EP0049656A1 - Purification device for removing heavy metals from contaminated aqueous effluents - Google Patents

Purification device for removing heavy metals from contaminated aqueous effluents Download PDF

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Publication number
EP0049656A1
EP0049656A1 EP19810401493 EP81401493A EP0049656A1 EP 0049656 A1 EP0049656 A1 EP 0049656A1 EP 19810401493 EP19810401493 EP 19810401493 EP 81401493 A EP81401493 A EP 81401493A EP 0049656 A1 EP0049656 A1 EP 0049656A1
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Prior art keywords
support
copolymer
heavy metals
complexing
monomer
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EP19810401493
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German (de)
French (fr)
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EP0049656B1 (en
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Aymé Cornu
Roger Massot
Gilbert Gaussens
Maryvonne Nicaise
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange

Definitions

  • the present invention relates to a purification device for the decontamination of aqueous effluents into heavy metals.
  • the most widely used methods for removing heavy metals present in aqueous effluents consist of -absorbing or capturing heavy metal ions, for example mercury, lead, cadmium, copper, silver or chromium, at using agents capable of forming sufficiently stable complexes with these metal ions.
  • sulfur-containing derivatives are of great interest because they have a large affinity for heavy metals, in particular sulfur derivatives such as thio-2-benzimidazole and its derivatives, for example its chlorinated, nitrated and dimethyl derivatives, thio-2-vinyl-2-benzimidazole, and thio-ureidobenzimidazole.
  • sulfur derivatives such as thio-2-benzimidazole and its derivatives, for example its chlorinated, nitrated and dimethyl derivatives, thio-2-vinyl-2-benzimidazole, and thio-ureidobenzimidazole.
  • Amino-2-benzimidazole and guanidines can also be used as complexing agent.
  • the present invention specifically relates to a purification device for the decontamination of heavy metals from aqueous effluents which makes it possible to ensure satisfactory decontamination of heavy metals, with the additional advantage of being able to be easily regenerated.
  • the device according to the invention is characterized in that it comprises a support in hydrophilic crosslinked copolymer in which is incorporated an agent capable of complexing said heavy metals, said support in crosslinked copolymer being capable of being swollen by said effluents.
  • the copolymer is a copolymer of at least one hydrophilic monounsaturated mononer and at least one polyunsaturated monomer.
  • monounsaturated monomer capable of being used, mention may be made of acrylic acid, methacrylic acid, vinylpyrrolidone, ethylene glycol acrylate, ethylene glycol methacrylate, acrylate diethylene glycol, diethylene glycol methacrylate, tetraethylene glycol acrylate, tetraethylene glycol methacrylate, polyethylene glycol acrylate and polyethylene glycol methacrylate.
  • polyunsaturated monomer capable of being used mention may be made of trimethylol propane triacrylate, trimethylol propane trimethacrylate and pentaerythrititol tetraacrylate.
  • the monounsaturated monomer and the polyunsaturated monomer are acrylic and / or methacrylic monomers.
  • the agent capable of complexing heavy metals can be constituted by the sulfur derivatives mentioned above, in particular by thio-2-benzimidazole and its derivatives.
  • This complexing agent can be trapped in the crosslinked network of the polymer, for example when it is constituted by thio-2-benzimidazole, or else fixed on the chain of the copolymer by a covalent bond in the case of thio-2-vinyl- 3-benzimidazole.
  • thio-2-benzimidazole is a known product which can be prepared for example according to the process described in Organic Syntheses, vol. 4, pages 569-570.
  • Thio-2-vinyl-3-benzimidazole can be prepared from thio-2-benzimidazole by glycation. According to a procedure similar to that described by H. HOPFF, U. WYSS, H. JUSSI, Helvetica Chi- mica Acta, vol. 13, Fasc. 1 (1960), p. 135, for the glycation of nitrogenous heterocycles.
  • the content of polyunsaturated monomer in the copolymer which determines its crosslinking rate, is large enough to obtain good mechanical properties, but it must not be too high so that the aqueous effluents can access the support and be in contact with the complexing agent included in this support.
  • a copolymer comprising from 85 to 95% by weight of hydrophilic monounsaturated monomer and from 5 to 15% by weight of polyunsaturated monomer.
  • the content of complexing agent in the support is advantageously from 2 to 20% by weight relative to the total weight of the support containing the complexing agent. and generally from 5 to 15% in the case of thio-2-benzimidazole and its derivatives.
  • the present invention also relates to a process for preparing a purification device for the decontamination of aqueous effluents.
  • This process consists in forming the support in crosslinked copolymer in which the agent is incorporated. complexing by polymerization of a solution comprising at least one hydrophilic monounsaturated monomer, at least one polyunsaturated monomer and an agent capable of complexing heavy metals.
  • this polymerization is carried out by irradiation of the solution by means of ionizing radiation.
  • an alcoholic solution for example a solution of different monomers and the complexing agent in ethanol, and the polymerization is carried out under vacuum or in an inert atmosphere.
  • the ionizing radiation capable of being used can consist of ultraviolet radiation, ⁇ radiation, y radiation, and electron beams.
  • the y radiation of cobalt 60 is used.
  • the inert support in crosslinked hydrophilic copolymer in which the complexing agent has been incorporated may be in the form of powder, granules, film or fibers, obtained by conventional techniques ; in this case, the powders, granules, films or fibers are arranged or maintained in an appropriate enclosure.
  • the purification device can comprise a fabric or a nonwoven such as a felt made, for example, of fluoropolymer, polyester or polyamide, this fabric or this felt supporting the hydrophilic copolymer crosslinked in which the complexing agent is incorporated.
  • the fabric or the felt is coated with a solution comprising at least one monounsaturated monomer, at least one polyunsaturated monomer and one agent capable of complexing heavy metals, then grafting and polymerizing this solution, preferably by subjecting it to irradiation by means of ionizing radiation, which leads to the formation of a crosslinked copolymer containing the complexing agent, this copolymer being grafted onto fabric or felt.
  • a purification device is prepared from a monounsaturated monomer constituted by acrylic acid and a polyunsaturated monomer constituted by trimethylol propane triacrylate.
  • a solution comprising 72% by weight of ethanol, 16.2% of acrylic acid, 1.8% of trimethylol propane triacrylate, and 10% of a complexing agent consisting either of thio- 2-benzimidazole, either by thio-2-vinyl-3-benzimidazole.
  • the support PVB-3 is designated. in which the complexing agent is thio-2-benzimidazole, and by PVB-4 the support in which the complexing agent is thio-2-vinyl-3-benzimidazole.
  • the solution is then filtered, and a first filtrate F 1 having a pH of 3.7 is collected.
  • the PVB-3 or PVB-4 support separated from the solution is then washed with 100 cm 3 of distilled water pen for 1 hour with stirring, then filtered, and the filtrate obtained F 2 is collected.
  • the PVB-3 or PVB-4 support is then washed a second time with 100 cm 3 of water containing 10% hydrochloric acid, for 1 hour with stirring, filtered and a filtrate F 3 is collected.
  • the copper content of each of the filtrates F 1 , F 2 and F 3 thus obtained is determined by colorimetry (reaction with ammonia).
  • the residual thio-2-benzimidazole or thio-2-vinyl-3-benzimidazole content of the filtrate F 1 is also determined by the Wavelet method, and it is found that these filtrates F 1 contain from 10 to 20 vpm of agent. complexing.
  • the supports of the invention make it possible to remove most of the copper, and that, moreover, the copper can then be recovered by an acid wash of the support.
  • a support of the PVB-4 type is used for the removal of mercury from a solution of mercury chloride HgCl 2 at 100 ppm of mercury and at pH 8.
  • lg of PVB-4 support is used which is added to 100 cm 3 of the mercury solution, and the same operations are carried out as in the case of Example 1 to obtain a first filtrate F 1 , then a filtrate F 2 .
  • the support is washed with 100 cm 3 of a 10% aqueous solution of nitric acid, for one hour, with stirring, then filtered and a filtrate F 3 is recovered.
  • Example 1 the mercury contents of each of the filtrates F 1 , F 2 and F 3 recovered are determined by colorimetry using dithizone as reagent.
  • PVB-3 and P VB-4 supports are used which have been regenerated after having been used for fixing copper or mercury.
  • the support is washed successively using hydrochloric acid or nitric acid N / 10, then using distilled water, sodium hydroxide N / 10 and finally distilled water.
  • the supports thus regenerated are then used for the copper decontamination of a solution consisting of 40 ml of a solution of copper sulphate at 93 ppm of copper and at pH 8.
  • lg of the support is mixed with 40 ml of the solution, and the same operations are carried out as in Example 1 to successively recover the filtrates F 1 , F 2 and F 3 and their copper content is determined by spec flameless atomic absorption trometry for better accuracy.
  • the PVB-4 support makes it possible to obtain a high rate of copper decontamination.
  • a regenerated PVB-4 support is used as in Example 3, and 1g of this support is mixed with 100 ml of a mercury HgCl 2 solution containing 90 ppm of mercury and at pH 8.
  • Example 2 The same operations are carried out as in Example 2 to recover the filtrates F 1 , F 2 and F 3 , and the mercury content is determined on each of these filtrates by flameless atomic absorption spectrometry.

Abstract

1. Purification device for removing heavy metal contaminants from aqueous effluents, characterized in that it comprises a crosslinked hydrophilic copolymer support derived from 85 to 95% by weight of a hydrophilic monounsaturated monomer and 5 to 15% by weight of a polyunsaturated monomer, and an agent capable of complexing heavy metals incorporated in said support in an amount from 2 to 20% by weight, based on total weight of agent and support, said agent being selected from 2-thiobenzimidazole, chloro-, nitro- or dimethyl derivatives of 2-thiobenzimidazole, 2-thio-3-vinylbenzimidazole, thioureidobenzimidazole, 2-aminobenzimidazole and guanidines.

Description

La présente invention a pour objet un dispositif d'épuration pour la décontamination d'effluents aqueux en métaux lourds.The present invention relates to a purification device for the decontamination of aqueous effluents into heavy metals.

De façon plus précise, elle concerne la réalisation de dispositifs d'épuration comportant un support inerte dans lequel est incorporé un agent capable de complexer les métaux lourds présents dans les effluents aqueux.More specifically, it relates to the production of purification devices comprising an inert support in which is incorporated an agent capable of complexing the heavy metals present in the aqueous effluents.

Les méthodes les plus largement utilisées pour éliminer les métaux lourds présents dans les effluents aqueux consistent à -absorber ou à capter les ions métalliques lourds, par exemple de mercure, de plomb, de cadmium, de cuivre, d'argent ou de chrome, au moyen d'agents capables de former avec ces ions métalliques des complexes suffisamment stables.The most widely used methods for removing heavy metals present in aqueous effluents consist of -absorbing or capturing heavy metal ions, for example mercury, lead, cadmium, copper, silver or chromium, at using agents capable of forming sufficiently stable complexes with these metal ions.

Parmi les agents chimiques capables de remplir ce rôle, on sait par l'article publié dans le BIST n° 230-231, juillet/octobre 1978, pages 203-204, que les dérivés -soufrés présentent un grand intérêt car ils possèdent une grande affinité pour les métaux lourds, en particulier les dérivés soufrés tels que le thio-2-benzimidazole et ses dérivés, par exemple ses dérivés chloré, nitré et diméthylé, le thio-2-vinyl-2-benzimidazole, et le thio-uréidobenzimidazole. On peut également utiliser comme agent complexant l'ami- no-2-benzimidazole et les guanidines.Among the chemical agents capable of fulfilling this role, it is known from the article published in the BIST n ° 230-231, July / October 1978, pages 203-204, that the sulfur-containing derivatives are of great interest because they have a large affinity for heavy metals, in particular sulfur derivatives such as thio-2-benzimidazole and its derivatives, for example its chlorinated, nitrated and dimethyl derivatives, thio-2-vinyl-2-benzimidazole, and thio-ureidobenzimidazole. Amino-2-benzimidazole and guanidines can also be used as complexing agent.

Cependant pour faciliter les opérations de décontamination, il est préférable d'incorporer ces agents complexants dans un support inerte pour retenir sur ce support les ions de métaux lourds captés par l'agent complexant. Par ailleurs, il est souhaitable .de pouvoir éliminer ensuite les ions de métaux lourds ainsi fixés afin de pouvoir régénérer le dispositif d'épuration.However, to facilitate decontamination operations, it is preferable to incorporate these complexing agents in an inert support to retain on this support the heavy metal ions captured by the complexing agent. Furthermore, it is desirable to be able to then remove the heavy metal ions thus fixed in order to be able to regenerate the purification device.

La présente invention a précisément pour objet un dispositif d'épuration pour la décontamination en métaux lourds d'effluents aqueux qui permet d'assurer une décontamination satisfaisante en métaux lourds, en présentant de plus l'avantage de pouvoir être régénérée facilement.The present invention specifically relates to a purification device for the decontamination of heavy metals from aqueous effluents which makes it possible to ensure satisfactory decontamination of heavy metals, with the additional advantage of being able to be easily regenerated.

Le dispositif selon l'invention se caractérise en ce qu'il comprend un support en copolymère réticulé hydrophile dans lequel est incorporé un agent capable de complexer lesdits métaux lourds, ledit support en copolymère réticulé étant capable d'être gonflé par lesdits effluents.The device according to the invention is characterized in that it comprises a support in hydrophilic crosslinked copolymer in which is incorporated an agent capable of complexing said heavy metals, said support in crosslinked copolymer being capable of being swollen by said effluents.

Avantageusement, .le copolymère est un-copolymère d'au moins un mononère hydrophile monoinsaturé et d'au moins un monomère polyinsaturé.Advantageously, the copolymer is a copolymer of at least one hydrophilic monounsaturated mononer and at least one polyunsaturated monomer.

A titre d'exemples de monomère monoinsaturé susceptible d'être utilisé, on peut citer l'acide acrylique, l'acide méthacrylique, la vinylpyrrolido- ne, l'acrylate d'éthylène glycol, le méthacrylate d'éthylène glycol, l'acrylate de diéthylène glycol, le méthacrylate de diéthylène glycol, l'acrylate de tétraéthylène glycol, le méthacrylate de tétraéthylène glycol, l'acrylate de polyéthylène glycol et le méthacrylate de polyéthylène glycol.As examples of monounsaturated monomer capable of being used, mention may be made of acrylic acid, methacrylic acid, vinylpyrrolidone, ethylene glycol acrylate, ethylene glycol methacrylate, acrylate diethylene glycol, diethylene glycol methacrylate, tetraethylene glycol acrylate, tetraethylene glycol methacrylate, polyethylene glycol acrylate and polyethylene glycol methacrylate.

A titre d'exemples de monomère polyinsaturé susceptible d'être utilisé, on peut citer le triacrylate de triméthylol propane, le triméthacrylate de triméthylol propane et le tétraacrylate de pentaéry- thritol.As examples of polyunsaturated monomer capable of being used, mention may be made of trimethylol propane triacrylate, trimethylol propane trimethacrylate and pentaerythrititol tetraacrylate.

De préférence, le monomère monoinsaturé et le monomère polyinsaturé sont des monomères acrylique et/ou méthacrylique.Preferably, the monounsaturated monomer and the polyunsaturated monomer are acrylic and / or methacrylic monomers.

Selon l'invention, l'agent capable de complexer les métaux lourds peut être constitué par les dérivés soufrés cités ci-dessus, en particulier par le thio-2-benzimidazole et ses dérivés.According to the invention, the agent capable of complexing heavy metals can be constituted by the sulfur derivatives mentioned above, in particular by thio-2-benzimidazole and its derivatives.

Cet agent complexant peut être piégé dans le réseau réticulé du polymère, par exemple lorsqu'il est constitué par le thio-2-benzimidazole, ou encore fixé sur la chaîne du copolymère par une liaison covalente dans le cas du thio-2-vinyl-3-benzimidazole.This complexing agent can be trapped in the crosslinked network of the polymer, for example when it is constituted by thio-2-benzimidazole, or else fixed on the chain of the copolymer by a covalent bond in the case of thio-2-vinyl- 3-benzimidazole.

On précise que le thio-2-benzimidazole est un produit connu qui peut être préparé par exemple selon le procédé décrit dans Organic Synthèses, vol. 4, pages 569-570. Le thio-2-vinyl-3-benzimidazole peut être préparé à partir du thio-2-benzimidazole par vi- nylations.Selon un mode opératoire similaire à celui décrit par H. HOPFF, U. WYSS, H. JUSSI, Helvetica Chi- mica Acta, vol. 13, Fasc. 1 (1960), p. 135, pour la vi- nylation des hétérocycles azotés.It is specified that thio-2-benzimidazole is a known product which can be prepared for example according to the process described in Organic Syntheses, vol. 4, pages 569-570. Thio-2-vinyl-3-benzimidazole can be prepared from thio-2-benzimidazole by glycation. According to a procedure similar to that described by H. HOPFF, U. WYSS, H. JUSSI, Helvetica Chi- mica Acta, vol. 13, Fasc. 1 (1960), p. 135, for the glycation of nitrogenous heterocycles.

Selon l'invention, la teneur en monomère polyinsaturé du copolymère, qui détermine son taux de réticulation, est suffisamment importante pour obtenir de bonnes propriétés mécaniques, mais elle ne doit pas être trop élevée afin que les effluents aqueux puissent accéder dans le support et être en contact avec l'agent complexant inclus dans ce support.According to the invention, the content of polyunsaturated monomer in the copolymer, which determines its crosslinking rate, is large enough to obtain good mechanical properties, but it must not be too high so that the aqueous effluents can access the support and be in contact with the complexing agent included in this support.

Avantageusement, on utilise un copolymère comprenant de 85 à 95% en poids de monomère hydrophile monoinsaturé et de 5 à 15% en poids de monomère polyinsaturé.Advantageously, a copolymer is used comprising from 85 to 95% by weight of hydrophilic monounsaturated monomer and from 5 to 15% by weight of polyunsaturated monomer.

La teneur en agent complexant du support est avantageusement de 2 à 20% en poids par rapport au poids total du support contenant l'agent complexant,. et généralement de 5 à 15% dans le cas du thio-2-benzimidazole et de ses dérivés.The content of complexing agent in the support is advantageously from 2 to 20% by weight relative to the total weight of the support containing the complexing agent. and generally from 5 to 15% in the case of thio-2-benzimidazole and its derivatives.

La présente invention a également pour objet un procédé de préparation d'un dispositif d'épuration pour la décontamination d'effluents aqueux.The present invention also relates to a process for preparing a purification device for the decontamination of aqueous effluents.

Ce procédé consiste à former le support en copolymère réticulé dans lequel est incorporé l'agent complexant par polymérisation d'une solution comprenant au moins un monomère hydrophile monoinsaturé, au moins un monomère polyinsaturé et un agent capable de complexer les métaux lourds.This process consists in forming the support in crosslinked copolymer in which the agent is incorporated. complexing by polymerization of a solution comprising at least one hydrophilic monounsaturated monomer, at least one polyunsaturated monomer and an agent capable of complexing heavy metals.

De préférence, on réalise cette polymérisation par irradiation de la solution au moyen de rayonnements ionisants.Preferably, this polymerization is carried out by irradiation of the solution by means of ionizing radiation.

Avantageusement on utilise une solution alcoolique, par exemple une solution de différents mono-mères et de l'agent complexant dans de l'éthanol, et on réalise la polymérisation sous vide ou en atmosphère inerte.Advantageously, an alcoholic solution is used, for example a solution of different monomers and the complexing agent in ethanol, and the polymerization is carried out under vacuum or in an inert atmosphere.

Les rayonnements ionisants susceptibles d'être utilisés peuvent être constitués par des rayonnements ultraviolets, des rayonnements α, des rayonnements y, et des faisceaux d'électrons.The ionizing radiation capable of being used can consist of ultraviolet radiation, α radiation, y radiation, and electron beams.

Avantageusement, on utilise le rayonnement y du cobalt 60.Advantageously, the y radiation of cobalt 60 is used.

Dans le dispositif d'épuration de l'invention, le support inerte en copolymère hydrophile réticulé dans lequel on a incorporé l'agent complexant, peut être sous la forme de poudre, de granulés, de film ou de fibres, obtenus par des techniques classiques ; dans ce cas, les poudres, granulés, films ou fibres sont disposés ou maintenus dans une enceinte appropriée.In the purification device of the invention, the inert support in crosslinked hydrophilic copolymer in which the complexing agent has been incorporated, may be in the form of powder, granules, film or fibers, obtained by conventional techniques ; in this case, the powders, granules, films or fibers are arranged or maintained in an appropriate enclosure.

Selon une variante de l'invention, le dispositif d'épuration peut comprendre un tissu ou un non tissé tel qu'un feutre réalisé, par exemple, en polymère fluoré, en polyester ou en polyamide, ce tissu ou ce feutre supportant le copolymère hydrophile réticulé dans lequel est incorporé l'agent complexant. Pour obtenir de tels dispositifs, on enduit le tissu ou le feutre d'une solution comprenant au moins un monomère monoinsaturé, au moins un monomère polyinsaturé et un agent capable de complexer les métaux lourds, puis on greffe et on polymérise cette solution, de préférence en la soumettant à une irradiation au moyen de rayonnements ionisants, ce qui conduit à la formation d'un copolymère réticulé contenant l'agent complexant, ce copolymère étant greffé sur le tissu ou le feutre.According to a variant of the invention, the purification device can comprise a fabric or a nonwoven such as a felt made, for example, of fluoropolymer, polyester or polyamide, this fabric or this felt supporting the hydrophilic copolymer crosslinked in which the complexing agent is incorporated. To obtain such devices, the fabric or the felt is coated with a solution comprising at least one monounsaturated monomer, at least one polyunsaturated monomer and one agent capable of complexing heavy metals, then grafting and polymerizing this solution, preferably by subjecting it to irradiation by means of ionizing radiation, which leads to the formation of a crosslinked copolymer containing the complexing agent, this copolymer being grafted onto fabric or felt.

D'autres avantages et caractéristiques de l'invention apparaîtront mieux à la lecture de la description qui suit, donnée bien entendu à titre d'exemple illustratif et non limitatif.Other advantages and characteristics of the invention will appear better on reading the description which follows, given of course by way of illustrative and nonlimiting example.

Selon l'invention, on prépare un dispositif d'épuration à partir d'un monomère monoinsaturé constitué par l'acide acrylique et d'un monomère polyinsaturé constitué par le triacrylate de triméthylol propane.According to the invention, a purification device is prepared from a monounsaturated monomer constituted by acrylic acid and a polyunsaturated monomer constituted by trimethylol propane triacrylate.

Dans ce but, on utilise une solution comprenant en poids 72% d'éthanol, 16,2% d'acide acrylique, 1,8% de triacrylate de triméthylol propane, et 10% d'un agent complexant constitué soit par du thio-2-benzimidazole, soit par du thio-2-vinyl-3-benzimidazole.For this purpose, a solution is used comprising 72% by weight of ethanol, 16.2% of acrylic acid, 1.8% of trimethylol propane triacrylate, and 10% of a complexing agent consisting either of thio- 2-benzimidazole, either by thio-2-vinyl-3-benzimidazole.

Le thio-2-vinyl-3-benzymidazole a été obtenu de la façon suivante.Thio-2-vinyl-3-benzymidazole was obtained as follows.

On maintient sous atmosphère d'azote pendant 2 semaines à 60-70°C, un mélange contenant 0,012 mole de thio-benzimidazole, 0,4 g de sulfate mercurique et 0,24 mole d'acétate de vinyle. On filtre le mélange réactionnel une première fois pour éliminer le thio-2-benzimidazole restant, puis on évapore sous vide l'acétate de vinyle n'ayant pas réagi. On reprend le résidu dans de l'éthanol, puis on le filtre afin d'éliminer le sulfate mercurique insoluble. Après évaporation de l'éthanol, on obtient le thio-2-vinyl-3-benzimidazole avec un rendement très faible de 1,2%. Le point de fusion de ce produit est sensiblement de 140°C.Is maintained under nitrogen for 2 weeks at 60-70 ° C, a mixture containing 0.012 mole of thio-benzimidazole, 0.4 g of mercuric sulfate and 0.24 mole of vinyl acetate. The reaction mixture is filtered a first time to remove the remaining thio-2-benzimidazole, then the unreacted vinyl acetate is evaporated in vacuo. The residue is taken up in ethanol, then filtered to remove the insoluble mercuric sulfate. After evaporation of the ethanol, thio-2-vinyl-3-benzimidazole is obtained with a very low yield of 1.2 % . The melting point of this product is approximately 140 ° C.

Ces solutions sont irradiées en ampoules scellées sous vide, sous rayonnement y d'une source de cobalt 60. La dose reçue est de 2 mégarads et elle est délivrée avec un débit de 0,1 mégarad/heure. Après irradiation, on récupère les phases solides formées dans l'ampoule, et après séchage et broyage on les utilise pour la décontamination en métaux lourds d'effluents aqueux.These solutions are irradiated in vacuum-sealed ampoules, under radiation y from a source of cobalt 60. The dose received is 2 megarads and it is delivered with a flow rate of 0.1 megarad / hour. After irradiation, the solid phases formed in the bulb are recovered, and after drying and grinding they are used for the decontamination of heavy metals from aqueous effluents.

Les exemples suivants illustrent l'efficacité des phases solides ainsi obtenues. Dans ces exemples, on désigne sous le terme PVB-3 le support. dans lequel l'agent complexant est le thio-2-benzimidazole, et par PVB-4 le support dans lequel l'agent complexant est le thio-2-vinyl-3-benzimidazole.The following examples illustrate the efficiency of the solid phases thus obtained. In these examples, the support PVB-3 is designated. in which the complexing agent is thio-2-benzimidazole, and by PVB-4 the support in which the complexing agent is thio-2-vinyl-3-benzimidazole.

Après avoir obtenu des. granulés de résine qui sont jaunâtres dans le cas du PVB-3 ou blanchâtres dans le cas du PVB-4, on lave ces granulés successivement à l'eau froide, à l'eau chaude, à l'alcool puis à l'alcool chaud jusqu'à disparition de l'agent complexant dans les filtrats obtenus, la teneur en agent complexant des filtrats étant déterminée par colorimétrie avec un seuil de détection de 10 ppm.After obtaining. resin granules which are yellowish in the case of PVB-3 or whitish in the case of PVB-4, these granules are washed successively with cold water, hot water, alcohol and then hot alcohol until the complexing agent disappears in the filtrates obtained, the content of complexing agent in the filtrates being determined by colorimetry with a detection threshold of 10 ppm.

On vérifie ensuite l'efficacité des supports ainsi traités pour la décontamination en cuivre ou en mercure de solutions aqueuses.The effectiveness of the supports thus treated is then checked for the decontamination of copper or mercury from aqueous solutions.

EXEMPLE 1 : Essais de décontamination en cuivre.EXAMPLE 1: Copper decontamination tests.

On introduit dans 100 cm3 d'une solution de sulfate de cuivre à 100 ppm de cuivre et à pH 8, lg du support PVB-3 ou PVB-4 et on agite à la température ambiante pendant 2 heures.Is introduced into 100 cm 3 of a copper sulphate solution with 100 ppm of copper and at pH 8, 1 g of the PVB-3 or PVB-4 support and the mixture is stirred at room temperature for 2 hours.

On constate que les solutions de cuivre passent du bleu au vert, rapidement dans le cas du PVB-3 et plus progressivement dans le cas du PVB-4, et que les résines deviennent également vertes.It can be seen that the copper solutions change from blue to green, rapidly in the case of PVB-3 and more gradually in the case of PVB-4, and that the resins also become green.

On filtre ensuite la solution, et on recueille un premier filtrat F1 ayant un pH de 3,7.The solution is then filtered, and a first filtrate F 1 having a pH of 3.7 is collected.

On lave ensuite le support PVB-3 ou PVB-4 séparé de la solution avec 100 cm3 d'eau distillée pendant 1 heure sous agitation, puis on filtre, et on recueille le filtrat obtenu F2.The PVB-3 or PVB-4 support separated from the solution is then washed with 100 cm 3 of distilled water pen for 1 hour with stirring, then filtered, and the filtrate obtained F 2 is collected.

On lave ensuite une deuxième fois le support PVB-3 ou PVB-4 avec 100 cm3 d'eau contenant 10% d'acide chlorhydrique, pendant 1 heure sous agitation, on filtre et on recueille un filtrat F3.The PVB-3 or PVB-4 support is then washed a second time with 100 cm 3 of water containing 10% hydrochloric acid, for 1 hour with stirring, filtered and a filtrate F 3 is collected.

On détermine la teneur en cuivre de chacun des filtrat F1, F2 et F3 ainsi obtenus, par colorimétrie (réaction avec l'ammoniaque).The copper content of each of the filtrates F 1 , F 2 and F 3 thus obtained is determined by colorimetry (reaction with ammonia).

Les résultats obtenus sont donnés dans le tableau 1 ci-après.

Figure imgb0001
The results obtained are given in Table 1 below.
Figure imgb0001

On détermine également la teneur résiduelle en thio-2-benzimidazole ou en thio-2-vinyl-3-benzimidazole du filtrat F1 par la méthode de Wavelet, et on constate que ces filtrats F1 contiennent de 10 à 20 vpm d'agent complexant.The residual thio-2-benzimidazole or thio-2-vinyl-3-benzimidazole content of the filtrate F 1 is also determined by the Wavelet method, and it is found that these filtrates F 1 contain from 10 to 20 vpm of agent. complexing.

Au vu de ces résultats, on constate que les supports de l'invention permettent d'éliminer la majeure partie du cuivre, et que par ailleurs, le cuivre peut être récupéré ensuite par un lavage acide du support.In view of these results, it can be seen that the supports of the invention make it possible to remove most of the copper, and that, moreover, the copper can then be recovered by an acid wash of the support.

EXEMPLE 2 : Essai de décontamination en mercure.EXAMPLE 2: Mercury decontamination test.

Dans cet essai, on utilise un support du type PVB-4 pour l'élimination de mercure à partir d'une solution de chlorure de mercure HgCl2 à 100 ppm de mercure et à pH 8.In this test, a support of the PVB-4 type is used for the removal of mercury from a solution of mercury chloride HgCl 2 at 100 ppm of mercury and at pH 8.

Comme précédemment, on utilise lg du support PVB-4 que l'on ajoute à 100 cm3 de la solution de mercure, et on effectue les mêmes opérations que dans le cas de l'exemple 1 pour obtenir un premier filtrat F1, puis un filtrat F2. Après récupération du filtrat F2 on lave le support avec 100 cm3 d'une solution aqueuse à 10% d'acide nitrique, pendant une heure, sous agitation, puis on filtre et on récupère un filtrat F3.As before, lg of PVB-4 support is used which is added to 100 cm 3 of the mercury solution, and the same operations are carried out as in the case of Example 1 to obtain a first filtrate F 1 , then a filtrate F 2 . After recovering the filtrate F 2, the support is washed with 100 cm 3 of a 10% aqueous solution of nitric acid, for one hour, with stirring, then filtered and a filtrate F 3 is recovered.

Comme dans l'exemple 1, on détermine les teneurs en mercure de chacun des filtrats F1, F2 et F3 récupérés, par colorimétrie en utilisant comme réactif la dithizone..As in Example 1, the mercury contents of each of the filtrates F 1 , F 2 and F 3 recovered are determined by colorimetry using dithizone as reagent.

Les résultats obtenus sont donnés dans le tableau 2 ci-après.

Figure imgb0002
The results obtained are given in Table 2 below.
Figure imgb0002

EXEMPLE 3 : Essais de décontamination en cuivre.EXAMPLE 3: Copper decontamination tests.

Dans cet essai, on utilise des supports PVB-3 et PVB-4 qui ont été régénérés après avoir été utilisés pour la fixation de cuivre ou de mercure.In this test, PVB-3 and P VB-4 supports are used which have been regenerated after having been used for fixing copper or mercury.

, Pour cette régénération, on lave successivement le support au moyen d'acide chlorhydrigue ou d'acide nitrique N/10, puis au moyen d'eau distillée, de soude N/10 et enfin d'eau distillée., For this regeneration, the support is washed successively using hydrochloric acid or nitric acid N / 10, then using distilled water, sodium hydroxide N / 10 and finally distilled water.

On utilise ensuite les supports ainsi régénérés pour la décontamination en cuivre d'une solution constituée par 40 ml d'une solution de sulfate de cuivre à 93 ppm de cuivre et à pH 8. Dans cet essai, on mélange lg du support avec 40 ml de la solution, et on effectue les mêmes opérations que dans l'exemple 1 pour récupérer successivement les filtrats F1, F2 et F3 et on détermine leur teneur en cuivre par spectrométrie d'absorption atomique sans flamme pour obtenir une meilleure précision.The supports thus regenerated are then used for the copper decontamination of a solution consisting of 40 ml of a solution of copper sulphate at 93 ppm of copper and at pH 8. In this test, lg of the support is mixed with 40 ml of the solution, and the same operations are carried out as in Example 1 to successively recover the filtrates F 1 , F 2 and F 3 and their copper content is determined by spec flameless atomic absorption trometry for better accuracy.

Les résultats obtenus sont donnés dans le tableau 3 ci-après.

Figure imgb0003
The results obtained are given in Table 3 below.
Figure imgb0003

Au vu de ces résultats, on constate que le support PVB-4 permet d'obtenir un taux élevé de décontamination en cuivre.In view of these results, it can be seen that the PVB-4 support makes it possible to obtain a high rate of copper decontamination.

EXEMPLE 4 : décontamination en mercure.EXAMPLE 4: mercury decontamination.

On utilise un support PVB-4 régénéré comme dans l'exemple 3, et on mélange 1g de ce support avec 100 ml d'une solution de mercure HgCl2 à 90 ppm de mercure et à pH 8.A regenerated PVB-4 support is used as in Example 3, and 1g of this support is mixed with 100 ml of a mercury HgCl 2 solution containing 90 ppm of mercury and at pH 8.

On effectue les mêmes opérations que dans l'exemple 2 pour récupérer les filtrats F1, F2 et F3, et on détermine sur chacun de ces filtrats la teneur en mercure par spectrométrie d'absorption atomique sans flamme.The same operations are carried out as in Example 2 to recover the filtrates F 1 , F 2 and F 3 , and the mercury content is determined on each of these filtrates by flameless atomic absorption spectrometry.

Les résultats obtenus sont donnés dans le tableau 4 ci-après.

Figure imgb0004
The results obtained are given in Table 4 below.
Figure imgb0004

Claims (13)

1. Dispositif d'épuration pour la décontamination en métaux lourds d'effluents aqueux, caractérisé en ce qu'il comprend un support en copolymère hydrophile réticulé dans lequel est incorporé un agent capable de complexer lesdits métaux lourds, ledit copolymère réticulé étant capable d'absorber lesdits effluents.1. Purification device for the heavy metal decontamination of aqueous effluents, characterized in that it comprises a support of crosslinked hydrophilic copolymer in which is incorporated an agent capable of complexing said heavy metals, said crosslinked copolymer being capable of absorb said effluents. 2. Dispositif selon la revendication 1, caractérisé en ce que le copolymère est un copolymère acrylique et/ou méthacrylique.2. Device according to claim 1, characterized in that the copolymer is an acrylic and / or methacrylic copolymer. 3. Dispositif selon l'une quelconque des revendications 1 et 2, caractérisé en ce que le copolymère hydrophile est un copolymère d'au moins un monomère hydrophile monoinsaturé et d'au moins un monomère polyinsaturé.3. Device according to any one of claims 1 and 2, characterized in that the hydrophilic copolymer is a copolymer of at least one hydrophilic monounsaturated monomer and at least one polyunsaturated monomer. 4. Dispositif selon la revendication 3, caractérisé en ce que le monomère monoinsaturé est l'acide acrylique.4. Device according to claim 3, characterized in that the monounsaturated monomer is acrylic acid. 5. Dispositif selon l'une quelconque des revendications 3 et 4, caractérisé en ce que le monomère polyinsaturé est le triacrylate de triméthylol propane.5. Device according to any one of claims 3 and 4, characterized in that the polyunsaturated monomer is trimethylol propane triacrylate. 6. Dispositif selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'agent capable de complexer lesdits métaux lourds est le thio-2-benzimidazole ou le thio-2-vinyl-3-benzimidazole.6. Device according to any one of claims 1 to 5, characterized in that the agent capable of complexing said heavy metals is thio-2-benzimidazole or thio-2-vinyl-3-benzimidazole. 7. Dispositif selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le support est un copolymère de 85 à 95% en poids de monomère hydrophile monoinsaturé et de 5 à 15% en poids de monomère polyinsaturé.7. Device according to any one of claims 1 to 6, characterized in that the support is a copolymer of 85 to 95% by weight of hydrophilic monounsaturated monomer and from 5 to 15% by weight of polyunsaturated monomer. 8. Dispositif selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la teneur du support en agent capable de complexer lesdits métaux lourds est de 2 à 20% en poids par rapport au poids total du support contenant ledit agent.8. Device according to any one of claims 1 to 7, characterized in that the content of support agent capable of complexing said heavy metals is from 2 to 20% by weight relative to the total weight of the support containing said agent. 9. Procédé de préparation d'un dispositif d'épuration pour la décontamination d'effluents aqueux selon l'une quelconque des revendications 1 à 8, caractérisé en ce que l'on forme le support en copolymère hydrophile réticulé contenant l'agent complexant par polymérisation d'une solution comprenant . au moins un monomère hydrophile monoinsaturé, au moins un monomère polyinsaturé et un agent capable de complexer les métaux lourds.9. A method of preparing a purification device for the decontamination of aqueous effluents according to any one of claims 1 to 8, characterized in that the support is formed in crosslinked hydrophilic copolymer containing the complexing agent by polymerization of a solution comprising. at least one hydrophilic monounsaturated monomer, at least one polyunsaturated monomer and an agent capable of complexing heavy metals. 10. Procédé selon la revendication 9, caractérisé en ce que l'on réalise la polymérisation par irradiation de la solution au moyen de rayonnements ionisants.10. Method according to claim 9, characterized in that the polymerization is carried out by irradiation of the solution by means of ionizing radiation. 11. Procédé selon l'une quelconque des revendications 9 et 10, caractérisé en ce que la solution est une solution-alcoolique.11. Method according to any one of claims 9 and 10, characterized in that the solution is an alcoholic solution. 12. Procédé selon l'une quelconque des revendications 9 à 11, caractérisé en ce que l'on réalise la polymérisation sous vide ou en atmosphère inerte.12. Method according to any one of claims 9 to 11, characterized in that the polymerization is carried out under vacuum or in an inert atmosphere. 13. Utilisation du dispositif d'épuration selon l'une quelconque des revendications 1 à 8, pour la décontamination en cuivre ou en mercure d'effluents aqueux.13. Use of the purification device according to any one of claims 1 to 8, for the decontamination of copper or mercury of aqueous effluents.
EP19810401493 1980-10-07 1981-09-25 Purification device for removing heavy metals from contaminated aqueous effluents Expired EP0049656B1 (en)

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FR8021407A FR2491670A1 (en) 1980-10-07 1980-10-07 PURIFYING DEVICE FOR DECONTAMINATING AQUEOUS EFFLUENTS OF HEAVY METALS
FR8021407 1980-10-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2813208A1 (en) * 2000-08-30 2002-03-01 Commissariat Energie Atomique COMPLEXING STRUCTURE, DEVICE AND METHOD FOR TREATING LIQUID EFFLUENTS

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2256111A1 (en) * 1973-12-29 1975-07-25 Kernforschungsanlage Juelich
US4156658A (en) * 1974-06-28 1979-05-29 The United States Of America As Represented By The United States Department Of Energy Fixation of radioactive ions in porous media with ion exchange gels

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2256111A1 (en) * 1973-12-29 1975-07-25 Kernforschungsanlage Juelich
US4156658A (en) * 1974-06-28 1979-05-29 The United States Of America As Represented By The United States Department Of Energy Fixation of radioactive ions in porous media with ion exchange gels

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2813208A1 (en) * 2000-08-30 2002-03-01 Commissariat Energie Atomique COMPLEXING STRUCTURE, DEVICE AND METHOD FOR TREATING LIQUID EFFLUENTS
WO2002018050A1 (en) * 2000-08-30 2002-03-07 Commissariat A L'energie Atomique Complexing structure, device and method for treating liquid effluents
KR100848582B1 (en) * 2000-08-30 2008-07-28 꼼미사리아 아 레네르지 아토미끄 Complexing structure, device and method for treating liquied effluents

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EP0049656B1 (en) 1985-05-29
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FR2491670B1 (en) 1982-09-10

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