ляпкин Александр Александрович | Method for detoxification of polychlorodiphenyls |
| DE10055360B4 (en) * | 2000-11-08 | 2004-07-29 | Mühlen, Heinz-Jürgen, Dr.rer.Nat. | Process for the gasification of liquid to pasty organic substances and mixtures |
| AT508100A2 (en) * | 2009-03-30 | 2010-10-15 | Erema | NEUTRALIZATION BY FILLER |
| CN102061008A (en) * | 2010-11-09 | 2011-05-18 | 佛山市高明区(中国科学院)新材料专业中心 | Method for reducing bromide content in pyrolysis gas of waste printed circuit board by high-temperature shock heating |
| 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 |
| CN110251877A (en) * | 2019-05-21 | 2019-09-20 | 山东大学 | A kind of method that uses silicon carbide as the mechanochemical method of catalyst to degrade hexachlorobenzene |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7710901A (en) * | 1977-10-05 | 1979-04-09 | Esmil B V Stationsstraat 48 | PROCESS FOR THE SIMULTANEOUS PROCESSING OF USED METAL AND / OR METAL WASTE FROM HALOGENATED HYDROCARBONS. |
| US4435379A (en) * | 1982-08-18 | 1984-03-06 | The Dow Chemical Company | Process for treating chlorinated hydrocarbons |
| US4541907A (en) * | 1984-04-16 | 1985-09-17 | Aluminum Company Of America | Process for decomposing chlorinated hydrocarbon compounds |
| GB8429709D0 (en) * | 1984-11-23 | 1985-01-03 | Alcan Int Ltd | Halogen-containing organic compounds |
| CA1236488A (en) * | 1985-06-25 | 1988-05-10 | Hydro-Quebec | Process for the destruction of toxic organic products |
| DE3623492A1 (en) * | 1986-07-11 | 1988-01-21 | Hagenmaier Hans Paul | METHOD FOR DEGRADING HALOGENATED AROMATES |
| DE3751094D1 (en) | 1986-11-27 | 1995-03-30 | Suppan Friedrich | Process and plant for the production of energy from toxic waste materials and their simultaneous disposal. |
| JPH06104183B2 (en) * | 1989-06-09 | 1994-12-21 | 三井・デュポンフロロケミカル株式会社 | Catalytic decomposition method of chlorofluoroalkane |
| DE4002437A1 (en) * | 1990-01-27 | 1991-08-01 | Man Technologie Gmbh | Catalytic gas phase decomposition of organic halogen cpds. |
| US5608136A (en) * | 1991-12-20 | 1997-03-04 | Kabushiki Kaisha Toshiba | Method and apparatus for pyrolytically decomposing waste plastic |
| DE4202862A1 (en) * | 1992-02-01 | 1993-08-05 | Gerhard Prof Barich | Cracking plastics scrap for reuse - using low temp., low pressure plasma |
| US5222448A (en) * | 1992-04-13 | 1993-06-29 | Columbia Ventures Corporation | Plasma torch furnace processing of spent potliner from aluminum smelters |
| US5280757A (en) * | 1992-04-13 | 1994-01-25 | Carter George W | Municipal solid waste disposal process |
| US5451388A (en) * | 1994-01-21 | 1995-09-19 | Engelhard Corporation | Catalytic method and device for controlling VOC. CO and halogenated organic emissions |
| US5673635A (en) * | 1995-06-12 | 1997-10-07 | L.E. Maxwitat | Process for the recycling of organic wastes |
| RU2093288C1 (en) * | 1996-03-13 | 1997-10-20 | Хасанов Ильмер Юсупович | Rolled sheet production method |
-
1997
- 1997-12-24 LU LU90191A patent/LU90191A7/en unknown
-
1998
- 1998-07-20 PT PT98940244T patent/PT999878E/en unknown
- 1998-07-20 ES ES98940244T patent/ES2172185T3/en not_active Expired - Lifetime
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- 1998-07-20 ES ES02004190T patent/ES2337769T3/en not_active Expired - Lifetime
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- 1998-07-20 AU AU88626/98A patent/AU747426B2/en not_active Ceased
- 1998-07-20 AT AT02004190T patent/ATE452689T1/en active
- 1998-07-20 DK DK98940244T patent/DK0999878T3/en active
- 1998-07-20 EP EP02004190A patent/EP1219324B1/en not_active Expired - Lifetime
- 1998-07-20 WO PCT/EP1998/004508 patent/WO1999004861A1/en not_active Ceased
- 1998-07-20 BR BR9810858-1A patent/BR9810858A/en not_active IP Right Cessation
- 1998-07-20 DE DE59814426T patent/DE59814426D1/en not_active Expired - Lifetime
- 1998-07-20 AT AT98940244T patent/ATE213657T1/en not_active IP Right Cessation
- 1998-07-20 PT PT02004190T patent/PT1219324E/en unknown
- 1998-07-20 CN CNB988074494A patent/CN1198669C/en not_active Expired - Fee Related
- 1998-07-20 EP EP98940244A patent/EP0999878B1/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2001510814A (en) | 2001-08-07 |
| CN1265043A (en) | 2000-08-30 |
| ES2172185T3 (en) | 2002-09-16 |
| ATE213657T1 (en) | 2002-03-15 |
| DE59814426D1 (en) | 2010-02-04 |
| EP1219324B1 (en) | 2009-12-23 |
| RU2200601C2 (en) | 2003-03-20 |
| US20030149325A1 (en) | 2003-08-07 |
| EP0999878B1 (en) | 2002-02-27 |
| US6645449B2 (en) | 2003-11-11 |
| PT999878E (en) | 2002-07-31 |
| CN1198669C (en) | 2005-04-27 |
| LU90191A7 (en) | 1999-06-24 |
| DE59803209D1 (en) | 2002-04-04 |
| ES2337769T3 (en) | 2010-04-29 |
| HK1047900B (en) | 2010-09-03 |
| DK1219324T3 (en) | 2010-04-06 |
| EP1219324A3 (en) | 2004-04-07 |
| CA2295907A1 (en) | 1999-02-04 |
| JP4208412B2 (en) | 2009-01-14 |
| CA2295907C (en) | 2005-10-18 |
| BR9810858A (en) | 2000-07-25 |
| AU8862698A (en) | 1999-02-16 |
| ATE452689T1 (en) | 2010-01-15 |
| DK0999878T3 (en) | 2002-06-10 |
| AU747426B2 (en) | 2002-05-16 |
| EP0999878A1 (en) | 2000-05-17 |
| PT1219324E (en) | 2010-03-25 |
| HK1047900A1 (en) | 2003-03-14 |
| WO1999004861A1 (en) | 1999-02-04 |
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