EP3807223A1 - Procédés pour éliminer l'iodure radioactif contenu dans des eaux usées - Google Patents

Procédés pour éliminer l'iodure radioactif contenu dans des eaux usées

Info

Publication number
EP3807223A1
EP3807223A1 EP19733436.0A EP19733436A EP3807223A1 EP 3807223 A1 EP3807223 A1 EP 3807223A1 EP 19733436 A EP19733436 A EP 19733436A EP 3807223 A1 EP3807223 A1 EP 3807223A1
Authority
EP
European Patent Office
Prior art keywords
iodide
water
salt
waste water
steps
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.)
Withdrawn
Application number
EP19733436.0A
Other languages
German (de)
English (en)
Inventor
Robert N. Grass
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.)
Turbobeads GmbH
Original Assignee
Turbobeads GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Turbobeads GmbH filed Critical Turbobeads GmbH
Publication of EP3807223A1 publication Critical patent/EP3807223A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • 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
    • G21F9/10—Processing by flocculation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/006—Radioactive compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/003—Wastewater from hospitals, laboratories and the like, heavily contaminated by pathogenic microorganisms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/09—Viscosity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/18—Removal of treatment agents after treatment

Definitions

  • the present invention relates to methods for reducing the iodide content in aqueous systems; in particular processes for cleaning with hospital wastewater which arise in connection with radiochemistry, diagnosis and therapy.
  • the present invention further relates to systems which can be used in these processes.
  • the present invention further relates to kits of chemicals which are suitable for these processes and / or can be used in these plants.
  • radioactive sodium iodide preparations are used to treat thyroid carcinomas; these contain 131J. Since the excretions (faeces, urine, sweat) of the patients radiate radioactively over the treatment period, the wastewater of the patients in clinics must be collected separately in decay tanks. The wastewater is stored in these decay tanks until it falls below a limit value (emission of permitted radiation in MBq per week) specified by the Federal Office of Public Health (in Switzerland, in other countries). Due to the half-life of 131J, the radioactive sodium iodide doses administered to the patients, and the permitted delivery limits, the required storage time of the waste water in the decay tank is determined (typically 1-2 months).
  • radioactive iodide The size of the decay tanks that a given clinic has available (permanently installed in the space provided) limits the number of patients who can be treated with radioactive iodine. Thus, in order to be able to treat more patients, a hospital has to do a great deal of construction work (increase the decay tank volume).
  • Other radioactive iodide compounds are also used in hospitals and other facilities. The term radioactive iodide therefore includes the isotopes 131J, 123J and 125J, with 131J being of special importance.
  • the radioactive iodide In order to reduce the radioactivity in the corresponding hospital wastewater, the radioactive iodide must be removed from the water.
  • hospital wastewater also contains high chlorine loads (as chloride), whereby the chloride concentration is usually considerably higher than the iodine concentration. If an lx-4x excess of silver or copper is added to iodine as in US5352367, the amount of metal is not sufficient to bind the entire iodide and chloride. Even if significantly more metal is added, a large part of the metal ions is bound by the chloride, so that only a small part remains for the reaction with the iodide. As a result, the precipitation of the iodide is only incomplete.
  • the object of the present invention is therefore to provide methods for removing the radioactivity from the decay tanks so that the water can be drained off more quickly.
  • the task is to provide methods for removing iodide, especially radioactive iodide, from aqueous systems.
  • the tasks outlined above are solved according to the independent claims.
  • the dependent claims represent advantageous embodiments. Further advantageous embodiments can be found in the description and the figures.
  • the general, preferred and particularly preferred embodiments, ranges etc. given in connection with the present invention can be combined with one another as desired. Likewise, individual definitions, embodiments, etc. can be omitted or not relevant.
  • Wastewater The term is well known and includes aqueous systems that arise when used in the past. Such aqueous systems are contaminated by their previous use, that is to say they have changed in properties or composition.
  • the term wastewater thus includes the radioactive contaminated hospital wastewater as well as gray water (according to EN12056-1), black water (according to EN6107-7: 1997), wastewater from industrial processing processes and wastewater from nuclear power plants.
  • the term wastewater describes in particular those aqueous systems which, in addition to iodide (in particular 131J), also contain chloride.
  • the task outlined above is carried out in a multi-stage process, i.e. in a multi-step process.
  • chemicals are added to the radioactive water in a predetermined sequence.
  • Each step fulfills a specific part of the task:
  • non-radioactive iodide as iodide-containing salt, e.g. Nal
  • non-radioactive iodide as iodide-containing salt, e.g. Nal
  • the flocculation of the iron hydroxides helps the separation of the previously precipitated salts by aggregation with copper iodide, copper chloride, silver iodide and silver chloride particles.
  • a polymeric flocculant can be added after the excess heavy metal has been precipitated.
  • Anionic polymers such as eg polyacrylic acids, cellulose derivatives, polysaccharides, polyamines, polyvinyl alcohol, and soaps.
  • the precipitated substances which largely consist of silver iodide, copper iodide (radioactive and non-radioactive), silver chloride, copper iodide and optionally iron hydroxides, are separated by a suitable solid / liquid process (eg by filtration, sedimentation in a tank and / or via a Flydrocyclone) removed from the waste water.
  • a suitable solid / liquid process eg by filtration, sedimentation in a tank and / or via a Flydrocyclone
  • the radioactive content of the wastewater is significantly reduced and the water does not contain any further ions or solids that limit the direct release of the water to the public wastewater network. This means that the wastewater can be disposed of more quickly (with a significantly shorter decay time, ideally without further decay in tanks).
  • the solid (which is radioactive by containing 1-131) is stored for decay.
  • the silver is purified from the solid (e.g. by dissolving the Agl and AgCI in acid and chemically reducing the silver with glucose).
  • the silver can now be used again (e.g. as water-soluble nitrate) in step 2.
  • the hospital waste water is treated in several steps and the radioactivity of the waste water is gradually reduced.
  • the first step at least 90% of the available halide ions (CI-, I.) Is generated by generating Cu (l) ions immediately before, or in the wastewater, and with the optional addition of non-radioactive halide ions (depending on the specific composition of the hospital wastewater) -, Br-) precipitated in the water.
  • silver ions are added to the water, which leads to a majority (> 80%) of the halide ions remaining after the 1st treatment step being precipitated.
  • the temperature before or after the addition of the metal salts and / or additional halide ions is reduced or raised by at least 10 ° C. by heating or cooling the waste water. Suitable methods for this are well known to the person skilled in the art and include the use of immersion heaters, instantaneous water heaters, heat exchangers or the addition of ice.
  • Hospital wastewater is stored for weeks now in order to ensure that radioactivity decays, which naturally requires large tanks with residence times of weeks to months.
  • the hospital wastewater is therefore treated continuously or semi-continuously. This is characterized by the fact that the residence time of the water in the purification process is less than 24 hours and the untreated, radioactive hospital wastewater is stored for less than 3 days. This can drastically reduce the space required for the storage of radioactive waste water for a typical hospital.
  • the metering of the metal ions and / or optional halide ions to the hospital wastewater is preferably carried out via a T-piece, followed (in the direction of flow) by a static mixer, e.g. commercially available from Sulzer-Chemtech, followed by a solid / liquid separation process.
  • a static mixer e.g. commercially available from Sulzer-Chemtech
  • Corresponding separation processes are well known to the person skilled in the art and include how they are used in traditional wastewater treatment. Filtration is the preferred method.
  • the filter load can be reduced using a hydrocyclone or an upstream sedimentation basin.
  • One-way filtration elements of compact construction are preferably used, e.g. commercially available from PALL or 3M.
  • At least one ion-selective electrode or an overall conductance electrode is used for process monitoring in the process described above.
  • Corresponding electrodes are commercially available from Mettler-Toledo.
  • the present invention furthermore relates to a kit comprising various chemical components.
  • This kit provides the chemicals suitable for the inventive method and is therefore suitable for carrying out the method as described here and also suitable for operating a system as described below.
  • kit A kit B and kit C.
  • aqueous solution of copper (II) sulfate preferably 0.5-1 mol / l, preferably buffered in the pH range 5-9;
  • aqueous solution of copper (II) sulfate preferably 0.5-1 mol / l, preferably buffered in the pH range 5-9;
  • a flocculant preferably chitosan
  • aqueous solution of copper (II) sulfate preferably 0.5-1 mol / l, preferably buffered in the pH range 5-9;
  • an improved radionucleotide decay system is provided.
  • the known radionucleotide decay systems essentially comprise one or more storage containers which are connected to the sewage system, e.g. a hospital.
  • the volume of the storage tanks is dimensioned so that a sufficient dwell time is ensured before the wastewater is discharged into the public network.
  • inventive decay system enables the addition of various chemicals, in particular copper (II) salts and suitable reducing agents (e.g. ascorbic acid) and non-radioactive halide solutions (e.g. Nal, NaCl, NaBr, Kl, KCl), in order to carry out the process described in the first aspect.
  • inventive decay system comprises, in addition to the storage container, means for adding liquid components, in particular
  • Radioactivity determination means
  • Example 1 Reference example according to ÜS5352367 with excess AgN0 3 :
  • Example 2 without addition of Nal, with precipitation of silver ions
  • Example 3 with addition of Nal with precipitation of silver ions
  • the supernatant could simply be drained off (98% of the original volume).
  • the remaining sediment (2% of the original volume of the above precipitation) was placed in a decay basin.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • High Energy & Nuclear Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

L'invention concerne des procédés pour réduire la teneur en iodure dans des systèmes aqueux, notamment des procédés pour purifier des eaux usées cliniques qui se forment dans le cadre de la radiochimie, du diagnostic et de la thérapie. De l'iodure radioactif est éliminé d'eaux usées grâce à sa précipitation par l'intermédiaire d'un excès d'ions argent ou cuivre. Les ions de métal lourd ainsi restant sont éliminés des eaux usées au cours d'une seconde étape, par précipitation au moyen d'un sel d'halogénure. La charge d'irradiation des eaux usées traitées se trouve ainsi réduite, tout comme sa teneur en métaux lourds, elles peuvent ainsi être évacuées dans les eaux usées publiques.
EP19733436.0A 2018-06-18 2019-06-18 Procédés pour éliminer l'iodure radioactif contenu dans des eaux usées Withdrawn EP3807223A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH00766/18A CH715104A2 (de) 2018-06-18 2018-06-18 Methode zur Entfernung von radioaktivem Jodid aus Abwässern.
PCT/EP2019/066023 WO2019243338A1 (fr) 2018-06-18 2019-06-18 Procédés pour éliminer l'iodure radioactif contenu dans des eaux usées

Publications (1)

Publication Number Publication Date
EP3807223A1 true EP3807223A1 (fr) 2021-04-21

Family

ID=67060384

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19733436.0A Withdrawn EP3807223A1 (fr) 2018-06-18 2019-06-18 Procédés pour éliminer l'iodure radioactif contenu dans des eaux usées

Country Status (3)

Country Link
EP (1) EP3807223A1 (fr)
CH (1) CH715104A2 (fr)
WO (1) WO2019243338A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116020398A (zh) * 2023-02-22 2023-04-28 西华师范大学 亚铜基阳离子水凝胶复合吸附剂及其制备方法、应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2422711C2 (de) * 1974-05-10 1983-02-10 Durcak, Herbert, Ing.(grad.), 8882 Lauingen Verfahren zur Aufbereitung von Abwässern mit radioaktiven Nukliden
CH626467A5 (fr) * 1976-01-14 1981-11-13 Benes Ivan
DE2903705A1 (de) * 1979-01-31 1980-09-11 Gilak Armin Verfahren zur abtrennung von jod- radionukliden aus waessrigen loesungen
JP2540401B2 (ja) 1991-11-05 1996-10-02 動力炉・核燃料開発事業団 放射性ヨウ素化合物の沈澱分離方法
JP3145176B2 (ja) * 1992-04-23 2001-03-12 株式会社日立製作所 放射性廃液中の放射性ヨウ素の除去方法
KR101490355B1 (ko) * 2014-01-09 2015-02-05 한국원자력연구원 방사성 폐수 내 고농도 요오드의 무기광물화 제거방법 및 제거장치

Also Published As

Publication number Publication date
WO2019243338A1 (fr) 2019-12-26
CH715104A2 (de) 2019-12-30

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