WO2002013202A1 - Reduction du volume de battitures d'huile - Google Patents

Reduction du volume de battitures d'huile Download PDF

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Publication number
WO2002013202A1
WO2002013202A1 PCT/SE2001/001723 SE0101723W WO0213202A1 WO 2002013202 A1 WO2002013202 A1 WO 2002013202A1 SE 0101723 W SE0101723 W SE 0101723W WO 0213202 A1 WO0213202 A1 WO 0213202A1
Authority
WO
WIPO (PCT)
Prior art keywords
radioactive
process according
solution
scale
barium
Prior art date
Application number
PCT/SE2001/001723
Other languages
English (en)
Inventor
Maria Lindberg
David Bradbury
George Richard Elder
Original Assignee
Studsvik Radwaste Ab
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 Studsvik Radwaste Ab filed Critical Studsvik Radwaste Ab
Priority to AU2001280375A priority Critical patent/AU2001280375A1/en
Publication of WO2002013202A1 publication Critical patent/WO2002013202A1/fr

Links

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
    • G21F9/28—Treating solids
    • G21F9/30—Processing
    • 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

  • Completion of the dissolution may be aided by the detailed design of the dissolver vessel and equipment.
  • certain other methods are well known in the art for increasing the effectiveness of dissolution reactions. Examples are counter-current contact, in which the solid passes through the dissolution vessel in the opposite sense to the solution - thus the emerging undissolved solid is contacting the cleanest solution. Contact of the solid and solution can also be enhanced by a "high-shear" mixer.
  • any undissolved solid from the dissolution reaction vessel is separated from the dissolution solution by conventional means, such as settling and filtration.
  • the solid is rinsed with clean water (if necessary) and sentenced, according to its radioactivity specific activity (in Becquerels per gram) , to radioactive or non- radioactive disposal.
  • the undissolved solid is likely to be either a significant proportion of the original oil scale and non-radioactive, or a very small proportion of the original solid and radioactive.
  • the scale solution is then subjected to an anion exchange resin so as to remove sulphate ion therefrom.
  • said anion exchange resin is in the chloride form, the chloride ions replacing the sulphate ions in the solution.
  • the optimum procedure is to absorb the combined radioactive (radium, etc.) and non-radioactive (Sr, Ba etc) constituents onto at least one cation exchange column. The separation of the constituents is then made by differential elution.
  • the most preferred embodiment is to use an eluting solution that has a chemical composition equivalent to the dissolving solution, but at a slightly different pH.
  • eluting solution that has a chemical composition equivalent to the dissolving solution, but at a slightly different pH.
  • alternatives are possible, such as different chelating agents, e.g. the use of EDTA in the dissolving solution and DCyTA in the eluting solution.
  • the output solution from the ion exchange column is diverted to collect radioactive and non-radioactive fractions separately. The correct collection of fractions may be facilitated by equipment which continuously analyses the radioactivity and chemical composition of the output solution.
  • the partial separation can be used to good effect by "cascading" ion exchange columns, i.e. feeding radium-depleted barium and barium-depleted radium to further ion exchange separation columns. It is also possible that the ion exchange conditions can be designed to concentrate the radium into a series of bands or "pulses" of radioactivity going down the ion exchange column, interspersed with bands of non- radioactive material.
  • the radioactive fraction and/or the non-radioactive fraction is (are) optionally converted into solid form(s) .
  • this is accomplished by means of precipitation operation (s) , which can be performed in accordance with techniques known per se, e.g. by sulphate precipitation (s) with sulphate ions.
  • the obtained radioactive and/or non- radioactive solids can then be used or disposed of in any suitable manner.
  • radioactive and non-radioactive cationic constituents have been recovered, recovery of dissolving constituents (e.g. chelating agent) can be achieved, e.g. by the appropriate pH adjustment of the effluent solutions to cause precipitation.
  • the filtered chelating agent can be recycled. Residual salt solutions can then be discarded as effluent, though if it is absolutely necessary to have a zero effluent operation, the salt solutions can be reconstituted into acid and alkali by appropriate electrical processes.
  • a simple and efficient apparatus for performing a process as defined above comprises:
  • the apparatus also preferably comprises a grinding unit, before said dissolver vessel, for reducing solid oil scale to a particulate material, preferably to a particle size of at most 50 ⁇ m.
  • Fig. 4 shows dissolution of activity and weight in oil scale samples as described below in Example 1;
  • Fig. 6 shows ion exchange separation with EDTA as described below in Example 3 ;
  • Fig. 2 shows how an input solution is subjected to a first separation stage in a cationic exchange resin, the barium rich and radium rich fractions from said first separation then being passed to separate new, cationic exchange resins, respectively, etc. Barium sulphate and radium sulphate solids are separately recovered for disposal, while radium and barium rich fractions, as shown, are recycled to the first exchange resin.
  • Example 1 Dissolution Duplicate oil scale samples from two sources (“A” and "B”) were heat treated to pyrolyse organics, and were separately ground to ⁇ 50 ⁇ m particle size and homogenised using a Retsch (S100) centrifugal ball mill with reversing mechanism. Two 5 g portions of each were accurately weighed and submitted for gamma-spectrometry counting to determine Ra-226 activity. The samples were counted in the same geometry as a 50 Bq standard prepared from 5 g of the natural mineral clinoptilolite spiked with an aqueous certified Ra-226 reference standard. Multiple contact dissolution tests were carried out on 5 g portions of the ground samples. In this technique, the oil scale was contacted with chemical dissolving solution, filtered and then contacted with a fresh batch of solution. The number of contacts was recorded and the cumulative dissolution of activity and weight measured.
  • a 75 cm 3 cation exchange column in the sodium form was prepared from Amberlite IR-120 resin (capacity
  • the overall capacity of the column provided approximately 75% excess.
  • the column was converted into the chloride form from the hydroxide form by passing through of 5 bv (bed volumes) 2 M sodium chloride solution, followed by a 2 bv deionised water rinse.
  • the pH 7 adjusted dissolution liquor spiked with additional Ra-226 (described above) was loaded onto a 75 cm 3 cation exchange column in the sodium form (pH 7) prepared in the manner described above .
  • the column was rinsed with 2 bv deionised water followed by an additional 1 bv deionised water.
  • 13 bv 0.05 M DCyTA at pH 8.5 was passed through the column to elute the barium taking column effluent fractions for counting and qualitative barium analysis after 5 bv, 10 bv and 13 bv.
  • 5 bv 0.05 M EDTA at pH 8.5 was passed through the column to elute the radium followed by a 2 bv deionised water rinse.
  • the first contact oil scale dissolution liquors from samples A (5) and B(5) were combined and subjected to sulphate removal by anion exchange as described above .
  • the combined anion exchange effluent was adjusted to pH 7 with 2 M HCl.
  • the entire solution (unspiked, combined Ra- 226 activity -500 Bq) was loaded onto a 75 cm 3 cation exchange column in the sodium form (pH 7) , prepared in the manner described above.
  • a total of 12 bv i.e.
  • Example 4 Ion Exchange Separation with EDTA using a loading and elution technique
  • the solution was measured for radium and barium after passing through the column, and no radium or barium was detected (ie all the barium and radium had been retained on the column.
  • the ion exchange column was then eluted with 10 bed volumes of 0.1 M EDTA adjusted to pH 7, followed by 3 bed volumes of 0.1 M EDTA adjusted to pH

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Fats And Perfumes (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de réduction du volume de battitures d'huile radioactives. Ce procédé consiste à déshuiler les matières battitures solides; à dissoudre le barium et les sulphates de strontium et leur radioactivité associée ; à retirer l'ion de sulphate de la solution obtenue par une opération d'échange anionique et à séparer les constituants radioactifs et non-radioactifs par une opération d'échange de cations. Un appareil destiné à une telle réduction de volume comprend un récipient de dissolution, au moins une colonne d'échange d'anions, au moins une colonne d'échange de cations et des récipients de récupération.
PCT/SE2001/001723 2000-08-10 2001-08-09 Reduction du volume de battitures d'huile WO2002013202A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001280375A AU2001280375A1 (en) 2000-08-10 2001-08-09 Oil scale volume reduction

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0002869-6 2000-08-10
SE0002869A SE517130C2 (sv) 2000-08-10 2000-08-10 Förfarande och anordning för volymreduktion av radioaktivt oljescaleavfall

Publications (1)

Publication Number Publication Date
WO2002013202A1 true WO2002013202A1 (fr) 2002-02-14

Family

ID=20280662

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE2001/001723 WO2002013202A1 (fr) 2000-08-10 2001-08-09 Reduction du volume de battitures d'huile

Country Status (3)

Country Link
AU (1) AU2001280375A1 (fr)
SE (1) SE517130C2 (fr)
WO (1) WO2002013202A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002083565A1 (fr) * 2001-04-11 2002-10-24 Gkss-Forschungszentrum Procede d'enrichissement de radium provenant de melanges de substances minerales contenant du sulfate de baryum
WO2003065381A1 (fr) * 2002-02-01 2003-08-07 Studsvik Radwaste Ab Procede et dispositif pour la reduction du volume des battitures dans l'industrie du petrole
EP2063433A1 (fr) 2007-11-08 2009-05-27 Electric Power Research Institute, Inc. Processus de préparation de particules magnétiques pour la suppression sélective des contaminants d'une solution
WO2011098765A1 (fr) * 2010-02-10 2011-08-18 M-I Drilling Fluids Uk Limited Procédé et système de décontamination de sable
US8889010B2 (en) 2010-10-22 2014-11-18 General Electric Company Norm removal from frac water
RU2714309C1 (ru) * 2019-07-11 2020-02-14 Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть" Способ очистки нефтезагрязненных грунтов от естественных радионуклидов
CN111292865A (zh) * 2018-12-06 2020-06-16 国家电投集团远达环保工程有限公司重庆科技分公司 放射性废油水泥固化体及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5026481A (en) * 1989-04-03 1991-06-25 Mobil Oil Corporation Liquid membrane catalytic scale dissolution method
US5322644A (en) * 1992-01-03 1994-06-21 Bradtec-Us, Inc. Process for decontamination of radioactive materials
US5550313A (en) * 1994-10-20 1996-08-27 Institute Of Gas Technology Treatment of norm-containing materials for minimization and disposal

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5026481A (en) * 1989-04-03 1991-06-25 Mobil Oil Corporation Liquid membrane catalytic scale dissolution method
US5322644A (en) * 1992-01-03 1994-06-21 Bradtec-Us, Inc. Process for decontamination of radioactive materials
US5550313A (en) * 1994-10-20 1996-08-27 Institute Of Gas Technology Treatment of norm-containing materials for minimization and disposal

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002083565A1 (fr) * 2001-04-11 2002-10-24 Gkss-Forschungszentrum Procede d'enrichissement de radium provenant de melanges de substances minerales contenant du sulfate de baryum
WO2003065381A1 (fr) * 2002-02-01 2003-08-07 Studsvik Radwaste Ab Procede et dispositif pour la reduction du volume des battitures dans l'industrie du petrole
EP2063433A1 (fr) 2007-11-08 2009-05-27 Electric Power Research Institute, Inc. Processus de préparation de particules magnétiques pour la suppression sélective des contaminants d'une solution
US8097164B2 (en) 2007-11-08 2012-01-17 Electric Power Research Institute, Inc. Process for preparing magnetic particles for selectively removing contaminants from solution
WO2011098765A1 (fr) * 2010-02-10 2011-08-18 M-I Drilling Fluids Uk Limited Procédé et système de décontamination de sable
US8889010B2 (en) 2010-10-22 2014-11-18 General Electric Company Norm removal from frac water
CN111292865A (zh) * 2018-12-06 2020-06-16 国家电投集团远达环保工程有限公司重庆科技分公司 放射性废油水泥固化体及其制备方法
CN111292865B (zh) * 2018-12-06 2022-02-25 国家电投集团远达环保工程有限公司重庆科技分公司 放射性废油水泥固化体及其制备方法
RU2714309C1 (ru) * 2019-07-11 2020-02-14 Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть" Способ очистки нефтезагрязненных грунтов от естественных радионуклидов

Also Published As

Publication number Publication date
SE0002869D0 (sv) 2000-08-10
SE0002869L (sv) 2002-02-11
AU2001280375A1 (en) 2002-02-18
SE517130C2 (sv) 2002-04-16

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