EP0687483A1 - Verfahren zur Behandlung und Konditionierung von schwermetallhaltigen Suspensionen und Flüssigkeiten - Google Patents

Verfahren zur Behandlung und Konditionierung von schwermetallhaltigen Suspensionen und Flüssigkeiten Download PDF

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Publication number
EP0687483A1
EP0687483A1 EP95401367A EP95401367A EP0687483A1 EP 0687483 A1 EP0687483 A1 EP 0687483A1 EP 95401367 A EP95401367 A EP 95401367A EP 95401367 A EP95401367 A EP 95401367A EP 0687483 A1 EP0687483 A1 EP 0687483A1
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EP
European Patent Office
Prior art keywords
treatment
solid
heavy metals
extraction
conditioning method
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
EP95401367A
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English (en)
French (fr)
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EP0687483B1 (de
Inventor
Jean Leybros
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.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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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
    • A62D3/33—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
    • A62D2101/20—Organic substances
    • A62D2101/24—Organic substances containing heavy metals
    • 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 present invention relates to a process for the treatment and conditioning of solid or liquid effluents loaded with heavy metals. It aims to treat effluents from, for example, chemical processes for surface treatment, waste incineration processes or any other process leading to the formation of effluents heavily loaded with heavy metals and therefore extremely toxic. This process allows, more particularly, the selective recovery of these heavy metals with respect to chlorine or to alkali or alkaline earth metals.
  • the solid waste produced by these different chemical processes is particularly toxic for the environment because it has a fairly large soluble fraction which prevents its storage in landfills.
  • the volumes of liquid effluents formed are generally very large.
  • a medium-sized company working in this type of industry can generate up to a tonne per year of sludge concentrated in metals. This represents extremely significant pollution throughout the national territory.
  • the purification technique for this type of effluent generally consists of carrying out a conventional neutralization and precipitation treatment, so as to form sludges liable to be stored in landfills of class "I" (that is to say an impermeable site intended to receive special industrial waste).
  • This waste or this residue comprises approximately 30% by weight of the initial bottom ash product, 3% by weight of the initial fly ash product and of the dechlorination products of the fumes (hereinafter referred to as REFIOM, i.e. REsidues Household Waste Incineration Smoke), the rest being non-condensable products.
  • REFIOM i.e. REsidues Household Waste Incineration Smoke
  • the bottom clinkers are relatively chemically inert and can be used after conditioning in road construction or be stored in landfills of class "II" (that is to say a semi-permeable site intended to receive ordinary industrial waste), or even in class III landfills (that is to say a permeable site receiving only inert waste).
  • fly ash formed by fine particles entrained by combustion gases and by gas neutralization products, have highly polluting characteristics, due to the high rate of the soluble fraction
  • the polluting fraction consists essentially of heavy metals, the most common of which are zinc, lead, cadmium and chromium.
  • composition of these "REFIOM” is very variable and depends on the techniques used for the purification of the fumes from the incineration processes (techniques by dry, semi-wet or wet routes).
  • REFIOMs can be washed with water, which allows the soluble fraction containing the majority of heavy metals to be entrained.
  • the leachate is treated with sodium hydroxide which allows on the one hand the precipitation of these metals in the form of hydroxide and their recycling with the insoluble part resulting from the preliminary washing operation, the whole being able to be vitrified, and on the other hand the production of a sodium effluent containing the non-toxic anions and cations to be treated later.
  • the wet processes can operate in a similar fashion, except washing, since the recovered effluent is already in the form of a suspension which undergoes the same precipitation treatment as previously described.
  • the solid residue obtained can also be vitrified.
  • vitrification requires compliance with a number of criteria.
  • the vitrified elements must be digestible in the glass, so as to avoid the formation of heterogeneous phases or precipitates in large quantities.
  • the anions (Cl, F, PO4, SO4) are the most troublesome elements due to their low solubility in glass which causes phase separations.
  • the glasses then obtained are non-homogeneous and of poor quality, because the molten salt phase which is not vitrified contains a non-negligible proportion of toxic cations.
  • the molten salt phases being lighter than the glass itself, the fairly high volatility of these salts is further increased by their contact with the gaseous atmosphere.
  • waste and glass must be compatible.
  • the treated effluents may contain a high proportion (that is to say more than 50% by weight) of alkali metal salts (sodium and potassium) or alkaline earth metal salts (magnesium and calcium ). These salts do not present any particular nuisance for the environment and it is not necessary to make them inert in a specific matrix.
  • the object of the invention is to carry out a process for the treatment and conditioning of solid or liquid effluents loaded with heavy metals which make it possible to selectively separate from the effluent, chlorine and alkali or alkaline-earth metals in order to make the toxic residual fraction of the effluent containing heavy metals vitrifiable.
  • This process applies to the treatment of various effluents and in particular solid or liquid effluents from chemical surface treatment processes or waste incineration processes.
  • the process according to the invention allows selective recovery of heavy metals with respect to chlorine and to alkali or alkaline-earth metals and this in a solid form which is perfectly suitable for vitrification.
  • the solvent containing an extractant and a hydrocarbon must be chosen appropriately.
  • the hydrocarbon used is generally hydrogenated tetrapropylene (TPH).
  • TPH tetrapropylene
  • an agent preventing the separation of the extractant and the diluent for example a heavy alcohol C10 to C14, may be necessary.
  • the dilution factor should not be too large in order to be able to strongly concentrate the metals and not to have to increase the size of the extraction apparatus.
  • the solvent is preferably diluted until it titers 0.2 to 1.0 mole of organophosphorus extractant per liter of hydrocarbon or better 0.6 mole per liter. This reduces the density of the viscosity of the organic solvent while increasing its interfacial tension with the aqueous contact solutions. Therefore, the first extraction step can take place at room temperature (20 to 25 ° C), which reduces its cost.
  • the quality of the extraction is highly dependent on the pH of the aqueous phase.
  • the acidity of the aqueous phase increases. Care should therefore be taken to maintain the pH value as constant as possible by injections of a neutralizing agent at predetermined positions in the extraction apparatus.
  • the pH of the aqueous phase is preferably maintained at a value between 4.5 and 6.5, or better still between 5.0 and 6.0 depending on the extractant used.
  • the neutralizing agent used to adjust the pH is a concentrated sodium hydroxide solution.
  • the second extraction step can be carried out at room temperature (approximately 20 to 25 ° C), it is preferable to carry it out hot, that is to say between approximately 40 and 60 ° C, preferably 50 ° C, if you wish to purify the solvent from all of the metals before recycling it in the first extraction device.
  • This hot treatment also has the advantage of avoiding the precipitation of lead chloride, the solubility of which is more limited in the second extraction apparatus.
  • the precipitation step transforms the metals into insoluble carbonates, that is to say a chemical form suitable for vitrification.
  • insoluble carbonates that is to say a chemical form suitable for vitrification.
  • powdered sodium carbonate or in solution at 200 g / l or powdered calcium carbonate which quantitatively precipitate the most troublesome heavy metals, such as cadmium, nickel, lead and zinc.
  • the precipitation pH is chosen at a value between 8 and 10, or better still 9, to limit the redissolution of aluminum and chromium hydroxides in particular.
  • This precipitation step is generally carried out between 40 and 60 ° C or better about 50 ° C, which increases the speed of formation and maturation of the precipitates and makes it possible to avoid the untimely precipitation of lead chloride.
  • the installation necessary for the implementation of the method according to the invention comprises six chemical engineering equipments, namely two extraction apparatuses, referenced 2 and 4 respectively, of the pulsed column type, an apparatus precipitation device 6, of the ripener-thickener type, a filtration device 8, of the continuous vacuum filter type with drum or strips or of the discontinuous filter type with press and vitrification equipment 10.
  • this device can also include concentration equipment 12.
  • a leaching device 14 advantageously consisting of an apparatus of the stirred tank type, mounted in cascade and the volume and number of which is adapted to the flow rate of the waste to be treated and by a filtration device 16, of the continuous vacuum type drum or band filter, or of the discontinuous press filter type.
  • the operation of this device will now be described in more detail, in the case of effluents to be treated which are in solid form.
  • the solid effluent 18 is introduced with concentrated hydrochloric acid 20 into the leaching device 14 where the reaction takes place between 40 and 80 ° C.
  • a control of the pH of the solid-liquid suspension 22 leaving the leaching device makes it possible to adjust the flow rate of hydrochloric acid 20.
  • the pH is maintained between 0.5 and 3.0.
  • the solid-liquid suspension 22 is introduced into the filtration device 16.
  • the solid cake is washed with water 24 and the liquid filtrate 26 is recovered.
  • the mother liquors from washing 28 are recycled to the leaching device 14 where they constitute the leaching solution.
  • the flow rate of washing water 24 is adapted to the flow rate of solid waste, so as to obtain a filtrate 26 containing between 5 and 20% by weight of solids and a washed residual solid 30 containing less than 1% of chlorides.
  • a reducing agent 32 and a filtrate 34 from the filtration device 8 are added to the filtrate 26 (or liquid effluent) as will be described later so as to form a mother solution 36.
  • This is introduced at one end of the extraction apparatus 2, in which the non-alkaline and non-alkaline earth cations are selectively extracted from the anions, against the flow of an organic extraction solvent 38 introduced at the other end of the apparatus .
  • the reducing agent 32 is, for example, sodium bisulfite, sodium metabisulfite, ferrous sulfate or sulfur dioxide.
  • the pH of the aqueous phase is adjusted by injections of a neutralizing agent at different points, referenced respectively 40, 42 and 44.
  • the relative flow rate of the two solutions is adjusted so that the raffinate 46 leaving the first device contain less than 15.0 mg / l of heavy metals.
  • the solvent 38 comes from the second extraction device 4.
  • the organic solution loaded with heavy metals 48 leaving the first extraction device 2 enters the second extraction device 4 where it is treated counter-current and hot with an aqueous solution of hydrochloric acid 50.
  • the acid titer of this aqueous solution of hydrochloric acid is such that the solvent 38 leaving the second extraction device 4 is sufficiently discharged not to generate leaks of heavy metals and in particular cadmium greater than 0.2 mg / l in the raffinate 46.
  • the aqueous extraction solution 52 loaded with heavy metals, originating from the extraction apparatus 4, is introduced hot into the precipitation apparatus 6 where it is treated using a precipitation agent 54 which can advantageously be sodium or calcium carbonate.
  • a precipitation agent 54 which can advantageously be sodium or calcium carbonate. This carbonate maintains a sufficiently alkaline pH for which the heavy metals are thus precipitated in the form of carbonates, the chloride anions remaining in solution.
  • the solid-liquid suspension 56 from the precipitation apparatus 6 is introduced into the filtration apparatus 8 and the filtrate obtained is recycled at 34.
  • the solid precipitate 64 is washed by introduction of water at 58, while the waters outgoing washing mothers 60 are recycled to the extraction apparatus 4.
  • the flow rate of washing water used is at least equal to the flow rate necessary for diluting the hydrochloric acid 62 introduced.
  • the mother liquors from washing 60 and hydrochloric acid form the aqueous solution 50 introduced into the second extraction device 4.
  • the aqueous solution 50 contains between 0.1 and 6.0 mol / l hydrochloric acid.
  • the relative flow rates of the washing water 58 and the hydrochloric acid are further adjusted so that the solvent 38 contains less than 50 mg / l of heavy metals.
  • the washed precipitate containing less than 1% of chlorides 64 is treated with the residual solid 30 in the vitrification device 10 to produce an inert glass 66.
  • the raffinate 46 can be treated in the concentration device 8 in order to recover, on the one hand, recyclable water 68, salts 70 crystallized or in the form of brine.
  • Sodium metabisulfite is added at a rate of 50 mg / l.
  • the mother solution 36 and the organic solvent 38 are introduced into the first extraction device 2 with a solvent flow rate equal to 0.2 times the flow rate of the aqueous phase.
  • the pH is checked at 5.5 by adding 1.0 N NaOH.
  • the organic solvent 38 titers 0.6 M / l of bis- (2,4,4-trimethylpentyl) -monothiophosphinic acid in TPH.
  • the organic solution loaded with heavy metals 48 is treated in the second extraction device 4, against the flow of a 3N hydrochloric acid solution whose volume flow is five times lower than the flow of organic phase.
  • the first extraction operation 2 is carried out at an average temperature of the order of 22 ° C, while the second extraction operation 4 is carried out at the average temperature of the order of 50 ° C.
  • the de-extracted solvent 38 recovered contains less than 15 mg / l of residual heavy metals.
  • the pH is equal to 1.8.
  • Sodium metabisulfite is added at a rate of 20 mg / l.
  • the mother solution 36 and the organic solvent 38 are introduced into the first extraction device 2 with a flow rate of solvent equal to 0.2 times the flow rate of aqueous phase.
  • the pH is checked at 5.5 by adding 1.0 N NaOH.
  • the organic solvent 38 titers 0.6 M / l of di- (2-ethylhexyl) -manothiophosphoric acid in TPH.
  • the organic solution loaded with heavy metals 48 is treated in the second extraction device 4, against the flow of a 3N hydrochloric acid solution whose volume flow is 5 times lower than the flow of organic phase.
  • the first extraction operation 2 is carried out at an average temperature of the order of 22 ° C, while the second extraction operation 4 is carried out at an average temperature of 50 ° C.
  • the de-extracted solvent 38 recovered contains less than 15 mg / l of residual heavy metals.

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  • 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)
  • Extraction Or Liquid Replacement (AREA)
  • Processing Of Solid Wastes (AREA)
  • Removal Of Specific Substances (AREA)
EP19950401367 1994-06-15 1995-06-13 Verfahren zur Behandlung und Konditionierung von schwermetallhaltigen Suspensionen und Flüssigkeiten Expired - Lifetime EP0687483B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9407297 1994-06-15
FR9407297A FR2721237B1 (fr) 1994-06-15 1994-06-15 Procédé de traitement et de conditionnement d'effluents solides ou liquides chargés en métaux lourds.

Publications (2)

Publication Number Publication Date
EP0687483A1 true EP0687483A1 (de) 1995-12-20
EP0687483B1 EP0687483B1 (de) 1998-08-26

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EP19950401367 Expired - Lifetime EP0687483B1 (de) 1994-06-15 1995-06-13 Verfahren zur Behandlung und Konditionierung von schwermetallhaltigen Suspensionen und Flüssigkeiten

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EP (1) EP0687483B1 (de)
DE (1) DE69504248T2 (de)
ES (1) ES2123221T3 (de)
FR (1) FR2721237B1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2760662A1 (fr) * 1997-03-11 1998-09-18 Recupyl Sa Procede de traitement de l'amiante par conversion thermochimique
FR2760663A1 (fr) * 1997-03-11 1998-09-18 Recupyl Sa Procede de traitement des residus provenant de l'incineration des ordures menageres (refiom) et des dechets industriels (refedi)
WO1999021619A1 (fr) * 1997-10-24 1999-05-06 Recupyl S.A. Procede de traitement des refus d'incineration d'ordures menageres

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2801521B1 (fr) * 1999-11-29 2002-04-26 Commissariat Energie Atomique Procede et dispositif de traitement et de conditionnement d'un effluent en vue d'une vitrification

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6161688A (ja) * 1984-08-31 1986-03-29 Daihachi Kagaku Kogyosho:Kk 銅および／もしくはカドミウムとコバルトおよび／もしくはニツケルとを分離する方法
US4873065A (en) 1986-05-02 1989-10-10 Kernforschungszentrum Karlsruhe Gmbh Flue gas purification process
EP0409140A1 (de) * 1989-07-17 1991-01-23 Coltec Industries Inc Verfahren zur Entfernung von sechswertigem Chrom aus Wasser
DD289030A5 (de) * 1989-10-05 1991-04-18 Ingenieurbetrieb Anlagenbau Leipzig Gmbh I.G.,De Verfahren zur reinigung blei- und chromathaltiger abwaesser mit gleichzeitiger wertstoffrueckgewinnung
US5041398A (en) 1989-02-22 1991-08-20 Wheaton Industries Method for treating incinerator ash
EP0480243A1 (de) * 1990-10-10 1992-04-15 Wiser Oy Verfahren zur Reinigung von Abwasser und/oder Trinkwasser

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6161688A (ja) * 1984-08-31 1986-03-29 Daihachi Kagaku Kogyosho:Kk 銅および／もしくはカドミウムとコバルトおよび／もしくはニツケルとを分離する方法
US4873065A (en) 1986-05-02 1989-10-10 Kernforschungszentrum Karlsruhe Gmbh Flue gas purification process
US5041398A (en) 1989-02-22 1991-08-20 Wheaton Industries Method for treating incinerator ash
EP0409140A1 (de) * 1989-07-17 1991-01-23 Coltec Industries Inc Verfahren zur Entfernung von sechswertigem Chrom aus Wasser
DD289030A5 (de) * 1989-10-05 1991-04-18 Ingenieurbetrieb Anlagenbau Leipzig Gmbh I.G.,De Verfahren zur reinigung blei- und chromathaltiger abwaesser mit gleichzeitiger wertstoffrueckgewinnung
EP0480243A1 (de) * 1990-10-10 1992-04-15 Wiser Oy Verfahren zur Reinigung von Abwasser und/oder Trinkwasser

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8619, Derwent World Patents Index; AN 86-122389 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2760662A1 (fr) * 1997-03-11 1998-09-18 Recupyl Sa Procede de traitement de l'amiante par conversion thermochimique
FR2760663A1 (fr) * 1997-03-11 1998-09-18 Recupyl Sa Procede de traitement des residus provenant de l'incineration des ordures menageres (refiom) et des dechets industriels (refedi)
WO1999021619A1 (fr) * 1997-10-24 1999-05-06 Recupyl S.A. Procede de traitement des refus d'incineration d'ordures menageres

Also Published As

Publication number Publication date
EP0687483B1 (de) 1998-08-26
DE69504248T2 (de) 1999-04-01
DE69504248D1 (de) 1998-10-01
ES2123221T3 (es) 1999-01-01
FR2721237B1 (fr) 1996-08-02
FR2721237A1 (fr) 1995-12-22

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