EP0136496A2 - Process for transporting and/or storing wastes - Google Patents

Process for transporting and/or storing wastes Download PDF

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Publication number
EP0136496A2
EP0136496A2 EP84109707A EP84109707A EP0136496A2 EP 0136496 A2 EP0136496 A2 EP 0136496A2 EP 84109707 A EP84109707 A EP 84109707A EP 84109707 A EP84109707 A EP 84109707A EP 0136496 A2 EP0136496 A2 EP 0136496A2
Authority
EP
European Patent Office
Prior art keywords
emulsion
waste
resin
monomer
derivatives
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Withdrawn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
EP84109707A
Other languages
German (de)
French (fr)
Other versions
EP0136496A3 (en
Inventor
Pierre Albert Crouzet
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.)
WR Grace and Co
Original Assignee
WR Grace and Co
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 WR Grace and Co filed Critical WR Grace and Co
Publication of EP0136496A2 publication Critical patent/EP0136496A2/en
Publication of EP0136496A3 publication Critical patent/EP0136496A3/en
Withdrawn legal-status Critical Current

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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
    • G21F9/16—Processing by fixation in stable solid media
    • G21F9/167—Processing by fixation in stable solid media in polymeric matrix, e.g. resins, tars
    • 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
    • G21F9/16—Processing by fixation in stable solid media
    • G21F9/162—Processing by fixation in stable solid media in an inorganic matrix, e.g. clays, zeolites
    • G21F9/165—Cement or cement-like matrix

Definitions

  • the present invention relates to a method for the transport and / or storage of chemical, radioactive or other waste.
  • the present invention provides an extremely simple and inexpensive solution to the problem, while providing security unknown until now.
  • waste in question provides for these purposes and according to the invention that an emulsion with a small volume of water, highly thixotropic, is prepared and that the additives are added to this emulsion.
  • waste in the form of a liquid, semi-liquid or muddy effluent.
  • the emulsion used also contains flame retardant additives and a catalyst which is stable in cold but active in hot.
  • this solution makes it possible to transport waste to an independent factory, freeing, for example, nuclear power plants from the problem of waste treatment.
  • the percentage of water in the emulsion is then reduced to a value allowing the addition of water or effluents. liquids accompanying the different forms of waste.
  • the emulsion will be of the maximum self-extinguishing type, by the use of all brominated, chlorinated, phosphated or other products from the manufacture of the base resin.
  • the emulsion can for example be mixed with cement to form blocks and to be coated for example according to the coating process described in Swiss patent no ........ (patent application no 2329/83, filed April 29, 1983).
  • This process consists in producing a mixture comprising waste (for example radioactive waste) in saturation in their storage water, a resin and a monomer, to form an emulsion with the waste, their water, the resin and the monomer and by adding to this emulsion a hydraulic binder to make a concrete.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Removal Of Specific Substances (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Catalysts (AREA)
  • Colloid Chemistry (AREA)
  • Treatment Of Sludge (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

A transport and/or storage process for waste, esp. chemical and/or radioactive waste, comprises prepg. a strongly thixotropic emulsion with low water content and adding the waste in (semi-) fluid or sludge form to the emulsion. Also claimed is an emulsion for use in the process, the emulsion contg. a resin (pref. an unsatd. polyester resin), a monomer (pref. an unsatd. monomer with an extremely high flame point) and a thixotropic agent.

Description

La présente invention est relative à un procédé pour le transport et/ou le stockage de déchets chimiques, radio-actifs ou autres.The present invention relates to a method for the transport and / or storage of chemical, radioactive or other waste.

Les problèmes en rapport avec le transport de déchets chimiques ou radioactifs sont complexes et rencontrent très souvent des problèmes faisant appel à des traitements extrêmement coûteux.The problems related to the transport of chemical or radioactive waste are complex and very often encounter problems requiring extremely expensive treatments.

Des règlements internationaux prévoient par conséquent des mesures pour le transport de tels déchets, tenant compte de possibles endommagements des récipients de transport, d'incendies etc.International regulations therefore provide for measures for the transport of such waste, taking into account possible damage to transport containers, fires, etc.

La présente invention propose une solution du problème extrêmement simple et peu coûteuse, tout en offrant une sécurité inconnue jusqu'à maintenant.The present invention provides an extremely simple and inexpensive solution to the problem, while providing security unknown until now.

Le procédé pour le transport et/ou le stockage de déchets en question prévoit à ces fins et selon l'invention que l'on prépare une émulsion à faible volume d'eau, fortement thixotropée, et que l'on ajoute à cette émulsion les déchets sous forme d'un effluent liquide, semi-liquide ou boueux.The process for the transport and / or storage of waste in question provides for these purposes and according to the invention that an emulsion with a small volume of water, highly thixotropic, is prepared and that the additives are added to this emulsion. waste in the form of a liquid, semi-liquid or muddy effluent.

De préférence l'émulsion utilisée contient en outre des additifs retardateurs de flamme et un catalyseur stable à froid mais actif à chaud.Preferably, the emulsion used also contains flame retardant additives and a catalyst which is stable in cold but active in hot.

Dans cette forme d'exécution, c'est-à-dire en utilisant tous ces additifs, l'émulsion peut être allongée par des déchets sous forme d'un effluent liquide, semi-liquide ou boueux provenant de travaux nucléaires, chimiques ou autres, autorisant alors leur transport et/ou stockage puisque:

  • a) En cas de choc et de fissuration du récipient, le produit est un gel nécessitant agitation pour se fluidifier, donc ne coule pas.
  • b) Les produits retardateurs de flamme, en cas d'incendie, n'autorisent pas la propagation rapide de la flamme.
  • c) Si, par suite du feu, la température dépasse par exemple 60°C, l'émulsion se solidifiera et permettra un enlèvement plus rapide et plus mécanique des déchets.
In this embodiment, that is to say in using all these additives, the emulsion can be extended by waste in the form of a liquid, semi-liquid or muddy effluent from nuclear, chemical or other work, then authorizing their transport and / or storage since:
  • a) In case of shock and cracking of the container, the product is a gel requiring agitation to thin, therefore does not flow.
  • b) Flame retardant products, in the event of fire, do not allow rapid flame spread.
  • c) If, as a result of the fire, the temperature exceeds for example 60 ° C, the emulsion will solidify and allow faster and more mechanical removal of the waste.

Donc conforme aux règlements internationaux actuels, cette solution permet de transporter les déchets vers une usine indépendante, libérant, par example, les centrales nucléaires du problème du traitement des déchets.Therefore, in accordance with current international regulations, this solution makes it possible to transport waste to an independent factory, freeing, for example, nuclear power plants from the problem of waste treatment.

L'invention est décrite ci-après à l'aide d'un exemple de mise en oeuvre particulier:

  • On prépare tout d'abord une émulsion du type décrit dans les brevets américains no. 4,115,336, 4,204,988 et australiens no. 513,486 et 515,778. Une telle émulsion contient une résine, plus particulièrement une résine polyester de préférence non-saturée et un monomère, de préférence non-saturé.
The invention is described below using a specific implementation example:
  • First of all, an emulsion of the type described in American patents no. 4,115,336, 4,204,988 and Australian no. 513,486 and 515,778. Such an emulsion contains a resin, more particularly a polyester resin, preferably unsaturated, and a monomer, preferably unsaturated.

On réduit alors le pourcentage d'eau de l'émulsion à une valeur permettant l'addition des eaux ou effluents . liquides accompagnant les différentes formes de déchets.The percentage of water in the emulsion is then reduced to a value allowing the addition of water or effluents. liquids accompanying the different forms of waste.

L'émulsion sera de type auto-extinction maximum, par emploi de tous produits bromés, chlorés, phosphatés ou autres dès la fabrication de la résine de base.The emulsion will be of the maximum self-extinguishing type, by the use of all brominated, chlorinated, phosphated or other products from the manufacture of the base resin.

On ajoute à l'émulsion les additifs suivants:

  • A) Un agent thixotropique compatible avec l'eau, type gel de silice, "Aerosil" de Degussa, "Homocal G 50" de Adriss, certains types d'acéto butyrates, etc.
  • B) Des agents anti-feu type tri-hydrate d'alumine, dérivés phosphatés TCEP (Tri-chloro-éthyle-phosphate) ou dérivés du chlore (paraffines chlorées), dérivés du brome et, en particulier, décabromodiphénile oxide dosage maximum, etc.
  • C) Des catalyseurs du marché, compatible aves les résins polyesters insaturées, stablesà froid, gamme ambiance de +15°C à +60°C et actif à partir de 60°C, tels que les perbenzoates de t-butyle ou le 1.1 bis (t-butyle peroxy) cycloxenane, etc.
The following additives are added to the emulsion:
  • A) A thixotropic agent compatible with water, such as silica gel, "Aerosil" from Degussa, "Homocal G 50" from Adriss, certain types of aceto butyrates, etc.
  • B) Alumina tri-hydrate type fire-fighting agents, TCEP phosphate derivatives (Tri-chloro-ethyl-phosphate) or chlorine derivatives (chlorinated paraffins), bromine derivatives and, in particular, decabromodiphenile oxide maximum dosage, etc. .
  • C) Catalysts on the market, compatible with unsaturated polyester resins, cold stable, ambient range from + 15 ° C to + 60 ° C and active from 60 ° C, such as t-butyl perbenzoates or 1.1 bis (t-butyl peroxy) cycloxenane, etc.

Des déchets pouvant être ajoutés à l'emulsion sont par exemple les suivants:

  • Des lits mélangés ou non de résines échangeuses d'ions avec leurs habituelles impuretés - bore, lithium, ammoniaque, graphite, fer, etc. - et de PH le plus généralement acide, mais dans certains cas, légèrement basique.
Waste which can be added to the emulsion are for example the following:
  • Beds mixed or not of ion exchange resins with their usual impurities - boron, lithium, ammonia, graphite, iron, etc. - and more generally acidic PH, but in some cases, slightly basic.

Les concentrés le plus généralement avec fort pourcentage d'acide borique, neutralisés par NaOH jusqu'à des PH compris entre 7 et 9 suivant le contenu solide, avec produits secondaires tels que agents anti-moussants, détergents, acide oxalique, acide citrique, chromate de potasse, etc.Concentrates most generally with a high percentage of boric acid, neutralized by NaOH up to pH between 7 and 9 depending on the solid content, with secondary products such as anti-foaming agents, detergents, oxalic acid, citric acid, chromate potash, etc.

Des boues de décontamination, mélanges ou solutions basiques et acides, avec impuretés Lype chromates, borates, oxalates, graphite, fer, Mn02, etc.Decontamination sludge, basic and acidic mixtures or solutions, with L ype impurities chromates, borates, oxalates, graphite, iron, Mn02, etc.

En principe tout déchet à faible, moyenne ou forte radioactivité.In principle any waste with low, medium or high radioactivity.

Autres déchets d'ordre chimique.Other chemical wastes.

Après le transport, l'émulsion peut par exemple être mélangée avec du ciment pour former des blocs et pour être enrobée par exemple selon le procédé d'enrobage décrit dans le brevet suisse no........ (demande de brevet no. 2329/83, déposée le 29 avril 1983). Ce procédé consiste à réaliser un mélange comprenant des déchets .(par exemple des déchets radioactifs) en saturation dans leur eau de stockage, une résine et un monomère, pour former une émulsion avec les déchets, leur eau, la résine et le monomère et en ajoutant à cette émulsion un liant hydraulique pour réaliser un béton.After transport, the emulsion can for example be mixed with cement to form blocks and to be coated for example according to the coating process described in Swiss patent no ........ (patent application no 2329/83, filed April 29, 1983). This process consists in producing a mixture comprising waste (for example radioactive waste) in saturation in their storage water, a resin and a monomer, to form an emulsion with the waste, their water, the resin and the monomer and by adding to this emulsion a hydraulic binder to make a concrete.

Claims (11)

1. Procédé pour le transport et/ou le stockage de déchets, particulièrement de déchets chimiques et/ou radioactifs, caractérisé en ce que l'on prépare une émulsion à faible volume d'eau, fortement thixotropée, et en ce que l'on ajoute à cette émulsion les déchets sous forme d'un effluent liquide, semi-liquide ou boueux.1. Method for the transport and / or storage of waste, particularly chemical and / or radioactive waste, characterized in that an emulsion with a low volume of water, highly thixotropic, is prepared, and in that one add to this emulsion the waste in the form of a liquid, semi-liquid or muddy effluent. 2. Procédé selon la revendication 1, caractérisé en ce que l'émulsion utilisée contient en plus des additifs retardateurs de flamme.2. Method according to claim 1, characterized in that the emulsion used additionally contains flame retardant additives. 3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'émulsion utilisée contient en outre un catalyseur qui est stable à basse température, comme par exemple entre 10°C et 60°C, mais actif à haute température, comme par exemple au-dessus de 60°C.3. Method according to claim 1 or 2, characterized in that the emulsion used also contains a catalyst which is stable at low temperature, such as between 10 ° C and 60 ° C, but active at high temperature, such as example above 60 ° C. 4. Procédé selon la revendication 1, caractérisé en ce que l'émulsion contient un agent thixotropique compatible avec l'eau, comme par exemple le gel de silice ou des acéto-butyrates.4. Method according to claim 1, characterized in that the emulsion contains a thixotropic agent compatible with water, such as for example silica gel or aceto-butyrates. 5. Procédé selon la revendication 2, caractérisé en ce que l'on utilise comme additifs des agents anti-feu type tri-hydrate d'alumine, des dérivés phosphatés tri-chloro-éthyle-phosphate ou des dérivés du chlore, comme des paraffines chlorées, ou des dérivés du brome, comme le décabromodiphénile oxide.5. Method according to claim 2, characterized in that as additives fire-fighting agents of the alumina tri-hydrate type, tri-chloro-ethyl-phosphate phosphate derivatives or chlorine derivatives, such as paraffins chlorinated, or bromine derivatives, such as decabromodiphenile oxide. 6. Procédé selon la revendication 3, caractérisé en ce que l'on utilise comme catalyseur les perbenzoates de t-butyle ou le l.l-bis-(t-butyle peroxy) cycloxenane.6. Method according to claim 3, characterized in that the catalyst used is t-butyl perbenzoates or l.l-bis- (t-butyl peroxy) cycloxenane. 7. Emulsion pour la mise en oeuvre du procédé selon les revendications 1-6, caractérisée en ce qu'elle contient une résine, un monomère et un agent thixotropique.7. Emulsion for implementing the method according to claims 1-6, characterized in that it contains a resin, a monomer and a thixotropic agent. 8. Emulsion selon la revendication 7, caractérisée en ce que la résine est une résine polyester, de préférence non-saturée.8. Emulsion according to claim 7, characterized in that the resin is a polyester resin, preferably unsaturated. 9. Emulsion selon la revendication 7, caractérisée en ce que le monomère est non-saturé et il peut être choisi pour que son point éclair soit le plus élevé possible.9. Emulsion according to claim 7, characterized in that the monomer is unsaturated and it can be chosen so that its flash point is as high as possible. 10. Emulsion selon la revendication 7, caractérisée en ce qu'elle contient en outre des additifs retardateurs de flamme et des catalyseurs stables à froid mais actifs à chaud.10. Emulsion according to claim 7, characterized in that it also contains flame retardant additives and catalysts stable in cold but active in hot. 11. Procédé selon l'une des revendications 1-6, caractérisé en ce que l'émulsion contenant les déchets est mélangée avec un liant hydraulique, comme par exemple du ciment, pour former des blocs de béton.11. Method according to one of claims 1-6, characterized in that the emulsion containing the waste is mixed with a hydraulic binder, such as for example cement, to form concrete blocks.
EP84109707A 1983-08-23 1984-08-15 Process for transporting and/or storing wastes Withdrawn EP0136496A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH4599/83A CH656539A5 (en) 1983-08-23 1983-08-23 PROCESS FOR TREATMENT OF CHEMICAL OR RADIOACTIVE WASTE.
CH4599/83 1983-08-23

Publications (2)

Publication Number Publication Date
EP0136496A2 true EP0136496A2 (en) 1985-04-10
EP0136496A3 EP0136496A3 (en) 1986-03-19

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EP84109707A Withdrawn EP0136496A3 (en) 1983-08-23 1984-08-15 Process for transporting and/or storing wastes

Country Status (11)

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EP (1) EP0136496A3 (en)
JP (1) JPS6122300A (en)
CH (1) CH656539A5 (en)
DE (1) DE3430165A1 (en)
FR (1) FR2550969A1 (en)
GB (1) GB2145405B (en)
IL (1) IL72751A (en)
IT (1) IT1213210B (en)
NL (1) NL8402581A (en)
SE (1) SE8404187L (en)
ZA (1) ZA846523B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4439173A1 (en) * 1994-11-07 1996-05-09 C & E Consulting Und Engineeri Immobilisation of harmful materials in dust or particle form
US6844036B2 (en) 2001-05-22 2005-01-18 Ausimont S.P.A. Fluoroelastomeric compositions
US6902676B2 (en) 2001-02-26 2005-06-07 Ausimont S.P.A. Porous hydrophilic membranes
CN109545418A (en) * 2018-11-29 2019-03-29 中国船舶重工集团公司第七〇九研究所 Marine nuclear power platform Liquid Radwaste Treatment and method

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2179645A (en) * 1985-08-02 1987-03-11 Alexander George Copson Waste management system

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2644472A1 (en) * 1975-10-03 1977-04-14 Dow Chemical Co METHOD OF ENCAPSULATING RADIOACTIVE WASTE
FR2361724A1 (en) * 1976-08-12 1978-03-10 Commissariat Energie Atomique STORAGE PROCESS FOR CONTAMINATED ION EXCHANGER RESINS
FR2366234A1 (en) * 1976-04-27 1978-04-28 Crouzet Pierre Building material contg. polyester - and siliceous material and a setting material e.g. hydraulic cement
DE2717656A1 (en) * 1977-04-21 1978-10-26 Nukem Gmbh PROCESS FOR THE PRODUCTION OF LEAK-RESISTANT AND SALINE-RESISTANT BLOCKS FROM CEMENT AND RADIOACTIVE WASTE
WO1980000047A1 (en) * 1978-06-08 1980-01-10 Bp Chem Int Ltd Encapsulating wastes
FR2505539A1 (en) * 1981-05-11 1982-11-12 Snial Resine Poliestere Spa METHOD OF SOLIDIFYING RADIO-ACTIVE WASTE CONTAINED IN ION-EXCHANGING RESINS, SOLID ARTICLES THUS OBTAINED, AND COMPOSITION CONTAINING RADIOACTIVE MATERIAL BASED ON ION-EXCHANGE RESINS

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2046499A (en) * 1979-04-06 1980-11-12 Astor Chemical Ltd Encapsulation of radioactive waste
US4379081A (en) * 1981-03-12 1983-04-05 Westinghouse Electric Corp. Method of encapsulating waste radioactive material
JPS58501503A (en) * 1981-09-30 1983-09-08 ラデツカ，インク Immobilization method for organic pollutants and non-flowable matrices obtained therefrom

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2644472A1 (en) * 1975-10-03 1977-04-14 Dow Chemical Co METHOD OF ENCAPSULATING RADIOACTIVE WASTE
FR2366234A1 (en) * 1976-04-27 1978-04-28 Crouzet Pierre Building material contg. polyester - and siliceous material and a setting material e.g. hydraulic cement
FR2361724A1 (en) * 1976-08-12 1978-03-10 Commissariat Energie Atomique STORAGE PROCESS FOR CONTAMINATED ION EXCHANGER RESINS
DE2717656A1 (en) * 1977-04-21 1978-10-26 Nukem Gmbh PROCESS FOR THE PRODUCTION OF LEAK-RESISTANT AND SALINE-RESISTANT BLOCKS FROM CEMENT AND RADIOACTIVE WASTE
WO1980000047A1 (en) * 1978-06-08 1980-01-10 Bp Chem Int Ltd Encapsulating wastes
FR2505539A1 (en) * 1981-05-11 1982-11-12 Snial Resine Poliestere Spa METHOD OF SOLIDIFYING RADIO-ACTIVE WASTE CONTAINED IN ION-EXCHANGING RESINS, SOLID ARTICLES THUS OBTAINED, AND COMPOSITION CONTAINING RADIOACTIVE MATERIAL BASED ON ION-EXCHANGE RESINS

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4439173A1 (en) * 1994-11-07 1996-05-09 C & E Consulting Und Engineeri Immobilisation of harmful materials in dust or particle form
US6902676B2 (en) 2001-02-26 2005-06-07 Ausimont S.P.A. Porous hydrophilic membranes
US6844036B2 (en) 2001-05-22 2005-01-18 Ausimont S.P.A. Fluoroelastomeric compositions
CN109545418A (en) * 2018-11-29 2019-03-29 中国船舶重工集团公司第七〇九研究所 Marine nuclear power platform Liquid Radwaste Treatment and method

Also Published As

Publication number Publication date
NL8402581A (en) 1985-03-18
SE8404187L (en) 1985-02-24
DE3430165A1 (en) 1985-03-14
EP0136496A3 (en) 1986-03-19
GB2145405A (en) 1985-03-27
GB2145405B (en) 1987-02-04
CH656539A5 (en) 1986-07-15
ZA846523B (en) 1985-04-24
JPS6122300A (en) 1986-01-30
IL72751A (en) 1988-06-30
FR2550969A1 (en) 1985-03-01
IT1213210B (en) 1989-12-14
IT8422394A0 (en) 1984-08-23
GB8421377D0 (en) 1984-09-26
SE8404187D0 (en) 1984-08-22

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