EP0049656A1 - 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
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
Authority
EP
European Patent Office
Prior art keywords
support
copolymer
heavy metals
complexing
monomer
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
EP19810401493
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English (en)
French (fr)
Other versions
EP0049656B1 (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
Original Assignee
Commissariat a lEnergie Atomique CEA
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.)
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Publication date
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Publication of EP0049656A1 publication Critical patent/EP0049656A1/de
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Publication of EP0049656B1 publication Critical patent/EP0049656B1/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 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.
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
FR8021407 1980-10-07
FR8021407A FR2491670A1 (fr) 1980-10-07 1980-10-07 Dispositif d'epuration pour la decontamination d'effluents aqueux en metaux lourds

Publications (2)

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

Family

ID=9246620

Family Applications (1)

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

Country Status (3)

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2813208A1 (fr) * 2000-08-30 2002-03-01 Commissariat Energie Atomique Structure complexante, dispositif et procede de traitement d'effluents liquides

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2256111A1 (de) * 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 (de) * 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 (fr) * 2000-08-30 2002-03-01 Commissariat Energie Atomique Structure complexante, dispositif et procede de traitement d'effluents liquides
WO2002018050A1 (fr) * 2000-08-30 2002-03-07 Commissariat A L'energie Atomique Structure complexante, dispositif et procede de traitement d'effluents liquides
KR100848582B1 (ko) * 2000-08-30 2008-07-28 꼼미사리아 아 레네르지 아토미끄 착화 구조체, 액상 유출물을 처리하는 장치 및 방법

Also Published As

Publication number Publication date
FR2491670A1 (fr) 1982-04-09
EP0049656B1 (de) 1985-05-29
FR2491670B1 (de) 1982-09-10
DE3170732D1 (en) 1985-07-04

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