EP0295454A2 - Process and apparatus for the purposeful destruction (cracking) of polychlorodibenzodioxines and/or polychlorinated dibenzofuranes and for the low-pollution processing of the cracked matter - Google Patents

Process and apparatus for the purposeful destruction (cracking) of polychlorodibenzodioxines and/or polychlorinated dibenzofuranes and for the low-pollution processing of the cracked matter Download PDF

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Publication number
EP0295454A2
EP0295454A2 EP88108074A EP88108074A EP0295454A2 EP 0295454 A2 EP0295454 A2 EP 0295454A2 EP 88108074 A EP88108074 A EP 88108074A EP 88108074 A EP88108074 A EP 88108074A EP 0295454 A2 EP0295454 A2 EP 0295454A2
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Prior art keywords
fluid mixture
substances
fluid
mixture
cracking
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EP88108074A
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German (de)
French (fr)
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EP0295454A3 (en
EP0295454B1 (en
Inventor
Henner Dipl.-Ing. Otromke
Uwe Dipl.-Ing. Theerkorn
Gerd Hedemann
Wolfgang Dr. Rer.Nat. Meiners
Lothar Dipl.-Ing. Hartung
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Dipl-Ing Lothar Hartung Te Kreuztal-Buschhuetten
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Hartung Lothar Dipl-Ing
Felten and Guilleaume Energietechnik AG
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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
    • A62D3/40—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by heating to effect chemical change, e.g. pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • 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
    • 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
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • 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
    • A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/10—Apparatus specially adapted for treating harmful chemical agents; Details thereof

Definitions

  • the invention relates to a method for the targeted decomposition (cracking) of organic-chemical substances in the production and for the environmentally friendly preparation of the cracked substances according to the preamble of claim 1.
  • a further embodiment of the method is specified in claim 2.
  • Devices for carrying out the method are characterized in the subclaims.
  • PCDD Polychlorodibenzodioxins
  • PCDF polychlorinated dibenzofurans
  • PCDD and PCDF arise as trace products in the chemical synthesis of chlorinated hydrocarbons, especially in the synthesis of more chlorinated aromatic hydrocarbons, and can also arise when aromatic chlorinated hydrocarbons are used as intermediates in chemical syntheses.
  • Preferred reaction conditions for the formation of PCDD and PCDF are high temperatures and alkaline medium.
  • PCDD and PCDF can also arise in all types of combustion processes if organic chlorine compounds are present.
  • a well-known example is waste incineration plants. Even when burning wood and fuel, small amounts of PCDD and PCDF must be expected.
  • PCDD and PCDF can today be detected as ubiquitous in nature as predominantly anthropogenic environmental contamination.
  • identification and especially the quantification of this class of substances, which is characterized by a large number of isomers - often referred to simply as "dioxins" by the public - was only possible through modern instrumental analysis.
  • PCDD and PCDf-containing waste The main requirement in the disposal of PCDD and PCDf-containing waste is the removal of this material from the natural cycle. However, the conditions of the applicable laws must be observed.
  • the yardstick for assessing which disposal path to take is the content of PCDD and PCDF in the waste on the one hand, and the level of the disposal facilities on the other.
  • the invention is therefore based on the object of finding a method which makes it possible to carry out an environmentally friendly removal of waste containing PCDD and PCDf and to provide an apparatus for using this method.
  • a further embodiment of the method is specified in claim 2, for which a device is specified in subclaims.
  • the main advantage of the process described in claims 1 and 2 is the treatment of organic chemical substances under defined reductive conditions with a very constant temperature over the entire reaction scheme. This means e.g. created the possibility of eliminating PCDD and PCDF-containing waste in an anaerobic atmosphere. A high reduction potential is built up through a high hydrogen content.
  • the reaction temperature can be kept very precisely at better than +/- 2 ° C for a long period of time.
  • Technical and chemical parameters are selected so that e.g. the formation or destruction of PCDD and PCDF is not only influenced kinetically, but also via the existing reaction partners.
  • the first part of the device is used to generate an anaerobic atmosphere.
  • a fluid mixture of nitrogen, hydrogen and residual gases is processed in a gas cracking plant 1.
  • the fluid mixture prepared in this way is further refined in a fine control stage 2 downstream of the gas gap system 1 with the aid of hydrogen and / or nitrogen, a manipulated variable from a computer-controlled gas analysis system 6 influencing the fine control.
  • the fluid mixture is preheated and enters a fluid bed 3 through gas inlet nozzles 32 below a nozzle plate 31.
  • solid substances in a defined sphere size, here aluminum oxide spheres 34.
  • a container 4 for the organic chemical substances to be treated which are injected into the fluid bed 3 via an injection pump 5 through injection nozzles 33.
  • a fluid mixture that is always processed is guided past the surfaces of the aluminum oxide spheres 34.
  • other elements such as chlorine and possibly existing oxygen are bound by the hydrogen of the fluid mixture.
  • the cracked low molecular weight substances are carried out of the fluid bed 3 according to the flow rate of the fluid mixture and sucked off or blown out.
  • the fluid mixture can also be fed to a piston compressor 11 via a charger 10.
  • the loader has the task of compressing and conveying the fluid mixture from a low initial pressure to a higher final pressure.
  • the piston compressor consists of a cylindrical compression chamber 12 as a working space with a piston reciprocating in a straight line.
  • the organic chemical substances to be treated in liquid form are initially in a container 4, from which they are injected into the piston compressor by means of an injection pump 5.
  • the fluid mixture passes from the charger 10 via inlet valves 14 into the piston compressor 11.
  • the mixture consisting of the fluid mixture and the cracked products leaves the piston compressor 11 via outlet valves 15, previously passing through a catalytic converter 16.
  • the mixture consisting of the fluid mixture and the cracking products is then analyzed in the gas analysis system 6.
  • This system consists of a gas chromatograph and other analysis systems, from which control values are transmitted to fine control level 2.
  • a subsequent one Filtering the mixture consisting of fluid mixture and cracking products in a washing system 7 has the result that the hydrochloric acid contained in the mixture is washed out.
  • a decision is then made as to whether the remainder is washed back to new substances 9 by recycling measures or is fed to a thermal afterburning 8.
  • manipulated variables of the gas analysis system 6 can influence the process sequence in the final stage. 2, the charger is influenced by manipulated variables of the gas analysis system 6.

Abstract

In the combustion of chlorinated organic compounds, small quantities of polychlorinated dibenzo-p-dioxines (PCDD) and dibenzofurans (PCDF) can be formed in addition to the comparatively highly concentrated gaseous and particulate combustion products such as, for example, carbon monoxide, nitrogen monoxide, sulphur dioxide, sulphur trioxide, hydrogen chloride, hydrogen fluoride, soot and solids. PCDD and PCDF have a considerable potential for polluting the environment. According to the invention, organic-chemical substances can be decomposed under defined conditions, so that, for example, toxic substances can be processed without polluting the environment. This is effected in an anaerobic atmosphere by means of a fluidised bed 3 and/or piston compressor 11, in which, for example, PCDD and PCDF are cracked. Such a process with the respective equipment can be used on site wherever polluting substances from the group indicated are formed. <IMAGE>

Description

Die Erfindung betrifft ein Verfahren zur gezielten Zerlegung (Cracken) organisch-chemischer Stoffe in der Produktion und zur umweltfreundlichen Aufbereitung der gecrackten Stoffe gemäß dem Oberbegriff des Anspruchs 1. Eine weitere Ausführungsart des Verfahrens ist in Anspruch 2 angegeben. Vorrichtungen zur Durch­führung des Verfahrens sind in den Unteransprüchen gekenn­zeichnet.The invention relates to a method for the targeted decomposition (cracking) of organic-chemical substances in the production and for the environmentally friendly preparation of the cracked substances according to the preamble of claim 1. A further embodiment of the method is specified in claim 2. Devices for carrying out the method are characterized in the subclaims.

Polychlordibenzodioxine (PCDD) und polychlorierte Dibenzofurane (PCDF) spielen hierbei eine besondere Rolle, und am Beispiel dieser Stoffgruppe soll die anstehende Problematik erläutert werden, wozu mehrere aktuelle Vorfälle Anlaß gegeben haben PCDD und PCDF haben sich als äußerst ungeliebte Substanzen erwiesen. Es gibt eine weitgehende Übereinstimmung in Wissenschaft, Wirt­schaft und Politik, diese Stoffe selbst nicht mehr zu handeln und auch ihre Entstehung zu verhindern. Solcher Vorsatz wird natürlich nur dann wirksam, wenn das Problem der "Altlasten" be­wältigt werden kann. Das bedeutet, daß die bereits vorhandenen "Altlasten" oder deren Erzeuger,wie z. B. polychlorierte Biphe­nyle (PCB), vernichtet werden müssen. Dabei ist es finanziell sinnvoller, die Altlasten PCDD und PCDF zu beseitigen, als sie zu verwalten und zu betreuen.Polychlorodibenzodioxins (PCDD) and polychlorinated dibenzofurans (PCDF) play a special role here, and the problem at hand is to be explained using the example of this group of substances, which has been caused by several recent incidents. PCDD and PCDF have proven to be extremely unloved substances. There is broad agreement in science, business and politics to stop trading these substances themselves and also to prevent their formation. Such a resolution will of course only be effective if the problem of "legacy issues" can be overcome. This means that the existing "contaminated sites" or their producers, such as. B. polychlorinated biphenyls (PCB) must be destroyed. It is financially more sensible to eliminate the legacy PCDD and PCDF than to manage and look after them.

PCDD und PCDF entstehen als Spurenprodukte bei der chemischen Synthese von Chlorkohlenwasserstoffen, vor allem bei der Syn­these von höher chlorierten aromatischen Kohlenwasserstoffen, und sie können auch entstehen, wenn aromatische Chlorkohlen­wasserstoffe bei chemischen Synthesen als Zwischenprodukte ein­gesetzt werden.PCDD and PCDF arise as trace products in the chemical synthesis of chlorinated hydrocarbons, especially in the synthesis of more chlorinated aromatic hydrocarbons, and can also arise when aromatic chlorinated hydrocarbons are used as intermediates in chemical syntheses.

Bevorzugte Reaktionsbedingungen zur Bildung von PCDD und PCDF sind hohe Temperaturen und alkalisches Medium.Preferred reaction conditions for the formation of PCDD and PCDF are high temperatures and alkaline medium.

Weiter können PCDD und PCDF auch bei Verbrennungsprozessen aller Art entstehen, wenn organische Chlorverbindungen gegenwärtig sind. Ein bekanntes Beispiel sind die Müllverbrennungsanlagen Aber auch beim Verbrennen von Holz und von Treibstoffen muß mit der Bildung von PCDD und PCDF in geringen Mengen gerechnet werden.Furthermore, PCDD and PCDF can also arise in all types of combustion processes if organic chlorine compounds are present. A well-known example is waste incineration plants. Even when burning wood and fuel, small amounts of PCDD and PCDF must be expected.

Die Bildung von größeren Mengen von PCDF wurde in mehreren Fällen bei Schwelbränden von Transformatoren, welche mit PCB gefüllt waren, berichtet.The formation of large quantities of PCDF has been reported in several cases in smoldering fires from transformers filled with PCB.

Durch eine Reihe von Unfällen in den vergangenen 40 Jahren ge­langten PCDD und PCDF in die Umwelt. Der bekannteste dieser Unfälle war 1976 in Seveso, Italien, als bei der Herstellung von 2,4,5-Trichlorphenol ca. 2,5 kg 2,3,7,8-TCDD in die Umwelt ge­langten.A number of accidents in the past 40 years have exposed PCDD and PCDF to the environment. The best known of these accidents was in Seveso, Italy in 1976, when approximately 2,5 kg 2,3,7,8-TCDD was released into the environment during the production of 2,4,5-trichlorophenol.

Die Gruppe der PCDD und PCDF ist heute als vorwiegend anthropo­gene Umweltkontamination praktisch ubiquitär in der Natur nach­weisbar. Die Identifizierung und besonders die Quantifizierung dieser durch eine große Anzahl von Isomeren gekennzeichneten Substanzklasse - in der Öffentlichkeit häufig vereinfachend als "Dioxine" bezeichnet - wurde erst durch die moderne instrumen- telle Analytik möglich.The group of PCDD and PCDF can today be detected as ubiquitous in nature as predominantly anthropogenic environmental contamination. The identification and especially the quantification of this class of substances, which is characterized by a large number of isomers - often referred to simply as "dioxins" by the public - was only possible through modern instrumental analysis.

Die Hauptforderung bei der Beseitigung von PCDD- und PCDf-halti­gen Abfällen ist die Entfernung dieses Materials aus dem Kreis­lauf der Natur. Dabei sind jedoch besonders die Gegebenheiten der jeweiligen geltenden Gesetze zu beachten. Der Beurteilungs­maßstab, welcher Beseitigungspfad eingeschlagen werden muß, ist zum einen der Gehalt an den Schadstoffen PCDD und PCDF in den Abfällen, zum anderen das Niveau der Beseitigungsanlagen.The main requirement in the disposal of PCDD and PCDf-containing waste is the removal of this material from the natural cycle. However, the conditions of the applicable laws must be observed. The yardstick for assessing which disposal path to take is the content of PCDD and PCDF in the waste on the one hand, and the level of the disposal facilities on the other.

Die bisherigen Methoden einer umweltgerechten Beseitigung von PCDF - haltigen Abfällen, wie Deponierung, Verbrennung, oder chemisch-physikalische Behandlung erwiesen sich als sehr proble matisch.The previous methods of environmentally friendly disposal of waste containing PCDF, such as landfill, incineration or chemical-physical treatment, proved to be very problematic.

Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren zu finden, das es ermöglicht, eine umweltfreundliche Beseitigung von PCDD- und PCDf-haltigen Abfällen durchzuführen und eine Vor­richtung zur Anwendung dieses Verfahrens zu schaffen.The invention is therefore based on the object of finding a method which makes it possible to carry out an environmentally friendly removal of waste containing PCDD and PCDf and to provide an apparatus for using this method.

Diese Aufgabe wird erfindungsgemäß durch das mit den kennzeich­nenden Merkmalen des Anspruchs 1 umrissene Verfahren bzw. eine in den Unteransprüchen angegebene Vorrichtung gelöst.This object is achieved according to the invention by the method outlined with the characterizing features of claim 1 or by a device specified in the subclaims.

Eine weitere Ausführungsform des Verfahrens ist in Anspruch 2 angegeben, wozu eine Vorrichtung in Unteransprüchen angegeben ist.A further embodiment of the method is specified in claim 2, for which a device is specified in subclaims.

Der wesentliche Vorteil der in den Ansprüchen 1 und 2 beschrie­benen Verfahren liegt in der Behandlung organisch-chemischer Stoffe unter definierten reduktiven Bedingungen bei gleichzei­tiger sehr konstanter Temperatur über das gesamte Reaktions­schema. Dadurch ist z.B. die Möglichkeit geschaffen, PCDD und PCDF- haltige Abfälle in einer anaeroben Atmosphäre zu besei­tigen. Durch einen hohen Wasserstoffanteil wird ein starkes Reduktionspotential aufgebaut. Die Reaktionstemperatur kann auch für längere Zeitdauer sehr exakt auf besser als +/- 2°C konstant gehalten werden. Anlagentechnische und chemische Parameter sind dabei so gewählt, daß z.B. die Bildung bzw. die Zerstörung von PCDD und PCDF nicht nur kinetisch, sondern auch über die vor­handenen Reaktionspartner beeinflußt wird.The main advantage of the process described in claims 1 and 2 is the treatment of organic chemical substances under defined reductive conditions with a very constant temperature over the entire reaction scheme. This means e.g. created the possibility of eliminating PCDD and PCDF-containing waste in an anaerobic atmosphere. A high reduction potential is built up through a high hydrogen content. The reaction temperature can be kept very precisely at better than +/- 2 ° C for a long period of time. Technical and chemical parameters are selected so that e.g. the formation or destruction of PCDD and PCDF is not only influenced kinetically, but also via the existing reaction partners.

Vorteilhafte Bestandteile einer Vorrichtung, die nach dem Ver­fahren nach Anspruch 1 arbeitet, sind in den Ansprüchen 12 und 13 gekennzeichnet, während vorteilhafte Bestandteile einer Vor richtung, die nach Anspruch 2 arbeitet, in den Ansprüchen 18 und 19 be­schrieben ist.Advantageous components of a device that works according to the method of claim 1 are characterized in claims 12 and 13, while advantageous components of a device, which operates according to claim 2, is described in claims 18 and 19.

Die Besonderheit liegt darin, daß bei den Vorrichtungen die Tem­peratur über das gesamte Reaktionsvolumen homogen und konstant eingestellt werden kann. Darüber hinaus kann die Gasatmosphäre für den Reaktionsraum gezielt ausgewählt werden. Speziell im Fluidbett haben die Feststoffkügelchen mehrere Funktionen:

  • 1. Nach der Benetzung der aufgeheizten Kügelchen wird die Wärme­energie schlagartig auf die behandelnden Stoffe übertragen.
  • 2. Kügelchen transportieren die zu behandelnden Stoffe durch das Fluidbett hindurch und erhalten den Kontakt mit frischem Reaktionsgas.
  • 3. Durch das Niederdruckfluidisieren ist die Verweilzeit beson­ders lang.
  • 4. Der dünne Film der zu behandelnden Stoffe zeigt an der Ober­fläche der Feststoffkügelchen eine besondere Reaktionsbereit­schaft.
The special feature is that the temperature of the devices can be set homogeneously and constantly over the entire reaction volume. In addition, the gas atmosphere for the reaction space can be specifically selected. The solid spheres have several functions, particularly in the fluid bed:
  • 1. After the heated beads have been wetted, the thermal energy is suddenly transferred to the treating substances.
  • 2. Beads transport the substances to be treated through the fluid bed and maintain contact with fresh reaction gas.
  • 3. Because of the low-pressure fluidization, the dwell time is particularly long.
  • 4. The thin film of the substances to be treated shows a special willingness to react on the surface of the solid spheres.

Ausführungsbeispiele der Erfindung sind in Zeichnungen darge­stellt und werden im foldenden näher erläutert. Es zeigen

  • Fig. 1 eine Vorrichtung mit einem Fluidbett
  • Fig. 2 eine weitere Vorrichtung mit einem Kolbenverdichter
Exemplary embodiments of the invention are shown in drawings and are explained in more detail below. Show it
  • Fig. 1 shows a device with a fluid bed
  • Fig. 2 shows another device with a piston compressor

Nach Fig. 1 und 2 dient der erste Teil der Vorrichtung zur Er­zeugung einer anaeroben Atmosphäre. Hierzu wird ein Fluidgemisch aus Stickstoff, Wasserstoff und Restgasen in einer Gasspaltan­lage 1 aufbereitet. Das so aufbereitete Fluidgemisch wird in einer der Gasspaltanlage 1 nachgeschalteten Feinregelungsstufe 2 mit Hilfe von Wasserstoff und /oder Stickstoff weiter veredelt, wobei eine Stellgröße aus einer rechnergesteuerten Gasanalyse­system 6 die Feinregelung beeinflußt.1 and 2, the first part of the device is used to generate an anaerobic atmosphere. For this purpose, a fluid mixture of nitrogen, hydrogen and residual gases is processed in a gas cracking plant 1. The fluid mixture prepared in this way is further refined in a fine control stage 2 downstream of the gas gap system 1 with the aid of hydrogen and / or nitrogen, a manipulated variable from a computer-controlled gas analysis system 6 influencing the fine control.

Nach Fig. 1 wird das Fluidgemisch vorgewärmt und tritt durch Gaseinlaßdüsen 32 unterhalb einer Düsenplatte 31 in ein Fluid­bett 3 ein. In dem Fluidbett befinden sich feste Stoffe in defi­nierter Kugelgröße, hier Aluminiumoxydkügelchen 34. Unterhalb des Fluidbetts befindet sich ein Behälter 4 für die zu behan­delnden organisch-chemischen Stoffe, die über eine Einspritz­pumpe 5 durch Einspritzdüsen 33 in das Fluidbett 3 eingespritzt werden. Durch ständiges Wirbeln der Fluidmasse wird ein stets aufbereitetes Fluidgemisch an den Oberflächen der Aluminium­oxydkügelchen 34 vorbeigeführt. Hierbei werden andere Elemente wie Chlor und eventuell vorhandener Sauerstoff vom Wasserstoff des Fluidgemisches gebunden. Die gecrackten niedermolekularen Stoffe werden entsprechend der Strömungsgeschwindigkeit des Fluidgemisches aus dem Fluidbett 3 herausgetragen und abgesaugt, bzw. ausgeblasen.According to FIG. 1, the fluid mixture is preheated and enters a fluid bed 3 through gas inlet nozzles 32 below a nozzle plate 31. In the fluid bed there are solid substances in a defined sphere size, here aluminum oxide spheres 34. Below the fluid bed there is a container 4 for the organic chemical substances to be treated, which are injected into the fluid bed 3 via an injection pump 5 through injection nozzles 33. By constantly swirling the fluid mass, a fluid mixture that is always processed is guided past the surfaces of the aluminum oxide spheres 34. Here other elements such as chlorine and possibly existing oxygen are bound by the hydrogen of the fluid mixture. The cracked low molecular weight substances are carried out of the fluid bed 3 according to the flow rate of the fluid mixture and sucked off or blown out.

Nach Fig. 2 kann das Fluidgemisch auch über einen Lader 10 einem Kolbenverdichter 11 zugeführt werden. Der Lader hat die Auf­gabe, das Fluidgemisch von einem niederen Anfangsdruck auf einen höheren Enddruck zu verdichten und zu fördern. Der Kolbenver­dichter besteht aus einer zylindrischen Verdichtungskammer 12 als Arbeitsraum mit einem geradlinig hin- und herbewegten Kol­ben. Die zu behandelnden organisch- chemischen Stoffe in flüs­siger Form befinden sich zunächst in einem Behälter 4, aus dem sie mittels einer Einspritzpumpe 5 in den Kolbenverdichter eingespritzt werden. Das Fluidgemisch gelangt vom Lader 10 über Einlaßventile 14 in den Kolbenverdichter 11. Über Auslaßventile 15 verläßt das aus dem Fluidgemisch und den Crackprodukten be­stehende Gemisch den Kolbenverdichter 11, wobei es zuvor einen Katalysator 16 passiert.According to FIG. 2, the fluid mixture can also be fed to a piston compressor 11 via a charger 10. The loader has the task of compressing and conveying the fluid mixture from a low initial pressure to a higher final pressure. The piston compressor consists of a cylindrical compression chamber 12 as a working space with a piston reciprocating in a straight line. The organic chemical substances to be treated in liquid form are initially in a container 4, from which they are injected into the piston compressor by means of an injection pump 5. The fluid mixture passes from the charger 10 via inlet valves 14 into the piston compressor 11. The mixture consisting of the fluid mixture and the cracked products leaves the piston compressor 11 via outlet valves 15, previously passing through a catalytic converter 16.

Nach Fig. 1 und 2 wird das aus dem Fluidgemisch und den Crack­produkten bestehende Gemisch anschließend im Gasanalysesystem 6 analysiert. Dieses System besteht aus einem Gaschromatographen und anderen Analysesystemen, von denen aus Stellgrößen an die Feinregelungsstufe 2 übermittelt werden. Eine anschließende Filterung des aus Fluidgemisch und Crackprodukten bestehenden Gemisches in einer Waschanlage 7 hat zur Folge, daß die in dem Gemisch enthaltene Salzsäure herausgewaschen wird. Danach wird entschieden, ob der Rest durch Recyclingsmaßnahmen zu neuen Stoffen 9 zurückgewaschen oder einer thermischen Nachverbrennung 8 zugeführt wird.. Auch in diesem Fall können Stellgrößen des Gasanalysesystems 6 den Prozeßablauf im Endstadium beeinflussen. Nach Fig. 2 wird der Lader durch Stellgrößen des Gasanalyse­systems 6 beeinflußt.1 and 2, the mixture consisting of the fluid mixture and the cracking products is then analyzed in the gas analysis system 6. This system consists of a gas chromatograph and other analysis systems, from which control values are transmitted to fine control level 2. A subsequent one Filtering the mixture consisting of fluid mixture and cracking products in a washing system 7 has the result that the hydrochloric acid contained in the mixture is washed out. A decision is then made as to whether the remainder is washed back to new substances 9 by recycling measures or is fed to a thermal afterburning 8. In this case too, manipulated variables of the gas analysis system 6 can influence the process sequence in the final stage. 2, the charger is influenced by manipulated variables of the gas analysis system 6.

Claims (19)

1. Verfahren zur gezielten Zerlegung (Cracken) organisch-chemi­scher Stoffe in der Produktion und zur umweltfreundlichen Aufbe­reitung der gecrackten Stoffe, die in einer Crackanlage nach dem Fluidbettverfahren in neue Verbindungen überführt werden, dadurch gekennzeichnet, daß 1.1 ein anaerobes, vorgewärmtes Fluidgemisch aus Stickstoff, Wasserstoff und Restgasen erzeugt wird, 1.2 vorgewärmte Stoffe in definierter Kugelgröße (Feststoffe 34) in dem Fluidbett (3) fluidiziert werden, 1.3 das Fluidgemisch in das Fluidbett (3) eingeblasen wird, 1.4 die aufzubereitenden Stoffe, wie Halogenkohlenwasserstoffe in das Fluidbett (3) eingespritzt werden, wo sie die Oberflächen der Feststoffe (34) benetzen und gleichzeitig 1.5 durch immerwährendes Wirbeln der Fluidmasse ein ständig auf­bereitetes Fluidgemisch an den Oberflächen der Feststoffe (34) vorbeigeführt wird, wobei andere Elemente, wie z.B. Chlor und eventuell vorhandener Sauerstoff vom Wasserstoff des Fluidgemisches gebunden werden 1.6 die gecrackten niedermolekularen Stoffe entsprechend der Strömungsgeschwindigkeit des Fluidgemisches aus dem Fluidbett (3) herausgetragen und abgesaugt werden, 1.7 das aus dem Fluidgemisch und den Crackprodukten bestehende Gemisch analysiert wird, 1.8 dieses Gemisch derart gefiltert wird, daß Reaktionsproduk­te, wie z.B. Salzsäure absorbiert zurückgewonnen werden oder einer thermischen Nachverbrennung (8) zugeführt werden. 1. A process for the targeted decomposition (cracking) of organic-chemical substances in the production and for the environmentally friendly preparation of the cracked substances, which are converted into new compounds in a cracking plant according to the fluid bed process, characterized in that 1.1 an anaerobic, preheated fluid mixture is generated from nitrogen, hydrogen and residual gases, 1.2 preheated substances in a defined ball size (solids 34) are fluidized in the fluid bed (3), 1.3 the fluid mixture is blown into the fluid bed (3), 1.4 the substances to be processed, such as halogenated hydrocarbons, are injected into the fluid bed (3), where they wet the surfaces of the solids (34) and at the same time 1.5 by constantly swirling the fluid mass, a constantly processed fluid mixture is guided past the surfaces of the solids (34), other elements, such as chlorine and possibly existing oxygen, being bound by the hydrogen of the fluid mixture 1.6 the cracked low-molecular substances are carried out of the fluid bed (3) and sucked off in accordance with the flow rate of the fluid mixture, 1.7 the mixture consisting of the fluid mixture and the cracking products is analyzed, 1.8 this mixture is filtered in such a way that reaction products, such as hydrochloric acid, are recovered in an absorbed manner or are fed to thermal afterburning (8). 2. Verfahren zur gezielten Zerlegung (Cracken) organisch-chemi­scher Stoffe in der Produktion und zur umweltfreundlichen Auf­bereitung der gecrackten Stoffe, die in einer Crackanlage in neue Verbindungen überführt werden, dadurch gekennzeichnet, daß 2.1 ein anaerobes, vorgewärmtes Fluidgemisch erzeugt wird, 2.2 das Fluidgemisch durch Einlaßventile (14) eines Kolben­verdichters (11) angesaugt wird, 2.3 in das verdichtete Fluidgemisch mit einer Temperatur von 350°C bis 550°C die zu behandelnden organisch-chemischen Stoffe, gegebenfalls in Lösung, eingespritzt werden, 2.4 durch Regulierung des Ansaugdrucks, der Ansaugtemperatur, der Kolbengeschwindigkeit und der Vorwärmung der zu behan­delnden organisch-chemischen Stoffe die Temperatur über den gesamten Volumenbereich auf einen definierten konstanten Wert gehalten wird, 2.5 die Reaktion durch anwesende Hilfsstoffe in der Verdich­tungskammer (12) des Kolbenverdichters (11) gesteuert wird, 2.6 das Gemisch aus den Crackprodukten und dem Fluidgemisch nach Austritt aus der Verdichtungskammer (12) durch einen Katalysator (16) geführt wird und 2.7 durch öffnen der Auslaßventile (15) durch ein Rohr abgesaugt wird, wobei 2.8 dieses Gemisch anschließend analysiert wird und 2.9 derart gefiltert wird, daß Reaktionsprodukte, wie z.B. Salz­säure, absorbiert werden, wobei der Rest durch Recyclingsmaß­nahmen zurückgewonnen oder einer thermischen Nachverbrennung (8) zugeführt wird. 2. Process for the targeted decomposition (cracking) of organic-chemical substances in the production and for the environmentally friendly preparation of the cracked substances which are converted into new compounds in a cracking plant, characterized in that 2.1 an anaerobic, preheated fluid mixture is generated, 2.2 the fluid mixture is sucked in through inlet valves (14) of a piston compressor (11), 2.3 the organic chemical substances to be treated, optionally in solution, are injected into the compressed fluid mixture at a temperature of 350 ° C to 550 ° C, 2.4 by regulating the suction pressure, the suction temperature, the piston speed and the preheating of the organic chemical substances to be treated, the temperature is kept at a defined constant value over the entire volume range, 2.5 the reaction is controlled by auxiliary substances present in the compression chamber (12) of the piston compressor (11), 2.6 the mixture of the cracked products and the fluid mixture after it leaves the compression chamber (12) is passed through a catalyst (16) and 2.7 is sucked off through a tube by opening the outlet valves (15) 2.8 this mixture is then analyzed and 2.9 is filtered in such a way that reaction products, such as hydrochloric acid, are absorbed, the remainder being recovered by recycling measures or being fed to thermal afterburning (8). 3. Verfahren nach den Ansprüchen 1 oder 2, dadurch gekennzeich­net, daß das anaerobe Fluidgemisch durch Teilverbrennung von Erdgas oder Propan mit atmosphärischer Luft und anschließender Entfernung von unerwünschten Verbrennungsgasen erzeugt wird.3. The method according to claims 1 or 2, characterized in that the anaerobic fluid mixture is generated by partial combustion of natural gas or propane with atmospheric air and subsequent removal of undesirable combustion gases. 4. Verfahren nach den Ansprüchen 1-3, dadurch gekennzeichnet, daß das anaerobe Fluidgemisch aus Stickstoff mit 4 bis 12%igem Was­serstoff und 0,l%igem Restgas besteht.4. Process according to claims 1-3, characterized in that the anaerobic fluid mixture consists of nitrogen with 4 to 12% hydrogen and 0.1% residual gas. 5. Verfahren nach den Ansprüchen 1,3 und 4, dadurch gekennzeichnet, daß das anaerobe Fluidgemisch durch eine am Boden des Fluidbetts (3) befindliche Düsenplatte (31) eingeblasen wird, wobei je nach Einblasdruck die Abstände der Bestandteile der Feststoffe (34) vergrößert oder verkleinert werden.5. Process according to claims 1, 3 and 4, characterized in that the anaerobic fluid mixture is injected through a nozzle plate (31) located at the bottom of the fluid bed (3), the distances between the constituents of the solids (34) being increased depending on the injection pressure or be reduced. 6. Verfahren nach den Ansprüchen 1,2, dadurch gekennzeichnet, daß die Zuführung der zu behandelnden organisch-chemischen Stoffe kontinuierlich oder diskontinuierlich erfolgt6. The method according to claims 1,2, characterized in that the supply of the organic chemical substances to be treated takes place continuously or discontinuously 7. Verfahren nach den Ansprüchen 1-6, dadurch gekennzeichnet, daß kontinuierlich Proben des Gemisches aus den Crackprodukten und des Fluidgemisches oberhalb des Fluidbades entnommen werden, die mit Hilfe vorher geeichter Substanzen in einem Gaschromato­graphen analysiert werden.7. The method according to claims 1-6, characterized in that samples of the mixture of the cracking products and the fluid mixture above the fluid bath are continuously taken, which are analyzed with the aid of previously calibrated substances in a gas chromatograph. 8. Verfahren nach den Ansprüchen 1-7, dadurch gekennzeichnet, daß mit Hilfe eines Gasanalysesystems (6) und eines Rechen­programms Stellgrößen, wie Zusammensetzung des Fluidgemisches, Temperatur, Strömungsgeschwindigkeit gemessen und ermittelt werden, und daß die Stellgrößen in Form von Signalen an Stellglieder weitergegeben werden.8. The method according to claims 1-7, characterized in that with the help of a gas analysis system (6) and a computer program manipulated variables, such as the composition of the fluid mixture, temperature, flow rate are measured and determined, and that the manipulated variables are passed on to actuators in the form of signals will. 9. Verfahren nach den Ansprüchen 1-8, dadurch gekennzeichnet, daß die Stellgrößen zur Feinregelung aller Anlagenkomponenten verwendet werden.9. The method according to claims 1-8, characterized in that the manipulated variables are used for fine control of all system components. 10. Verfahren nach den Ansprüchen 1-9, dadurch gekennzeichnet, daß die Proben bei Vorhandensein von kritischen Stoffen (z.B. Dioxin) der thermischen Nachverbrennung (8) zugeführt werden, wobei die Temperatur der Nachverbrennung kurzzeitig auf 1000 C erhöht wird.10. The method according to claims 1-9, characterized in that the samples in the presence of critical substances (eg dioxin) are fed to the thermal afterburning (8), whereby the temperature of the afterburning is briefly raised to 1000 ° C. 11. Vorrichtung zur Durchführung des Verfahrens nach den Ansprü­chen 1-10, dadurch gekennzeichnet, daß die Gasaufbereitung zur Erzeugung des anaeroben Fluidgemisches in einer Gasspaltanlage (1) durchgeführt wird, der eine Feinregelungsstufe (2) für die Zufuhr von Wasser- und / oder Stickstoff sowie von Stellgrößen aus dem Gasanalysesystem (6) nachgeschaltet ist.11. Device for performing the method according to claims 1-10, characterized in that the gas treatment for generating the anaerobic fluid mixture is carried out in a gas gap system (1), which has a fine control stage (2) for the supply of water and / or nitrogen and downstream of manipulated variables from the gas analysis system (6). 12. Vorrichtung zur Durchführung des Verfahrens nach Anspruch 1, dadurch gekennzeichnet, daß die Crackanlage aus einem Fluidbett (3) besteht, unter dessen Düsenplatte (31) sich neben Gasein­laßdüsen (32) für das Fluidgemisch Einspritzdüsen (33) für die zu behandelnden organisch- chemischen Stoffe befinden.12. The apparatus for performing the method according to claim 1, characterized in that the cracking system consists of a fluid bed (3), under the nozzle plate (31) in addition to gas inlet nozzles (32) for the fluid mixture, injection nozzles (33) for the organic to be treated chemical substances. 13. Vorrichtung nach Anspruch 12, dadurch gekennzeichnet, daß eine Einspritzpumpe (5) für die zubehandelnden orga­nisch-chemischen Stoffe eingesetzt ist.13. The apparatus according to claim 12, characterized in that an injection pump (5) is used for the organic chemical substances to be treated. 14. Vorrichtung nach den Ansprüchen 11-13, dadurch gekenn­zeichnet, daß das Gasanalysesystem(6) mit einer Regelung für die Stellgrößen versehen ist.14. Device according to claims 11-13, characterized in that the gas analysis system (6) is provided with a control for the manipulated variables. 15. Vorrichtung nach den Ansprüchen 11-14, dadurch gekenn­zeichnet, daß die gesamte Anlage stationär ausgebildet ist.15. Device according to claims 11-14, characterized in that the entire system is stationary. 16. Vorrichtung nach den Ansprüchen 11-14, dadurch gekenn­zeichnet, daß die gesamte Anlage in mobilen Einheiten unter­gebracht ist.16. Device according to claims 11-14, characterized in that the entire system is housed in mobile units. 17. Vorrichtung nach Anspruch 16, dadurch gekennzeichnet, daß die Anlage in Containern angeordnet ist, wobei jeweils ein Con­tainer für die Gasaufbereitung, den Crackvorgang, und für ein Labor einschließlich der Regelung und Fernüberwachung vorgesehen ist.17. The apparatus according to claim 16, characterized in that the system is arranged in containers, one container for the gas processing, the cracking process, and for a laboratory including the control and remote monitoring is provided. 18. Vorrichtung zur Durchführung des Verfahrens nach den Ansprü­chen 2 bis 4 und 6 bis 10, dadurch gekennzeichnet, daß der Kol­benverdichter (11) eine Verdichtungskammer (12) besitzt, in welcher sich ein Kolben geradlinig hin - und herbewegt und daß die Verdichtungskammer Gaseinlaßdüsen (13) für das Fluidgemisch, Einlaßventile (14) für die zu behandelnden organisch-chemischen Stoffe und Auslaßventile (15) hierfür aufweist.18. Device for performing the method according to claims 2 to 4 and 6 to 10, characterized in that the piston compressor (11) has a compression chamber (12) in which a piston reciprocates in a straight line and that the compression chamber gas inlet nozzles ( 13) for the fluid mixture, inlet valves (14) for the organic chemical substances to be treated and outlet valves (15) therefor. 19. Vorrichtung nach Anspruch 18, dadurch gekennzeichnet, daß in dem Kolbenverdichter (11) ein Katalysator (16) eingesetzt ist19. The apparatus according to claim 18, characterized in that a catalyst (16) is used in the piston compressor (11)
EP19880108074 1987-06-13 1988-05-20 Process and apparatus for the purposeful destruction (cracking) of polychlorodibenzodioxines and/or polychlorinated dibenzofuranes and for the low-pollution processing of the cracked matter Expired - Lifetime EP0295454B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88108074T ATE60347T1 (en) 1987-06-13 1988-05-20 PROCESS AND DEVICE FOR THE TARGETED BREAKDOWN (CRACKING) OF POLYCHLORDIBENZODIOXINS AND/OR POLYCHLORORATED DIBENZOFURANES AND FOR THE ENVIRONMENTALLY FRIENDLY PROCESSING OF THE CRACKED SUBSTANCES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3719824 1987-06-13
DE3719824A DE3719824C1 (en) 1987-06-13 1987-06-13 Method and device for the targeted decomposition (cracking) of halogenated hydrocarbons with subsequent environmentally friendly preparation of the cracked substances

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EP0295454A2 true EP0295454A2 (en) 1988-12-21
EP0295454A3 EP0295454A3 (en) 1989-03-15
EP0295454B1 EP0295454B1 (en) 1991-01-23

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
FR2671990A1 (en) * 1991-01-24 1992-07-31 Chaussonnet Pierre System for treating liquid or gaseous products by thermal decomposition (thermolysis) under vacuum, the dumping of which products is harmful to the environment
EP0570645A1 (en) * 1992-05-20 1993-11-24 Societe Francaise De Thermolyse System and process for the vacuum thermolysis of liquid or gaseous products whose disposal is damaging to the environment
WO1993023497A1 (en) * 1992-05-20 1993-11-25 Societe Francaise De Thermolyse System and process for vacuum thermolysis treatment of liquid or gas products, the disposal of which is detrimental to the environment
US5730947A (en) * 1991-01-24 1998-03-24 Societe Francaise De Thermolyse System and process for vacuum thermolysis treatment of liquid or gas products the disposal of which is detrimental to the environment

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GB2159137A (en) * 1984-05-21 1985-11-27 Univ Southern California Conversion of halogenated toxic substances
EP0257893A1 (en) * 1986-08-08 1988-03-02 655901 Ontario Inc. Process for the destruction of organic waste material

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US3542532A (en) * 1968-01-11 1970-11-24 Exxon Research Engineering Co Process for the production of hydrogen from petroleum coke
US3597327A (en) * 1969-04-02 1971-08-03 Arthur M Squires Process for pyrolyzing a solid or liquid hydrocarbonaceous fuel in a fluidized bed
GB2058828A (en) * 1979-09-21 1981-04-15 Monsanto Co Oxidatively gasifying carbon- containing materials
DE3616785A1 (en) * 1986-05-17 1987-11-19 Union Rheinische Braunkohlen METHOD FOR PROCESSING CARBON-CONTAINING WASTE AND BIOMASS

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GB2159137A (en) * 1984-05-21 1985-11-27 Univ Southern California Conversion of halogenated toxic substances
EP0257893A1 (en) * 1986-08-08 1988-03-02 655901 Ontario Inc. Process for the destruction of organic waste material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2671990A1 (en) * 1991-01-24 1992-07-31 Chaussonnet Pierre System for treating liquid or gaseous products by thermal decomposition (thermolysis) under vacuum, the dumping of which products is harmful to the environment
US5730947A (en) * 1991-01-24 1998-03-24 Societe Francaise De Thermolyse System and process for vacuum thermolysis treatment of liquid or gas products the disposal of which is detrimental to the environment
EP0570645A1 (en) * 1992-05-20 1993-11-24 Societe Francaise De Thermolyse System and process for the vacuum thermolysis of liquid or gaseous products whose disposal is damaging to the environment
WO1993023497A1 (en) * 1992-05-20 1993-11-25 Societe Francaise De Thermolyse System and process for vacuum thermolysis treatment of liquid or gas products, the disposal of which is detrimental to the environment

Also Published As

Publication number Publication date
DE3719824C1 (en) 1989-03-09
EP0295454A3 (en) 1989-03-15
DE3861632D1 (en) 1991-02-28
EP0295454B1 (en) 1991-01-23
ES2021113B3 (en) 1991-10-16
ATE60347T1 (en) 1991-02-15

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