EP0400130B1 - Aufbereiten von radioaktivem abwasser - Google Patents

Aufbereiten von radioaktivem abwasser Download PDF

Info

Publication number
EP0400130B1
EP0400130B1 EP90900069A EP90900069A EP0400130B1 EP 0400130 B1 EP0400130 B1 EP 0400130B1 EP 90900069 A EP90900069 A EP 90900069A EP 90900069 A EP90900069 A EP 90900069A EP 0400130 B1 EP0400130 B1 EP 0400130B1
Authority
EP
European Patent Office
Prior art keywords
boric acid
alcohol
water
residues
concentrate
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 - Lifetime
Application number
EP90900069A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0400130A1 (de
Inventor
Klaus Rose
Aloys DÖRR
Uwe KÄLBERER
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.)
GG Noell GmbH
Original Assignee
GG Noell 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 GG Noell GmbH filed Critical GG Noell GmbH
Publication of EP0400130A1 publication Critical patent/EP0400130A1/de
Application granted granted Critical
Publication of EP0400130B1 publication Critical patent/EP0400130B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • G21F9/08—Processing by evaporation; by distillation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S159/00—Concentrating evaporators
    • Y10S159/12—Radioactive
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S203/00—Distillation: processes, separatory
    • Y10S203/06—Reactor-distillation

Definitions

  • the invention relates to a method according to the preamble of claim 1.
  • Wastewater of this type occurs, for example, as an evaporator concentrate in nuclear power plants that are equipped with a pressurized water reactor.
  • the invention is therefore based on the object of proposing a process for the treatment and disposal of waste water which contains boric acid and other boron compounds and radionuclides, in particular radioactive antimony, in which the ultimately unusable constituents of the waste water can be reduced very greatly in volume and that is as quick, environmentally friendly and inexpensive as possible.
  • the invention is based on the knowledge that, as stated in EP-A-0 125 017, azeotropes from methanol or ethanol and boric acid esters are difficult to separate and should therefore be avoided if possible, while azeotropes from water and alcohols are easy to separate. In contrast to methanol, the esterification does not require sulfuric acid as the catalyst and therefore larger amounts of salt can be avoided and not contaminated with the radionuclides.
  • the waste water is essentially evaporated to dryness or already evaporated waste water from intermediate stores with butyl alcohol or longer-chain single alcohols, i.e. not methanol, but for example n-butanol, with alcohol for complete esterification of the boric acid and the water of reaction formed and the excess alcohol be distilled off.
  • the boric acid ester formed initially remains in the bottom in this distillation stage.
  • the azeotrope of butanol and water has a boiling point of almost 93 ° C, which can still be reduced by distillation at a pressure below atmospheric pressure.
  • the evaporator concentrate may have to be cooled below the azeotropic boiling point beforehand.
  • the ester can also be distilled off by further increasing the process temperature or further reducing the process pressure. Since the boiling point of butyl ester is 227 ° C, the temperature range is large enough to master the process safely.
  • the boric acid ester has also been distilled off, all remain non-volatile Components in the swamp return as solid products. All radionuclides as well as all non-radioactive contaminants of the concentrate are included in this solid residue and can therefore be disposed of. Due to the special procedure, the intermediate storage of the residues is not necessary in order to wait until the antimony activity has subsided before the radionuclides can be chemically precipitated.
  • evaporator concentrates or wastewater can thus be worked up either immediately or only after a long storage period.
  • the method according to the invention also gives the possibility of circulating the alcohol recovered in the saponification of the boric acid ester and of using further concentrates in the re-esterification.
  • the alcohol can also be separated from the azeotrope initially distilled off and recycled for further esterification.
  • the boric acid which is recovered analytically pure during the saponification and can be returned to the primary water of the nuclear reactor without further purification after water has been separated off.
  • a very inexpensive separation of the azeotrope can be carried out by simple condensation of the azeotrope in the first stage and subsequent separation of the two-phase mixture, for example in a decanter.
  • the Residues to be disposed of can be reduced by first precipitating the non-radioactive salts by conventional chemical processes.
  • the wastewater can be filtered before evaporation and the solids can be conditioned separately. If alkaline evaporators are used, the concentrate must be neutralized before starting the process according to the invention.
  • Waste water or pre-concentrated waste water K is evaporated or dried in the first process stage ET.
  • the concentrate V can then be subjected to an esterification VE to boric acid ester together with boric acid, borates and residual water S coming from interim storage facilities or contaminated sites with slow addition of an excess of longer-chain single alcohol (e.g. butanol) A.
  • a first distillation stage D1 separates the azeotrope butanol / water A / W from ester E and residues R, which is then subjected to further drying FT, which, for. B. happens directly in the final storage container (barrels) to separate the ester E from the remaining solids F.
  • the solids F can go directly to a Repository LA are spent while the ester E is saponified with water (VS).
  • the resulting pure analytical, crystalline boric acid R is conditioned by filtering FI and drying TK and returned to the power plant; the filtrate F is fed to the saponification VS again.
  • the azeotrope butanol / water A / W from the saponification VS and the distillation D1 is separated in a second distillation stage D2 and the constituents are returned.
  • the resulting pure process water W is released for general disposal after a control analysis KA.
  • Pre-concentrated wastewater from a nuclear power plant has a boric acid content of 10% by weight and a specific gamma activity of 0.5 Ci / t, the majority of which is due to antimony and the radioactive nuclides cobalt and manganese.
  • This concentrate is concentrated almost to dryness in an evaporator.
  • N-Butanol is gradually added to this concentrate in an esterification device in a multiple excess.
  • the reaction is carried out under reflux for several hours at boiling temperature in order to complete it Sales to reach boric acid esters.
  • the residual water, the water of reaction generated and the excess butyl alcohol are then distilled off as an azeotropic mixture.
  • a residue of insoluble salts and boric acid tributyl ester remains in the sump. After the azeotrope has been distilled off, the tributyl ester is driven off from this remainder at an absolute pressure of 800 hPa.
  • the remaining residue is now practically free of boric acid and can be placed directly in the appropriate repository.
  • the volume to be disposed of can be reduced to approximately 1% of the concentrate mass with the process according to the invention, depending on the initial concentration of the impurities in the water.
  • the distilled azeotrope of butanol and water and the pure butanol are then first condensed and then broken down into the two phases of butanol and water in a decanter.
  • the water can be used to saponify the boric acid ester, while the butanol is available for re-esterification.
  • the boric acid tributyl ester is hydrolyzed with water and the boric acid which precipitates out in crystalline form is separated from the rest of the water by means of a separator and removed from the process in order to be used for conditioning the primary water of the pressurized water reactor.
  • the remaining water (excess) can be circulated; the alcohol obtained during the saponification is also separated off for the further esterification of concentrates.
  • a special pre-evaporator in a nuclear power plant is operated with sodium hydroxide solution.
  • the boron is present in the concentrate as sodium borate.
  • the evaporator concentrate is first neutralized with hydrochloric acid. The process continues as shown in Example 1. In this case, however, a larger amount of sodium chlorite must be precipitated out by neutralization and disposed of separately or disposed of together with the contaminated constituents of the residues. In such cases, with alkaline concentrate as the starting mass, experience has shown that a residue of about 10% of the original concentrate remains.

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Removal Of Specific Substances (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
EP90900069A 1988-12-14 1989-12-13 Aufbereiten von radioaktivem abwasser Expired - Lifetime EP0400130B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3842655 1988-12-14
DE3842655 1988-12-14

Publications (2)

Publication Number Publication Date
EP0400130A1 EP0400130A1 (de) 1990-12-05
EP0400130B1 true EP0400130B1 (de) 1993-10-06

Family

ID=6369492

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90900069A Expired - Lifetime EP0400130B1 (de) 1988-12-14 1989-12-13 Aufbereiten von radioaktivem abwasser

Country Status (11)

Country Link
US (1) US5096624A (cs)
EP (1) EP0400130B1 (cs)
BG (1) BG60569B1 (cs)
CS (1) CS274556B2 (cs)
DD (1) DD293219A5 (cs)
DE (1) DE58905848D1 (cs)
ES (1) ES2047313T3 (cs)
FI (1) FI903997A0 (cs)
HU (2) HUT69123A (cs)
RU (1) RU1809930C (cs)
WO (1) WO1990007186A1 (cs)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6103127A (en) * 1993-06-08 2000-08-15 Cortex Biochem, Inc. Methods for removing hazardous organic molecules from liquid waste
US5564104A (en) * 1993-06-08 1996-10-08 Cortex Biochem, Inc. Methods of removing radioactively labled biological molecules from liquid radioactive waste
BE1007223A3 (nl) * 1993-06-16 1995-04-25 Studiecentrum Kernenergi Werkwijze voor het afscheiden van boorzuur.
US5998690A (en) * 1997-08-26 1999-12-07 Institute Of Nuclear Energy Research Method and agents for solidification of boric acid and/or borates solutions
BG65037B1 (bg) * 2001-11-09 2006-12-29 ВЛАДИМИРОВ Владимир Метод и инсталация за преработване на радиоактивни отпадъци
US7107686B2 (en) * 2003-02-06 2006-09-19 Buck Knives, Inc. Spring assist knife
RU2370836C1 (ru) * 2008-03-24 2009-10-20 Федеральное государственное унитарное предприятие "Научно-исследовательский технологический институт имени А.П. Александрова" Способ переработки жидких радиоактивных отходов
CN103400626B (zh) * 2013-07-02 2016-09-14 中国核电工程有限公司 一种处理核电站含Ag-110m废液的方法
EP2887359B1 (de) * 2013-12-20 2018-01-31 GNS Gesellschaft für Nuklear-Service mbH Verfahren zur Trocknung von Transport- und/oder Lagerbehältern für radioaktive Abfälle

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3100741A (en) * 1957-08-07 1963-08-13 Exxon Research Engineering Co Alcohol dehydration process
US3044943A (en) * 1958-02-12 1962-07-17 United States Borax Chem Separation of methyl borate-methanol azeotrope
US3214347A (en) * 1963-11-18 1965-10-26 Pan American Petroleum Corp Azeotropic distillation process
CH588148A5 (cs) * 1972-10-24 1977-05-31 Nordostschweizerische Kraftwer
DE2714672A1 (de) * 1976-04-02 1977-11-10 Bofors Ab Verfahren zum abtrennen von festen, radioaktiven bestandteilen aus fluessigem abfall und ueberfuehren in einheiten fuer die langzeitlagerung
DE2723025C3 (de) * 1977-05-21 1980-03-13 Rheinisch-Westfaelisches Elektrizitaetswerk Ag, 4300 Essen Verfahren zum Aufbereiten von Borsäure, radioaktives Antimon und weitere radioaktive Nuklide enthaltendem Abwasser
DE2910677C2 (de) * 1979-03-19 1983-12-22 Kraftwerk Union AG, 4330 Mülheim Verfahren zur Behandlung von borhaltigen radioaktiven Konzentraten aus Abwässern von Druckwasserreaktoren
US4440680A (en) * 1980-09-24 1984-04-03 Seton Company Macromolecular biologically active collagen articles
US4434074A (en) * 1981-04-02 1984-02-28 General Electric Company Volume reduction and encapsulation process for water containing low level radioactive waste
US4430257A (en) * 1981-06-12 1984-02-07 The United States Of America As Represented By The United States Department Of Energy Alcohol-free alkoxide process for containing nuclear waste
US4504317A (en) * 1983-03-07 1985-03-12 Westinghouse Electric Corp. Encapsulation of boric acid slurries
US4540512A (en) * 1983-04-06 1985-09-10 Westinghouse Electric Corp. Recovery of boric acid from nuclear waste
US4595528A (en) * 1984-05-10 1986-06-17 The United States Of America As Represented By The United States Department Of Energy Process for immobilizing radioactive boric acid liquid wastes
US4800042A (en) * 1985-01-22 1989-01-24 Jgc Corporation Radioactive waste water treatment

Also Published As

Publication number Publication date
EP0400130A1 (de) 1990-12-05
FI903997A7 (fi) 1990-08-13
DE58905848D1 (de) 1993-11-11
BG60569B1 (en) 1995-08-28
WO1990007186A1 (de) 1990-06-28
CS274556B2 (en) 1991-08-13
US5096624A (en) 1992-03-17
FI903997A0 (fi) 1990-08-13
DD293219A5 (de) 1991-08-22
HU900475D0 (en) 1992-01-28
RU1809930C (ru) 1993-04-15
HUT69123A (en) 1995-08-28
CS708489A2 (en) 1990-10-12
BG92683A (bg) 1993-12-24
ES2047313T3 (es) 1994-02-16

Similar Documents

Publication Publication Date Title
EP0400130B1 (de) Aufbereiten von radioaktivem abwasser
EP0402347B1 (de) Verfahren zur Abtrennung von Aminen
DE2855821A1 (de) Verfahren zur wiedergewinnung von palladium und technetium
DE2540311C2 (de) Verfahren zur Beseitigung radioaktiv kontaminierter organischer Abfallstoffe
EP1793387B1 (de) Extraktion von radionukliden unter verwendung von kronenether enthaltenden extraktionsmitteln
EP0189799B1 (de) Verfahren zum Abtrennen von Cäsiumionen aus wässrigen Lösungen
DE19703884A1 (de) Verfahren zur Reinigung von Naßverfahrensphosphorsäure
DE2652164C2 (de) Verfahren zur Minimierung organischer Abfallstoffe aus wäßrigen Produkt- und Raffinat-Strömen von Flüssig-flüssig-Extraktionsprozessen
DE2723025C3 (de) Verfahren zum Aufbereiten von Borsäure, radioaktives Antimon und weitere radioaktive Nuklide enthaltendem Abwasser
DE3346405A1 (de) Verfahren zur verbesserten abtrennung von die rueckgewinnung der spaltstoffe uran und plutonium stoerenden stoffen und zum verbesserten trennen der rueckzugewinnenden spaltstoffe voneinander in einem wiederaufarbeitungsprozess
DE2504786A1 (de) Verfahren zur verbesserung der extraktionseigenschaften einer tributylphosphatloesung, insbesondere beim verfahren zur trennung von plutoniumund uranwerten
EP0170796A2 (de) Verfahren zur Trennung von grossen Mengen Uran von geringen Mengen von radioaktiven Spaltprodukten, die in wässrigen, basischen, karbonathaltigen Lösungen vorliegen
DE3941587A1 (de) Aufbereiten von radioaktivem abwasser
DE4030331C2 (cs)
EP0090308A2 (de) Verfahren zur Abtrennung von Methanol aus Wasser enthaltenden Mischungen von Methylmethacrylat und Methanol
DD259274A1 (de) Verfahren zur rueckgewinnung von in atomkraftwerken erneut verwendbaren borsaeureloesungen aus in diesen anfallenden radioaktiven abfaellen und loesungen
DE2929298A1 (de) Verfahren zur wiedergewinnung von aktiniden-werten
US5344624A (en) Method for recovering with the aid of a crown compound plutonium (IV) present in solutions, such as aqueous effluents, concentrated solutions of fission products and concentrated solutions of plutonium
DE2837694C3 (de) Verfahren zur Herstellung von reiner Phosphorsäure
DE2842050A1 (de) Entfernung von radionukliden aus wasser
EP0574756A1 (de) Verfahren zur Entfernung olefinischer Verunreinigungen aus fluorierten C3-C6-Kohlenwasserstoffen
DE2444384A1 (de) Chemische falle
EP0064722A2 (de) Verfahren zur Reinigung von Wasser, Salze, Glykolationen und organische Lösemittel enthaltenden Gemischen und die Verwendung des Verfahrens bei der Herstellung von Natriumcarboxymethylgruppen aufweisenden Polysaccharidethern
DE2238694A1 (de) Verfahren zur vorbereitung von bei der wiederaufarbeitung bestrahlter kernbrenn- und/oder brutstoffe verwendeten fluessigkeiten zur lagerung
US2882129A (en) Nitric acid recovery from waste solutions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19900814

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE ES FR GB LI NL SE

17Q First examination report despatched

Effective date: 19930318

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE ES FR GB LI NL SE

REF Corresponds to:

Ref document number: 58905848

Country of ref document: DE

Date of ref document: 19931111

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19940112

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2047313

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
EAL Se: european patent in force in sweden

Ref document number: 90900069.7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19951114

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19951121

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19961213

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19970701

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19961213

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19970701

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20001113

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20001117

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20001120

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20001211

Year of fee payment: 12

Ref country code: DE

Payment date: 20001211

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20001218

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011231

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011231

BERE Be: lapsed

Owner name: NOELL G.M.B.H.

Effective date: 20011231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020702

EUG Se: european patent has lapsed

Ref document number: 90900069.7

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020830

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021214

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030113