EP0635282B1 - Method for treatment of residual material of incinerators - Google Patents
Method for treatment of residual material of incinerators Download PDFInfo
- Publication number
- EP0635282B1 EP0635282B1 EP94108750A EP94108750A EP0635282B1 EP 0635282 B1 EP0635282 B1 EP 0635282B1 EP 94108750 A EP94108750 A EP 94108750A EP 94108750 A EP94108750 A EP 94108750A EP 0635282 B1 EP0635282 B1 EP 0635282B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- slag
- wash water
- water
- flue gas
- washing
- 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.)
- Revoked
Links
Images
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
- A62D3/36—Detoxification by using acid or alkaline reagents
-
- 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
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
-
- 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
- A62D2101/08—Toxic combustion residues, e.g. toxic substances contained in fly ash from waste incineration
-
- 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
- A62D2101/40—Inorganic substances
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
-
- 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
- A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40
Definitions
- the invention relates to a method for treating residues in waste incineration plants, in which, in addition to slag, hydrogen chloride is also obtained from the flue gas scrubbing.
- Filter dust is classified as hazardous waste due to the high content of heavy metals and organic materials.
- a recycling e.g. in sidewalk construction, but is possible by glazing the dust.
- Gypsum can be produced from sulfur dioxide as a material by skillful process control.
- the processing of the hydrogen chloride is problematic since extremely complex processes with multi-stage rectification are necessary to produce usable hydrochloric acid of technical quality.
- the slag is contaminated with heavy metals and is therefore often disposed of in an orderly manner.
- the invention has for its object to provide a method for treating waste in waste incineration plants, which leads to a practically heavy metal-free end product with good hydraulic properties.
- This object is achieved according to the invention in a process of the type mentioned at the outset by washing the slag with the crude hydrochloric acid from the wet scrubber of the flue gas cleaning system after prior mechanical comminution, and reducing the chloride content in the slag treated in this way by washing with water.
- the heavy metal chlorides in both wash waters are precipitated by adding a precipitant, preferably soda.
- the invention is based on the following considerations, which have been confirmed by practical tests:
- hydrochloric acid is now suitable for such a washing process, since this acid is obtained in any case in the flue gas cleaning of the system.
- Alkaline material such as CaO
- a major advantage of the invention is that in a single process, two critical residues, heavy metal-containing slag and crude are economically available Hydrochloric acid, can be eliminated or converted into reusable material.
- the end products of this treatment are slag in building material quality and usable table salt.
- slag is discharged from the incinerator 1 of a waste incineration plant by means of tappet deslagger 2 through a water bath from the furnace 1.
- the so-called coarse or oversize is separated in a mechanical separation device 3.
- Coarse or oversize are not or incompletely burned components of the waste with diameters of approximately 250 mm or larger.
- the iron fraction is then separated in a magnetic separator 4, which can be done, for example, by overband magnets.
- the grain fraction between about 30 and 250 mm leaving the magnetic separator is mechanically comminuted in a mill 5, for example a hammer mill, to a grain size of 32 mm and less.
- the grain fraction prepared in this way then passes into a first scrubber, the acid scrubber 6, where it is washed with crude hydrochloric acid.
- An acid scrubber suitable for this purpose includes, for example, a stainless steel tank with an integrated agitator.
- the crude hydrochloric acid comes from the wet scrubber 7 of the flue gas cleaning system which is already present in waste incineration plants 8. This washing process predominantly forms soluble compounds which can be separated from the slag by a known solid-liquid separation.
- the residue obtained in this way has a not inconsiderable residue of chlorides, which is reduced by washing with water in a second washer 9, the water washer.
- the separation of slag and washing water loaded with chlorides takes place, as in the first washing process, by means of a solid-liquid separation which is known per se.
- the slag separated in the previous process step can now optionally in a lime stage 10 with lime, e.g. in the form of milk of lime. This measure serves to stabilize the slag. Traces of heavy metal remaining in the slag are immobilized in this way and are no longer leached out.
- Soda Na 2 (CO 3 )
- Soda Na 2 (CO 3 )
- MeCO 3rd + 2 NaCl
- the heavy metal concentration can be reduced very deeply by adding sulfidic reagents, for example trimercaptotriazine (trade name TMT15).
- sulfidic reagents for example trimercaptotriazine (trade name TMT15).
- Recyclable table salt e.g. NaCl for chlor-alkali electrolysis.
Landscapes
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Processing Of Solid Wastes (AREA)
- Treating Waste Gases (AREA)
Description
Die Erfindung bezieht sich auf ein Verfahren zur Reststoffbehandlung in Müllverbrennungsanlagen, in welchen neben Schlacke unter anderem auch Chlorwasserstoff aus der Rauchgaswäsche anfällt.The invention relates to a method for treating residues in waste incineration plants, in which, in addition to slag, hydrogen chloride is also obtained from the flue gas scrubbing.
Bei der Verbrennung von Siedlungsabfällen fallen im Prozess verschiedene Reststofffraktionen an: Schlacke (250 kg/Tonne Müll), Filterstaub (20 - 30 kg/Tonne Müll), Chlorwasserstoff (7 kg/Tonne Müll) aus dem Nasswäscher der Rauchgasreinigungsanlage und Schwefeldioxid (2 kg/Tonne Müll). Eine Verwendung dieser Reststoffe ist ohne vorgängige Aufarbeitung nicht möglich.When municipal waste is incinerated, various residual material fractions occur in the process: slag (250 kg / ton of waste), filter dust (20 - 30 kg / ton of waste), hydrogen chloride (7 kg / ton of waste) from the wet scrubber of the flue gas cleaning system and sulfur dioxide (2 kg / Ton of garbage). It is not possible to use these residues without previous work-up.
Filterstaub ist wegen des hohen Gehalts an Schwermetallen und organischen Materialien als Sondermüll einzustufen. Eine Verwertung, z.B. im Gehwegebau, ist jedoch durch Verglasung des Staubs möglich. Aus Schwefeldioxid kann durch geschickte Prozessführung Gips als Werkstoff erzeugt werden. Problematisch ist die Aufarbeitung des Chlorwasserstoffs, da zur Herstellung von verwertbarer Salzsäure in technischer Qualität extrem aufwendige Verfahren mit mehrstufiger Rektifikation notwendig sind. Die Schlacke schliesslich ist mit Schwermetallen belastet und wird daher heute oftmals geordnet deponiert.Filter dust is classified as hazardous waste due to the high content of heavy metals and organic materials. A recycling, e.g. in sidewalk construction, but is possible by glazing the dust. Gypsum can be produced from sulfur dioxide as a material by skillful process control. The processing of the hydrogen chloride is problematic since extremely complex processes with multi-stage rectification are necessary to produce usable hydrochloric acid of technical quality. Finally, the slag is contaminated with heavy metals and is therefore often disposed of in an orderly manner.
Verschiedene Verfahren zur Reststoffbehandlung in Müllverbrennungsanlagen sind aus EP-A-0 538 598 und DE-A-40 35 042 bekanntVarious methods for treating waste in waste incineration plants are known from EP-A-0 538 598 and DE-A-40 35 042
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Reststoffbehandlung in Müllverbrennungsanlagen anzugeben, das zu einem praktisch schwermetallfreien Endprodukt mit guten hydraulischen Eigenschaften führt.The invention has for its object to provide a method for treating waste in waste incineration plants, which leads to a practically heavy metal-free end product with good hydraulic properties.
Diese Aufgabe wird bei einem Verfahren der eingangs genannten Gattung erfindungsgemäss dadurch gelöst, dass die Schlacke nach vorgängiger mechanischer Zerkleinerung mit der rohen Salzsäure aus dem Nasswäscher der Rauchgasreinigungsanlage gewaschen wird, der Chloridgehalt in der so behandelten Schlacke durch Waschen mit Wasser reduziert wird. Die Schwermetallchloride in beiden Waschwassern werden durch Zugabe eines Fällungsmittels, vorzugsweise Soda, ausgefällt.This object is achieved according to the invention in a process of the type mentioned at the outset by washing the slag with the crude hydrochloric acid from the wet scrubber of the flue gas cleaning system after prior mechanical comminution, and reducing the chloride content in the slag treated in this way by washing with water. The heavy metal chlorides in both wash waters are precipitated by adding a precipitant, preferably soda.
Der Erfindung liegen dabei die folgenden, durch praxisnahe Versuche bestätigte Ueberlegungen zugrunde:The invention is based on the following considerations, which have been confirmed by practical tests:
Die Reduzierung des Schwermetallgehalts in Schlacken aus Müllverbrennungsanlagen ist durch Waschen mit Wasser allein nicht möglich. Schlacke reagiert wegen ihres Gehalts an Calciumoxid (CaO) alkalisch.
Aus diesem Grunde werden beim Eluieren mit Wasser unlösliche Schwermetallverbindungen gebildet
Ein ausreichend hoher Gehalt an alkalisch wirkenden Substanzen ist erwünscht, da auf diese Weise Schwermetall-Ionen immobilisiert werden. Ausserdem verleiht CaO der Schlacke gute Baustoffeigenschaften. Für die Alkalinität sind in den einschlägigen Verordnungen Mindestwerte festgelegt. So ist beispielsweise in der "Schweizerischen technischen Verordnung über Abfälle" (TVA) ein Mindestwert von 1 mol/kg vorgeschrieben, was umgerechnet auf CaO 2,8% sind.A sufficiently high content of alkaline substances is desirable because heavy metal ions are immobilized in this way. In addition, CaO gives the slag good building material properties. For the alkalinity are in the relevant Regulations set minimum values. For example, the "Swiss Technical Ordinance on Waste" (TVA) stipulates a minimum value of 1 mol / kg, which is converted to CaO 2.8%.
Bei einem sauren Waschprozess bilden sich überwiegend lösliche Verbindungen, die durch eine Fest-Flüssig-Separation von der Schlacke abgetrennt werden können. Für einen solchen Waschprozess bietet sich nun erfindungsgemäss Salzsäure an, da diese Säure ohnehin in der Rauchgasreinigung der Anlage anfällt.In an acidic washing process, predominantly soluble compounds are formed, which can be separated from the slag by a solid-liquid separation. According to the invention, hydrochloric acid is now suitable for such a washing process, since this acid is obtained in any case in the flue gas cleaning of the system.
Schwermetalle, die als Oxide vorliegen, werden so in eine lösliche Form überführt.
Alkalisches Material, wie CaO, wird durch eine saure Wäsche zum Teil neutralisiert.
Wie Laboruntersuchungen ergeben haben, kann die gesamte Alkalinität nur dann zerstört werden, wenn das Material sehr klein gemahlen vorliegt. In diesem Fall müsste der Anteil CaO, der beim Waschprozess neutralisiert wird, anschliessend zur Stabilisierung des Reststoffes wieder zugefügt werden. Wird also das Ausgangsprodukt nur vergleichsweise grob zerkleinert, z.B. auf Korngrössen zwischen 5 und 30 mm in einer Hammermühle, entfällt die Notwendigkeit, den Reststoff zu stabilisieren. Dies bedeutet, dass eine saure Wäsche auch mit einer kleineren als der theoretisch aus der Gesamtalkalinität berechneten Menge an Salzsäure möglich ist.As laboratory studies have shown, the total alkalinity can only be destroyed if the material is ground very small. In this case, the proportion of CaO that is neutralized in the washing process would then have to be added again to stabilize the residue. So if the starting product is only crushed comparatively roughly, e.g. on grain sizes between 5 and 30 mm in a hammer mill, there is no need to stabilize the residue. This means that acidic washing is also possible with a smaller amount of hydrochloric acid than that theoretically calculated from the total alkalinity.
Ein wesentlicher Vorteil der Erfindung besteht darin, dass in einem einzigen Verfahren auf wirtschaftliche Weise zwei kritische Reststoffe, schwermetallhaltige Schlacke und rohe Salzsäure, beseitigt bzw. in wiederverwendbares Material umgewandelt werden können. Endprodukte dieser Behandlung sind Schlacke in Baustoffgualität und verwertbares Kochsalz.A major advantage of the invention is that in a single process, two critical residues, heavy metal-containing slag and crude are economically available Hydrochloric acid, can be eliminated or converted into reusable material. The end products of this treatment are slag in building material quality and usable table salt.
Ein Ausführungsbeispiel der Erfindung sowie die damit erzielbaren Vorteile werden nachfolgend anhand der Zeichnung näher erläutert.An exemplary embodiment of the invention and the advantages which can be achieved thereby are explained in more detail below with reference to the drawing.
In der Zeichnung ist ein Ausführungsbeispiel der Erfindung schematisch in Form eines Flussdiagramms schematisch dargestellt.In the drawing, an embodiment of the invention is shown schematically in the form of a flow chart.
Gemäss der Figur wird Schlacke aus dem Verbrennungsofen 1 einer Müllverbrennungsanlage durch Stösselentschlacker 2 durch ein Wasserbad hindurch aus dem Ofen 1 ausgetragen. In einem ersten Verfahrensschritt wird in einer mechanischen Trennvorrichtung 3 das sogenannte Grob- oder Ueberkorn abgetrennt. Grob- oder Ueberkorn sind nicht oder unvollständig verbrannte Bestandteile des Mülls mit Durchmessern von etwa 250 mm oder grösser. Danach schliesst sich in einem Magnetabscheider 4 die Abtrennung der Eisenfraktion an, was z.B. durch Ueberbandmagnete erfolgen kann. Die den Magnetscheider verlassende Kornfraktion zwischen etwa 30 bis 250 mm wird mechanisch in einer Mühle 5, z.B. einer Hammermühle, zerkleinert, und zwar auf Korngrössen von 32 mm und weniger. Die derart aufbereitete Kornfraktion gelangt dann in einen ersten Wäscher, dem Säurewäscher 6, wo sie mit roher Salzsäure gewaschen wird. Ein für diesen Zweck geeigneter Säurewäscher umfasst beispielsweise einen Edelstahltank mit integriertem Rührwerk. Die rohe Salzsäure kommt vom Nasswäscher 7 der bei Müllverbrennungsanlagen ohnehin vorhandenen Rauchgasreinigungsanlage 8. Bei diesem Waschprozess bilden sich überwiegend lösliche Verbindungen, die durch eine an sich bekannte Fest-Flüssig-Separation von der Schlacke abgetrennt werden können.According to the figure, slag is discharged from the
Der so erhaltene Rückstand weist einen nicht unerheblichen Rückstand an Chloriden auf, welcher durch Waschen mit Wasser in einem zweiten Wäscher 9, dem Wasserwäscher, reduziert wird. Die Separation von Schlacke und mit Chloriden beladenem Waschwasser erfolgt wie beim ersten Waschvorgang durch eine an sich bekannte Fest-Flüssig-Separation.The residue obtained in this way has a not inconsiderable residue of chlorides, which is reduced by washing with water in a
Die im vorangegangenem Verfahrensschritt separierte Schlacke kann nun optional in einer Kalkstufe 10 mit Kalk, z.B. in Form von Kalkmilch, weiterbehandelt werden. Diese Massnahme dient zur Stabilisierung der Schlacke. In der Schlacke verbliebene Schwermetallspuren werden auf diese Weise immobilisiert und nicht weiter ausgelaugt.The slag separated in the previous process step can now optionally in a
Die Waschwässer aus dem Säurewäscher 6 und dem Wasserwäscher 9 - sie enthalten als wesentliche Verunreinigungen Schwermetallchloride (MeCl2) und Calciumchlorid (CaCl2) - werden einer Abwasserreinigungsanlage 11 zugeführt und dort weiterbehandelt. Vorzugsweise wird dabei Soda (Na2(CO3)) als Fällungsmittel verwendet, mit welcher eine Neutralisierung und gleichzeitige Ausfällung möglich ist:
Die Schwermetallkonzentration kann durch Zugabe sulfidischer Reagenzien, z.B. Trimercaptotriazin (Handelsname TMT15) sehr tief herabgesetzt werden.The heavy metal concentration can be reduced very deeply by adding sulfidic reagents, for example trimercaptotriazine (trade name TMT15).
Aus der verbleibenden Lösung kann verwertbares Kochsalz, z.B. NaCl für die Chloralkali-Elektrolyse, kristallisiert werden.Recyclable table salt, e.g. NaCl for chlor-alkali electrolysis.
In einer typischen Müllverbrennungsanlage fallen pro Tonne Müll 250 bis 300 kg Schlacke an. Messungen haben gezeigt, dass die Alkalinität - berechnet als CaO - zwischen 10 und 13% beträgt. Dies sind umgerechnet auf die Stoffmenge zwischen 800 und 1000 mol alkalische Aequivalente pro Tonne Müll. In der Rauchgasreinigungsanlage fallen ca. 7 kg HCl entsprechend etwa 200 mol Säure an.In a typical waste incineration plant, 250 to 300 kg of slag are produced per ton of waste. Measurements have shown that the alkalinity - calculated as CaO - is between 10 and 13%. These are converted to the amount of substance between 800 and 1000 mol of alkaline equivalents per ton of waste. In the flue gas cleaning system, approx. 7 kg of HCl are produced, corresponding to around 200 mol of acid.
Eingehende Laborversuche haben gezeigt, dass auch mit diesen Stoffmengen-Verhältnissen der pH-Wert beim Waschen (in der Säurestufe) im sauren liegt. Schwermetalle, die an den Oberflächen der Schlackekörner sitzen, werden durch den Waschprozess wirkungsvoll herausgelöst.In-depth laboratory tests have shown that even with these substance quantity ratios, the pH during washing (in the acid level) is acidic. Heavy metals that sit on the surfaces of the slag grains are effectively removed by the washing process.
- 11
- VerbrennungsofenIncinerator
- 22nd
- StösselentschlackerPestle purifier
- 33rd
- TrennvorrichtungSeparator
- 44th
- MagnetscheiderMagnetic separator
- 55
- HammermühleHammer mill
- 66
- SäurewäscherAcid scrubber
- 77
- Nasswäscher von 8Wet scrubber from 8
- 88th
- RauchgasreinigungsanlageFlue gas cleaning system
- 99
- WasserwäscherWater washer
- 1010th
- KalkstufeLime scale
- 1111
- AbwasserreinigungsanlageWastewater treatment plant
Claims (4)
- Process for residue treatment in refuse incineration plants in which, in addition to slag, hydrogen chloride arises from the flue gas scrubbing, characterized in that the slag, after prior mechanical comminution, is washed with the crude hydrochloric acid from the wet scrubber of the flue gas purification plant, and the chloride content in the slag thus treated is reduced by washing with water.
- Process according to Claim 1, characterized in that after the separation of slag and wash water, the metal chlorides are precipitated in both wash waters by addition of soda.
- Process according to Claim 2, characterized in that, for the further reduction of the heavy metal concentration in the wash water, sulphide reagents, preferably trimercaptotriazine, are added to the wash water.
- Process according to one of Claims 1 to 3, characterized in that, after the separation of slag and wash water, the slag is treated with lime, preferably in the form of milk of lime, for the purpose of immobilizing the traces of heavy metals remaining in the slag.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4324796 | 1993-07-23 | ||
DE4324796A DE4324796A1 (en) | 1993-07-23 | 1993-07-23 | Process for the treatment of residues in waste incineration plants |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0635282A1 EP0635282A1 (en) | 1995-01-25 |
EP0635282B1 true EP0635282B1 (en) | 1997-04-02 |
Family
ID=6493565
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94108750A Revoked EP0635282B1 (en) | 1993-07-23 | 1994-06-08 | Method for treatment of residual material of incinerators |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0635282B1 (en) |
DE (2) | DE4324796A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2749772B1 (en) * | 1996-06-14 | 1998-10-16 | Rhone Poulenc Chimie | REMOVAL OF HEAVY METALS FROM WASTE INCINERATION WASTE OR GLASS OVEN |
DE19747504A1 (en) * | 1997-10-28 | 1999-04-29 | Babcock Anlagen Gmbh | Process for the treatment of combustion residues |
AT5356U1 (en) * | 2001-07-16 | 2002-06-25 | Uv & P Umweltman Verfahrenstec | METHOD FOR IMMOBILIZING COMBUSTION RESIDUES |
JP3795022B2 (en) * | 2002-03-27 | 2006-07-12 | 三菱重工業株式会社 | Method for improving the characteristics of combustion residues produced in a combustion plant and method for treating the residues |
CN102416288B (en) * | 2011-12-06 | 2015-01-07 | 中南大学 | Method for separating and recovering valuable metal chloride and hydrogen chloride from high-temperature chloridizing metallurgy flue gas |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3324133C2 (en) * | 1983-06-07 | 1994-06-16 | Kernforschungsz Karlsruhe | Process for cleaning flue gas |
DE3320466C2 (en) * | 1983-06-07 | 1987-04-30 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe | Process for cleaning flue gas |
DE3702306A1 (en) * | 1987-01-27 | 1988-08-04 | Hoelter Heinz | Process for separating off heavy metals from the exhaust gases of furnaces |
DE3812986A1 (en) * | 1988-04-19 | 1989-11-02 | Landesgewerbeanstalt Bayern Lg | Decontamination process for soils contaminated by heavy metal, especially for mercury |
DE3918292C2 (en) * | 1988-10-04 | 1993-11-25 | Steinmueller Gmbh L & C | Process for the treatment of fly ash containing heavy metals from the flue gas of incineration plants, in particular waste or waste incineration plants |
DE4035042A1 (en) * | 1990-11-05 | 1992-05-07 | Westfael Elekt Werke | Working-up flue-ash obtd. from exhaust gas cleaning - by forming suspension with sulphuric acid and recovering calcium sulphate as filter cake |
AT396104B (en) * | 1991-10-25 | 1993-06-25 | Waagner Biro Ag | METHOD FOR CONVERTING WATER-SOLUBLE INTO HEAVY OR NON-SOLUBLE METAL COMPOUNDS |
-
1993
- 1993-07-23 DE DE4324796A patent/DE4324796A1/en not_active Withdrawn
-
1994
- 1994-06-08 DE DE59402284T patent/DE59402284D1/en not_active Revoked
- 1994-06-08 EP EP94108750A patent/EP0635282B1/en not_active Revoked
Also Published As
Publication number | Publication date |
---|---|
DE4324796A1 (en) | 1995-01-26 |
DE59402284D1 (en) | 1997-05-07 |
EP0635282A1 (en) | 1995-01-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0110240B1 (en) | Process and apparatus for the removal of heavy metals from waste water | |
DE69500608T2 (en) | Treatment of sludge and waste containing sulfates and heavy metals by sulfate reducing bacteria and lactobacilli | |
DE69019643T2 (en) | Process and system for the disposal of aqueous sewage sludge. | |
DE3634650A1 (en) | METHOD FOR DISPOSAL OF POLLUTANT-laden SUBSTANCES AND USE OF THE PRODUCT PRODUCED THEREOF | |
DE69802281T2 (en) | METHOD FOR TREATING RESIDUES OF CLEANING COMBUSTION COMBUSTION GASES AND INDUSTRIAL WASTE | |
EP0635282B1 (en) | Method for treatment of residual material of incinerators | |
DE102008018854B4 (en) | Process for the treatment of mine waters | |
EP3868905B1 (en) | Method and system for implementing a limestone-carbon dioxide cycle in iron and steel production | |
DE102004044291B4 (en) | Process for purifying flue gas from an incineration plant containing HCI, SO2 and Hg and flue gas purification plant | |
DE3805722C1 (en) | Process for purifying glass industry waste waters | |
DE3626885C2 (en) | ||
DE4307468A1 (en) | Process for precipitation of heavy metals, uranium and toxic metals in the rehabilitation of mining installations, in particular from contaminated waters | |
WO2001008753A1 (en) | Mixture for the treatment of waste materials | |
DE2808012A1 (en) | PROCEDURE FOR NEUTRALIZING ACID LIQUIDS | |
DE4318535C2 (en) | Processes for the preparation, stabilization, inertization, detoxification, landfill and disposal of mineral waste, residues and residues as well as for the recovery of metals and for the production of soil substrates | |
DE69707800T2 (en) | Process for solidifying the cleaning residues of waste incineration gases and industrial waste | |
DE2160312A1 (en) | Coagulating lacquer impurities in effluent waters - - with calcium chloride obtained from waste materials | |
DE102007006916A1 (en) | Treatment or stabilization of residues comprising boiler ashes, silicate filter dust from combustion plant and/or sewage sludge combustion residues, comprises reacting the residues with a calcium sulfite-containing additives and water | |
EP0884092A1 (en) | Process for removing sulfur dioxide from an exhaust gas | |
EP0695912B1 (en) | Treatment process for residual materials in incinerator plants | |
DE4444033A1 (en) | Detoxification of builder's rubble, soil etc. contaminated by chromate | |
DE19522704A1 (en) | Processing incinerator slag and filter dust | |
DE4015489A1 (en) | Freeing waste material from heavy metals and dioxin(s) - by treating aq. slurry with active gas mixt. and precipitating heavy metals | |
DE4229662C2 (en) | Process for the removal of mercury from waste water from flue gas scrubbers | |
EP3000522A1 (en) | Method for treating waste gases |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): CH DE FR LI NL |
|
17P | Request for examination filed |
Effective date: 19950714 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
17Q | First examination report despatched |
Effective date: 19960528 |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): CH DE FR LI NL |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 59402284 Country of ref document: DE Date of ref document: 19970507 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: ASEA BROWN BOVERI AG |
|
ET | Fr: translation filed | ||
PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
26 | Opposition filed |
Opponent name: VON ROLL UMWELTTECHNIK AG Effective date: 19971231 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: VON ROLL UMWELTTECHNIK AG |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19980518 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19980520 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19980527 Year of fee payment: 5 |
|
PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
RDAH | Patent revoked |
Free format text: ORIGINAL CODE: EPIDOS REVO |
|
RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
27W | Patent revoked |
Effective date: 19980926 |
|
NLR2 | Nl: decision of opposition |