EP0049656B1 - Reinigungsvorrichtung zur Dekontamination von Schwermetallen aus kontaminierten Abwässern - Google Patents

Reinigungsvorrichtung zur Dekontamination von Schwermetallen aus kontaminierten Abwässern Download PDF

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Publication number
EP0049656B1
EP0049656B1 EP19810401493 EP81401493A EP0049656B1 EP 0049656 B1 EP0049656 B1 EP 0049656B1 EP 19810401493 EP19810401493 EP 19810401493 EP 81401493 A EP81401493 A EP 81401493A EP 0049656 B1 EP0049656 B1 EP 0049656B1
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EP
European Patent Office
Prior art keywords
thio
agent
weight
support
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19810401493
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English (en)
French (fr)
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EP0049656A1 (de
Inventor
Aymé Cornu
Roger Massot
Gilbert Gaussens
Maryvonne Nicaise
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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Publication of EP0049656A1 publication Critical patent/EP0049656A1/de
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Classifications

    • 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 from aqueous effluents are to absorb or capture heavy metal ions, for example mercury, lead, cadmium, copper, silver or chromium, using agents capable of forming sufficiently stable complexes with these metal ions.
  • heavy metal ions for example mercury, lead, cadmium, copper, silver or chromium
  • sulfur derivatives are of great interest because they have a great 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-3-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-3-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 heavy metal decontamination of aqueous effluents which ensures 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 of crosslinked hydrophilic copolymer, consisting of 85 to 95% by weight of monounsaturated hydrophilic monomer and 5 to 15% by weight of polyunsaturated monomer, and an agent capable of complexing said heavy metals, incorporated into said support, at a rate of 2 to 20% by weight relative to the total weight of the support and of the agent, said agent being chosen from thio-2-benzimidazole, chlorinated, nitrated and thio-2-benzimidazole dimethyl, thio-2-vinyl-3-benzimidazole, thio-ureido benzimidazole, amino-2-benzimidiazole and guanidines.
  • the copolymer is a copolymer of at least one hydrophilic monounsaturated monomer 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, diethylene acrylate 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 pentaerythritol 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 vinylation. According to a procedure similar to that described by H. Hopff, U. Wyss, H. Jussi, Helvetica Chimica Acta, vol. 13, Fasc. 1 (1960), p. 135, for the vinylation of nitrogen heterocycles.
  • the content of polyunsaturated monomer in the copolymer 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.
  • This is obtained using 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 generally 5 to 15% by weight relative to the total weight of the support containing the complexing agent, 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 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, a 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 feture 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 an 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 the fabric or the 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.
  • PVB-3 denotes the support in which the complexing agent is thio-2-benzimidazole
  • PVB-4 denotes 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 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.
  • 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 PVB-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 constituted by 40 ml of a solution of copper sulphate at 93 ppm of copper and at pH 8.
  • 1 g 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 i , F 2 and F3 and their copper content is determined by flameless atomic absorption spectrometry to obtain better precision.
  • 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 1 g of this support is mixed with 100 ml of a HgCl 2 mercury 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 ,, F 2 and F 3 , and the mercury content is determined on each of these filtrates by flameless atomic absorption spectrometry.

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Claims (10)

1. Reinigungsvorrichtung zur Dekontaminierung von Schwermetallen aus kontaminierten Abwässern, dadurch gekennzeichnet, daß sie aufweist einen Träger aus einem vernetzten hydrophilen Copolymeren, das zu 85 bis 95 Gew.% aus einem hydrophilen, einfach ungesättigten Monomeren und zu 5 bis 15 Gew.% aus einem mehrfach ungesättigten Monomeren sowie aus einem Agens besteht, das in den Träger in einer Menge von 2 bis 20 Gew.%, bezogen auf das Gesamtgewicht von Träger und Agens, eingearbeitet ist und mit den Schwermetallen einen Komplex bilden kann, wobei das Agens ausgewählt wird aus der Gruppe Thio-2-benzimidazol, der Chlor-, Nitro- und Dimethylderivate von Thio-2-benzimidazol, Thio-2-vinyl-3-benzimidazol, Thioureidobenzimidazol, Amino-2-benzimidazol und der Guanidine.
2. Vorrichtung nach Anspruch 1, dadurch gekennzeichnet, daß es sich bei dem Copolymeren um ein Acryl- und/oder Methacryl-Copolymeres handelt.
3. Vorrichtung nach Anspruch 1, dadurch gekennzeichnet, daß es sich bei dem einfach ungesättigten Monomeren um die Acrylsäure handelt.
4. Vorrichtung nach einem der Ansprüche 1 und 3, dadurch gekennzeichnet, daß es sich bei dem mehrfach ungesättigten Monomeren um das Triacrylat von Trimethylolpropan handelt.
5. Vorrichtung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es sich bei dem Agens, das mit den Schwermetallen einen Komplex bilden kann, um Thio-2-benzimidazol oder Thio-2-vinyl-3-benzimidazol handelt.
6. Verfahren zur Herstellung einer Reinigungsvorrichtung zur Dekontamination von Abwässern nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß ein Träger aus einem vernetzten hydrophilen Copolymeren, der ein komplexbildendes Agens enthält, hergestellt wird durch Polymerisieren einer Lösung, die enthält:
a) ein Monomeren-Gemisch, das umfaßt:
-85 bis 95 Gew.% mindestens eines einfach ungesättigten hydrophilen Monomeren und
- bis 15 Gew.% mindestens eines mehrfach ungesättigten Monomeren; und
b) ein Agens, das mit den Schwermetallen einen Komplex bilden kann, das ausgewählt wird aus der Gruppe Thio-2-benzimidazol, der Chlor-, Nitro- und Dimethylderivate von Thio-2-benzimidazol, Thio-2-vinyl-3-benzimidazol, Thio-ureidobenzimidazol, Amino-2-benzimidazol und der Guanidine, wobei die Menge des in der Lösung vorliegenden Agens 2 bis 20 Gew.% des Gesamtgewichtes der Monomeren und des Agens darstellt.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß die Polymerisation durch Bestrahlen der Lösung mit ionisierenden Strahlen erfolgt.
8. Verfahren nach einem der Ansprüche 6 und 7, dadurch gekennzeichnet, daß es sich bei der Lösung um eine alkoholische Lösung handelt.
9. Verfahren nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, daß die Polymerisation unter Vakuum oder in einer inerten Atmosphäre durchgeführt wird.
10. Verwendung der Reinigungsvorrichtung nach einem der Ansprüche 1 bis 5 zur Dekontamination von Kupfer oder Quecksilber aus Abwässern.
EP19810401493 1980-10-07 1981-09-25 Reinigungsvorrichtung zur Dekontamination von Schwermetallen aus kontaminierten Abwässern Expired EP0049656B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8021407A FR2491670A1 (fr) 1980-10-07 1980-10-07 Dispositif d'epuration pour la decontamination d'effluents aqueux en metaux lourds
FR8021407 1980-10-07

Publications (2)

Publication Number Publication Date
EP0049656A1 EP0049656A1 (de) 1982-04-14
EP0049656B1 true EP0049656B1 (de) 1985-05-29

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Application Number Title Priority Date Filing Date
EP19810401493 Expired EP0049656B1 (de) 1980-10-07 1981-09-25 Reinigungsvorrichtung zur Dekontamination von Schwermetallen aus kontaminierten Abwässern

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EP (1) EP0049656B1 (de)
DE (1) DE3170732D1 (de)
FR (1) FR2491670A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2813208B1 (fr) * 2000-08-30 2003-03-28 Commissariat Energie Atomique Structure complexante, dispositif et procede de traitement d'effluents liquides

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2365114C2 (de) * 1973-12-29 1975-11-13 Kernforschungsanlage Juelich Gmbh, 5170 Juelich Verfahren zum Reinigen von Plutonium und/oder Neptunium enthaltenden Lösungen durch Abtrennen von Plutonium und/oder Neptunium
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

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Publication number Publication date
DE3170732D1 (en) 1985-07-04
EP0049656A1 (de) 1982-04-14
FR2491670A1 (fr) 1982-04-09
FR2491670B1 (de) 1982-09-10

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