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EP1219324A2 - Procédé d élimination de déchets halogénés et non halogénés - Google Patents

Procédé d élimination de déchets halogénés et non halogénés Download PDF

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Publication number
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
Authority
EP
European Patent Office
Prior art keywords
halogenated
waste materials
carbon
waste
materials
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP02004190A
Other languages
German (de)
English (en)
Other versions
EP1219324B1 (fr
EP1219324A3 (fr
Inventor
Guy Rollinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pac Holding SA
Original Assignee
Pac Holding SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from LU90109A external-priority patent/LU90109B1/xx
Application filed by Pac Holding SA filed Critical Pac Holding SA
Publication of EP1219324A2 publication Critical patent/EP1219324A2/fr
Publication of EP1219324A3 publication Critical patent/EP1219324A3/fr
Application granted granted Critical
Publication of EP1219324B1 publication Critical patent/EP1219324B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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 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.

Landscapes

  • 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)
  • Health & Medical Sciences (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)
EP02004190A 1997-07-23 1998-07-20 Procédé d élimination de déchets halogénés et non halogénés Expired - Lifetime EP1219324B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
LU90109 1997-07-23
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
LU90191 1997-12-24
LU90191A LU90191A7 (de) 1997-07-23 1997-12-24 Verfahren zur entsorgung von halogenierten und nicht halogenierten abfallstoffen
EP98940244A EP0999878B1 (fr) 1997-07-23 1998-07-20 Procede d'elimination de dechets halogenes et non halogenes

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP98940244A Division EP0999878B1 (fr) 1997-07-23 1998-07-20 Procede d'elimination de dechets halogenes et non halogenes

Publications (3)

Publication Number Publication Date
EP1219324A2 true EP1219324A2 (fr) 2002-07-03
EP1219324A3 EP1219324A3 (fr) 2004-04-07
EP1219324B1 EP1219324B1 (fr) 2009-12-23

Family

ID=26640365

Family Applications (2)

Application Number Title Priority Date Filing Date
EP98940244A Expired - Lifetime EP0999878B1 (fr) 1997-07-23 1998-07-20 Procede d'elimination de dechets halogenes et non halogenes
EP02004190A Expired - Lifetime EP1219324B1 (fr) 1997-07-23 1998-07-20 Procédé d élimination de déchets halogénés et non halogénés

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP98940244A Expired - Lifetime EP0999878B1 (fr) 1997-07-23 1998-07-20 Procede d'elimination de dechets halogenes et non halogenes

Country Status (16)

Country Link
US (1) US6645449B2 (fr)
EP (2) EP0999878B1 (fr)
JP (1) JP4208412B2 (fr)
CN (1) CN1198669C (fr)
AT (2) ATE213657T1 (fr)
AU (1) AU747426B2 (fr)
BR (1) BR9810858A (fr)
CA (1) CA2295907C (fr)
DE (2) DE59803209D1 (fr)
DK (2) DK1219324T3 (fr)
ES (2) ES2172185T3 (fr)
HK (1) HK1047900B (fr)
LU (1) LU90191A7 (fr)
PT (2) PT999878E (fr)
RU (1) RU2200601C2 (fr)
WO (1) WO1999004861A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2178115C2 (ru) * 2000-01-12 2002-01-10 Ляпкин Александр Александрович Способ обезвреживания полихлордифенилов
DE10055360B4 (de) * 2000-11-08 2004-07-29 Mühlen, Heinz-Jürgen, Dr.rer.Nat. Verfahren zur Vergasung von flüssigen bis pastösen organischen Stoffen und Stoffgemischen
AT508100A2 (de) * 2009-03-30 2010-10-15 Erema Neutralisierung durch füllstoff
CN102061008A (zh) * 2010-11-09 2011-05-18 佛山市高明区(中国科学院)新材料专业中心 高温骤热降低废印刷线路板热解气体中溴化物含量的方法
CN104147745B (zh) * 2014-08-22 2017-02-15 上海化工研究院 一种化学转化去除环境中挥发性卤代烃的方法
RU2667566C1 (ru) * 2017-09-04 2018-09-21 Федеральное государственное бюджетное образовательное учреждение высшего образования "Ярославский государственный технический университет" ФГБОУВО "ЯГТУ" Способ подготовки гальваношлама к утилизации
CN110251877A (zh) * 2019-05-21 2019-09-20 山东大学 一种以碳化硅为催化剂的机械化学法降解六氯苯的方法

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7710901A (nl) * 1977-10-05 1979-04-09 Esmil B V Stationsstraat 48 Werkwijze voor het gelijktijdig verwerken van gebruikt metaal en/of metaalafval van gehaloge- neerde koolwaterstoffen.
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 (fr) 1985-06-25 1988-05-10 Hydro-Quebec Procede pour la destruction de produits organiques toxiques
DE3623492A1 (de) 1986-07-11 1988-01-21 Hagenmaier Hans Paul Verfahren zum abbau von halogenierten aromaten
EP0306540B1 (fr) 1986-11-27 1995-02-22 Friedrich Dipl.-Chem. Suppan Procédé et installation pour la production d'énergie à partir de déchets toxiques et leur enlèvement simultané
JPH06104183B2 (ja) 1989-06-09 1994-12-21 三井・デュポンフロロケミカル株式会社 塩弗化アルカンの接触分解方法
DE4002437A1 (de) * 1990-01-27 1991-08-01 Man Technologie Gmbh Verfahren zur zersetzung organischer halogenverbindungen
US5608136A (en) * 1991-12-20 1997-03-04 Kabushiki Kaisha Toshiba Method and apparatus for pyrolytically decomposing waste plastic
DE4202862A1 (de) * 1992-02-01 1993-08-05 Gerhard Prof Barich Verfahren und vorrichtung zur wiederverwertung von sortenreinen oder gemischten, sauberen oder verunreinigten kunststoffabfaellen
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 (ru) * 1996-03-13 1997-10-20 Хасанов Ильмер Юсупович Способ получения листового проката

Also Published As

Publication number Publication date
RU2200601C2 (ru) 2003-03-20
DK1219324T3 (da) 2010-04-06
DE59803209D1 (de) 2002-04-04
JP2001510814A (ja) 2001-08-07
CN1198669C (zh) 2005-04-27
HK1047900B (zh) 2010-09-03
US6645449B2 (en) 2003-11-11
LU90191A7 (de) 1999-06-24
EP1219324B1 (fr) 2009-12-23
EP0999878A1 (fr) 2000-05-17
WO1999004861A1 (fr) 1999-02-04
ATE213657T1 (de) 2002-03-15
ES2172185T3 (es) 2002-09-16
AU747426B2 (en) 2002-05-16
CA2295907C (fr) 2005-10-18
AU8862698A (en) 1999-02-16
HK1047900A1 (zh) 2003-03-14
PT1219324E (pt) 2010-03-25
DE59814426D1 (de) 2010-02-04
ATE452689T1 (de) 2010-01-15
ES2337769T3 (es) 2010-04-29
EP0999878B1 (fr) 2002-02-27
DK0999878T3 (da) 2002-06-10
JP4208412B2 (ja) 2009-01-14
PT999878E (pt) 2002-07-31
BR9810858A (pt) 2000-07-25
EP1219324A3 (fr) 2004-04-07
US20030149325A1 (en) 2003-08-07
CA2295907A1 (fr) 1999-02-04
CN1265043A (zh) 2000-08-30

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