EP1219324B1 - Verfahren zur Entsorgung von halogenierten und nicht halogenierten Abfallstoffen - Google Patents

Verfahren zur Entsorgung von halogenierten und nicht halogenierten Abfallstoffen Download PDF

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

Definitions

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

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)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Silicon Compounds (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
EP02004190A 1997-07-23 1998-07-20 Verfahren zur Entsorgung von halogenierten und nicht halogenierten Abfallstoffen Expired - Lifetime EP1219324B1 (de)

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
LU90191A LU90191A7 (de) 1997-07-23 1997-12-24 Verfahren zur entsorgung von halogenierten und nicht halogenierten abfallstoffen
LU90191 1997-12-24
EP98940244A EP0999878B1 (de) 1997-07-23 1998-07-20 Verfahren zur entsorgung von halogenierten und nicht halogenierten abfallstoffen

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP98940244A Division EP0999878B1 (de) 1997-07-23 1998-07-20 Verfahren zur entsorgung von halogenierten und nicht halogenierten abfallstoffen

Publications (3)

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

Family

ID=26640365

Family Applications (2)

Application Number Title Priority Date Filing Date
EP02004190A Expired - Lifetime EP1219324B1 (de) 1997-07-23 1998-07-20 Verfahren zur Entsorgung von halogenierten und nicht halogenierten Abfallstoffen
EP98940244A Expired - Lifetime EP0999878B1 (de) 1997-07-23 1998-07-20 Verfahren zur entsorgung von halogenierten und nicht halogenierten abfallstoffen

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP98940244A Expired - Lifetime EP0999878B1 (de) 1997-07-23 1998-07-20 Verfahren zur entsorgung von halogenierten und nicht halogenierten abfallstoffen

Country Status (16)

Country Link
US (1) US6645449B2 (enExample)
EP (2) EP1219324B1 (enExample)
JP (1) JP4208412B2 (enExample)
CN (1) CN1198669C (enExample)
AT (2) ATE213657T1 (enExample)
AU (1) AU747426B2 (enExample)
BR (1) BR9810858A (enExample)
CA (1) CA2295907C (enExample)
DE (2) DE59803209D1 (enExample)
DK (2) DK1219324T3 (enExample)
ES (2) ES2337769T3 (enExample)
HK (1) HK1047900B (enExample)
LU (1) LU90191A7 (enExample)
PT (2) PT1219324E (enExample)
RU (1) RU2200601C2 (enExample)
WO (1) WO1999004861A1 (enExample)

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
US4631183A (en) 1985-06-25 1986-12-23 Hydro-Quebec Process for the destruction of toxic organic products
DE3623492A1 (de) 1986-07-11 1988-01-21 Hagenmaier Hans Paul Verfahren zum abbau von halogenierten aromaten
ATE118688T1 (de) 1986-11-27 1995-03-15 Suppan Friedrich Verfahren und anlage zur energiegewinnung aus giftigen abfallstoffen bei deren gleichzeitiger entsorgung.
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
US5280757A (en) * 1992-04-13 1994-01-25 Carter George W Municipal solid waste disposal process
US5222448A (en) * 1992-04-13 1993-06-29 Columbia Ventures Corporation Plasma torch furnace processing of spent potliner from aluminum smelters
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
AU8862698A (en) 1999-02-16
ATE213657T1 (de) 2002-03-15
ES2172185T3 (es) 2002-09-16
US6645449B2 (en) 2003-11-11
BR9810858A (pt) 2000-07-25
EP1219324A3 (de) 2004-04-07
HK1047900A1 (zh) 2003-03-14
LU90191A7 (de) 1999-06-24
DK0999878T3 (da) 2002-06-10
JP2001510814A (ja) 2001-08-07
US20030149325A1 (en) 2003-08-07
DE59803209D1 (de) 2002-04-04
RU2200601C2 (ru) 2003-03-20
AU747426B2 (en) 2002-05-16
CN1265043A (zh) 2000-08-30
EP0999878B1 (de) 2002-02-27
EP1219324A2 (de) 2002-07-03
WO1999004861A1 (de) 1999-02-04
PT1219324E (pt) 2010-03-25
ATE452689T1 (de) 2010-01-15
ES2337769T3 (es) 2010-04-29
CA2295907A1 (en) 1999-02-04
PT999878E (pt) 2002-07-31
DE59814426D1 (de) 2010-02-04
DK1219324T3 (da) 2010-04-06
CN1198669C (zh) 2005-04-27
EP0999878A1 (de) 2000-05-17
HK1047900B (zh) 2010-09-03
CA2295907C (en) 2005-10-18
JP4208412B2 (ja) 2009-01-14

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