WO1994005603A1 - Procede d'elimination de metaux lourds, notamment de mercure, contenus dans les eaux usees provenant de laveurs de gaz de fumee - Google Patents

Procede d'elimination de metaux lourds, notamment de mercure, contenus dans les eaux usees provenant de laveurs de gaz de fumee Download PDF

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Publication number
WO1994005603A1
WO1994005603A1 PCT/EP1993/002254 EP9302254W WO9405603A1 WO 1994005603 A1 WO1994005603 A1 WO 1994005603A1 EP 9302254 W EP9302254 W EP 9302254W WO 9405603 A1 WO9405603 A1 WO 9405603A1
Authority
WO
WIPO (PCT)
Prior art keywords
heavy metals
mercury
oxidizing agent
flue gas
separated
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.)
Ceased
Application number
PCT/EP1993/002254
Other languages
German (de)
English (en)
Inventor
Hermann Winkler
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.)
Steag GmbH
Original Assignee
Steag GmbH
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
Application filed by Steag GmbH filed Critical Steag GmbH
Publication of WO1994005603A1 publication Critical patent/WO1994005603A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing

Definitions

  • the invention relates to a method for removing heavy metals, in particular mercury from waste water coming from flue gas scrubbers.
  • the exhaust gases from combustion power plants contain pollutants that must be removed in accordance with today's environmental regulations.
  • Most new combustion power plants today are therefore equipped with flue gas cleaning systems, which are primarily intended to remove sulfur dioxide, nitrogen oxides and hydrogen halide contained in the exhaust gas, but also to remove heavy metals.
  • flue gas cleaning systems which are primarily intended to remove sulfur dioxide, nitrogen oxides and hydrogen halide contained in the exhaust gas, but also to remove heavy metals.
  • the invention is therefore based on the object of making the sludges from flue gas scrubbers heavy metal - in particular mercury-free - in order to reduce the amount of mercury-containing waste to be deposited and thus to reduce the costs of the overall process.
  • This object is achieved according to the invention in that, in a process for removing heavy metals, in particular mercury, from waste water coming from flue gas scrubbers, firstly the raw waste water carrying solids coming from the flue gas scrubber is treated with an oxidizing agent in excess based on the heavy metal content, whereby the heavy metals are oxidized and go into solution ionically, secondly remaining solids are separated and washed and thirdly the heavy metals dissolved are bound and separated from the waste water treated with oxidizing agent.
  • the method offers the advantage that the disruptive mercury is converted practically quantitatively into the readily water-soluble divalent form before the solids carried along in the raw sewage are separated off, so that the sludge separated off in the course of the sewage treatment is free or low in mercury and, for example can be supplied to a combustion.
  • the mercury which is quantitatively in solution can be separated off either with the aid of an ion exchanger or by precipitation of an insoluble mercury compound.
  • sulfide precipitation can be carried out for this purpose.
  • a water-soluble sulfide such as sodium sulfide or sodium hydrogen sulfide is preferably used for the precipitation.
  • the wastewater can be subjected to a further fine cleaning step, preferably a lime milk treatment, after separating the entrained solids and after separating the bound heavy metals in the form of heavy metal salts freed separated solids can then be incinerated.
  • a further fine cleaning step preferably a lime milk treatment
  • a hypohalite preferably NaOCl
  • chlorine or alternatively oxygen preferably in the presence of divalent copper ions, can also be used.
  • Fig. 2 is a schematic representation of the sequence of cleaning steps within the overall system.
  • raw water coming from the FGD scrubber which carries solids with it, is fed via a line 2 into a stirred tank 4, in which the raw waste water is treated with an oxidizing agent.
  • an oxidizing agent 6 NaOCl solution is fed in, specifically 2.5 l
  • the mercury-free or very low-mercury sludge can then be returned via line 18 and burned.
  • the heavy metal contaminated waste water from this washing process is returned via line 20 upstream of the round thickener 10 by being fed into line 8.
  • the wastewater treated with the oxidizing agent and freed from insoluble solids is now passed via line 22 at a pH of still about 6 over an ion exchange resin in column 24, where in particular the mercury ions are bound and retained with other heavy metal ions reacting similarly.
  • Qecksilber as a heavy metal-containing raw sewage is here acting selectively resin ilberionen on Quecks' is used (for example Lewatit TP 214).
  • the loaded exchange resin of the column 24 contaminated with mercury ions is exchanged for fresh resin at certain intervals and must then be deposited. However, this amount of resin is significantly less than the amount of sludge removed from line 18.
  • the cleaned wastewater freed from mercury is then fed to a further fine cleaning, ie residual metal precipitation.
  • the wastewater purified so far is passed via line 26 into a stirred tank 28, which can be supplied with lime milk via line 30.
  • the pH in this process step is adjusted to approximately 8.5.
  • the mixture leaving the boiler 28 is passed through line 32 to a filtration, ie supplied to a separation step in round thickener 34, which the pure water finally obtained leaves via line 36.
  • the remaining lime cake is combined via line 38 with the sludge made in line 12, which has been freed from mercury and subsequently washed together with this in scrubber 14 and fed to the combustion via line 18.
  • Na2S precipitation can also be carried out, the process engineering handling of which is known as such and which therefore need not be shown separately here.
  • the raw sewage in boiler 4 can be treated with chlorine or with oxygen.
  • 0.2 to 0.4 g of Cu 2+ / 1 are added as a catalyst. Then air is blown in via a gas supply line instead of line 6 for 30 minutes, the air flow being set to 1.1 m * air per hour and m ⁇ container content.
  • FIG. 2 shows the sequence of the cleaning steps in connection with the overall power plant.
  • the flue gas drawn off from a power plant boiler 10 is first fed to a selective catalytic reduction in the SCR 20, then passes through the electrostatic precipitator 30 and passes through the flue gas desulfurization system 40. From this, the cleaned exhaust gas leaves the system via line 46 and is discharged to the outside .
  • the flue gas desulfurization in the REA 40 produces gypsum, which is discharged via line 42, and the raw waste water from the REA scrubber, which is fed to the associated waste water treatment 50.
  • the mercury-containing waste is reduced to a minimum.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

L'invention concerne un procédé visant à éliminer le mercure contenu dans les eaux usées provenant d'installations d'épuration de gaz de fumée. L'eau brute qui sort du laveur de gaz de fumée et entraîne avec elle des matières solides, est traitée avec un oxydant en surplus, afin de réduire quantitativement le mercure à sa forme bivalente soluble (4). Les matières solides restantes ne peuvent être séparées et lavées (10; 14) qu'après cette étape. Le mercure passé dans la solution est lié par l'intermédiaire d'une résine échangeuse d'ions et est séparé (24). Ce procédé permet d'éliminer pratiquement tout le mercure contenu dans les boues qui retombent en grandes quantités dans les installations d'épuration de gaz de fumée, tandis que la proportion de déchets spéciaux contenant du mercure à évacuer à la décharge est maintenue réduite.
PCT/EP1993/002254 1992-09-04 1993-08-21 Procede d'elimination de metaux lourds, notamment de mercure, contenus dans les eaux usees provenant de laveurs de gaz de fumee Ceased WO1994005603A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19924229662 DE4229662C2 (de) 1992-09-04 1992-09-04 Verfahren zur Entfernung von Quecksilber aus aus Rauchgaswäschern stammenden Abwässern
DEP4229662.5 1992-09-04

Publications (1)

Publication Number Publication Date
WO1994005603A1 true WO1994005603A1 (fr) 1994-03-17

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/002254 Ceased WO1994005603A1 (fr) 1992-09-04 1993-08-21 Procede d'elimination de metaux lourds, notamment de mercure, contenus dans les eaux usees provenant de laveurs de gaz de fumee

Country Status (2)

Country Link
DE (1) DE4229662C2 (fr)
WO (1) WO1994005603A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19800699A1 (de) 1998-01-10 1999-07-15 Bayer Ag Entfernung von Schwermetallionen aus wäßrigen Medien
CN1303018C (zh) * 2003-11-21 2007-03-07 同济大学 污泥土地利用时所含重金属的处理方法
ITMI20062524A1 (it) * 2006-12-28 2008-06-29 Itea Spa Processo per la purificazione di fumi di combustione

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617563A (en) * 1968-08-19 1971-11-02 Res Ab Process and a product for the purification of polluted water from heavy metal ions present therein
DE3309772A1 (de) * 1983-03-18 1984-09-20 GOEMA, Dr. Götzelmann KG, Physikalisch-chemische Prozeßtechnik, 7000 Stuttgart Verfahren zum abtrennen von schwermetallen aus schlaemmen
US5154833A (en) * 1992-01-08 1992-10-13 Connaught Laboratories Inc. Removal of mercury from waste streams

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2960474D1 (en) * 1978-04-15 1981-10-22 Carves Simon Ltd A method of removing metallic impurities from sewage sludge
DE4015489A1 (de) * 1990-05-14 1991-11-21 Aquamot Ag Verfahren zur simultanen reinigung von fluessigen, pulverfoermigen oder geschlemmten abfaellen landwirtschaftlicher, kommunaler oder industrieller herkunft
US5051191A (en) * 1990-10-31 1991-09-24 Green Environmental Systems Ltd. Method to detoxify sewage sludge

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617563A (en) * 1968-08-19 1971-11-02 Res Ab Process and a product for the purification of polluted water from heavy metal ions present therein
DE3309772A1 (de) * 1983-03-18 1984-09-20 GOEMA, Dr. Götzelmann KG, Physikalisch-chemische Prozeßtechnik, 7000 Stuttgart Verfahren zum abtrennen von schwermetallen aus schlaemmen
US5154833A (en) * 1992-01-08 1992-10-13 Connaught Laboratories Inc. Removal of mercury from waste streams

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Patent Abstracts of Japan, Band 7, Nr 209, C-186, Zusammenfasung von JP, 58-109192 (NIPPON KOKAN K.K.), *
Patent Abstracts of Japan, Band 8, Nr 34, C-210, Zusammenfasung von JP, 58-196888 (MITSUBISHI JUKOGYO K.K.), *

Also Published As

Publication number Publication date
DE4229662A1 (de) 1994-03-17
DE4229662C2 (de) 1996-08-14

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