EP1252635A2 - Method for conditioning soda effluents in the form of nepheline - Google Patents
Method for conditioning soda effluents in the form of nephelineInfo
- Publication number
- EP1252635A2 EP1252635A2 EP01907692A EP01907692A EP1252635A2 EP 1252635 A2 EP1252635 A2 EP 1252635A2 EP 01907692 A EP01907692 A EP 01907692A EP 01907692 A EP01907692 A EP 01907692A EP 1252635 A2 EP1252635 A2 EP 1252635A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- metakaolin
- suspension
- zeolite
- aqueous solution
- phase
- 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
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
- G21F9/04—Treating liquids
- G21F9/06—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
- G21F9/16—Processing by fixation in stable solid media
- G21F9/162—Processing by fixation in stable solid media in an inorganic matrix, e.g. clays, zeolites
Definitions
- the subject of the present invention is a process for conditioning waste constituted by aqueous sodium hydroxide solutions.
- radioactive soda solutions obtained as waste from fast neutron nuclear reactors.
- This waste can come from the operation of industrial and experimental reactors, but also from research laboratories. They can contain radioactive elements, such as 22Na and other radioelements originating from nuclear power activity in general such as uranium, plutonium, cesium, cobalt, etc.
- the silico-aluminous clays which can be used for this conversion, belong to the group comprising kaolin, bentonite, dickite, halloysite and pyrophillite.
- the intermediate product (cancrinite) in diagram (1) during the calcination, either a loose powder or objects molded by compression of the intermediate product in the desired form are formed, followed by sintering to at least 600 ° C. In this process, it is therefore necessary to manipulate powders in order to obtain solid shaped products and to use mechanical or hydraulic presses to compress these powders.
- a gel is formed by dissolving the calcined kaolin in the sodium hydroxide solution, then a solid product is prepared, by heating the gel, by crystallization.
- kaolin quantities such as the Na 2 O / Si0 2 molar ratio are chosen, that is from 1.8 to 3.8, preferably 2.8.
- the amount of water is such that the molar ratio H 2 0 / Na 2 0 either in the range from 30 to 50, which corresponds to soda solutions 2.23 to 3.7 M. This gives zeolite powders usable in the formulation of detergents, the size of the particles being in the range of 1 to 10 ⁇ m for 99% by weight of the particles.
- a zeolite A is obtained by reaction of metakaolin with an alkaline aqueous medium, using a 7 to 30% solution of sodium hydroxide and an amount of NaOH, representing 1.3 to 3 times the stoichiometric quantity required for the formation of zeolite A.
- This corresponds to an Na 2 0 / Si0 2 ratio of 0.05 to 10 and an H 2 0 / Na 2 0 molar ratio of 15 to 70, i.e. a sodium hydroxide solution 1, 58 to 7.4 M.
- this zeolite in powder form is intended for use in detergents and that is why we are looking for a brighter and less yellow zeolite A, a result which is obtained by using, as a product of departure, metakaolin.
- the present invention specifically relates to a method of packaging a waste consisting of an aqueous sodium hydroxide solution, which makes it possible to obtain solid products, of the nepheline type, without having to treat a powder and compact it.
- the process for conditioning a waste consisting of an aqueous solution comprising 3 to 10 mol / 1 of NaOH soda, comprises the following steps: a) adding to the aqueous solution a metakaolin powder in an amount such that 'A suspension capable of solidifying and forming a crystalline phase of the zeolite A type is obtained; b) introducing the suspension into a mold; c) allow the suspension to solidify in the mold to obtain a solid molded product based on zeolite A; d) drying the molded product; and e) converting the zeolite A phase to a nepheline type phase by heat treatment at a temperature of 1000 to 1500 ° C.
- the fact of starting from a concentrated aqueous solution of sodium hydroxide and adding thereto metakaolin powder in an appropriate amount makes it possible to obtain a suspension capable of solidifying to form a crystalline phase of the zeolite type A.
- this zeolite A can therefore be obtained directly in the form of a solid molded product, then transformed into the nepheline type phase by a heat treatment.
- This is very advantageous when the aqueous sodium hydroxide solutions contain radioactive products, since the handling of powder is eliminated, which could lead to a dispersion of the radioactivity, the investment in material is reduced since it is no longer necessary to use mechanical or hydraulic presses, and we can also reduce the size of the installation and produce molded products corresponding to the dimensions of the waste containers.
- the use of a nepheline-type phase makes it possible to confine the radioactivity to a stable phase, which prevents the leaching of the radioactive products trapped in this structure.
- the fact of starting from an aqueous soda solution, comprising practically no sodium nitrate and nitrite makes it possible to obtain, by reaction with metakaolin, a crystalline phase of zeolite A type. .
- the zeolite phase only appears in the case of the use of metakaolin.
- the quantity of metakaolin and the reaction temperature a proportion of hydroxysodalite phase can form.
- this second phase even in significant proportion, does not prevent solidification of the suspension and conversion to nepheline.
- the sodium hydroxide concentration is too low, the reaction takes place, leaving a supernatant liquid and a dense solid.
- the quantity of metakaolin added should be chosen so that it corresponds substantially to the stoichiometry of the reaction (3) described above, i.e. a molar ratio of metakaolin to soda, which is close to the stoichiometry of the reaction, that is to say a molar ratio of 0.4 to 0.6, preferably about 0.5.
- the water content of the suspension obtained by adding metakaolin to the sodium hydroxide solution should also be adjusted to an appropriate value.
- the water content of this suspension depends on the sodium hydroxide concentration of the starting aqueous solution, since no addition of water is made after adding metakaolin to this solution.
- suspensions containing 30 to 70% are obtained. weight of water, in the case where the quantity of metakaolin added corresponds substantially to the stoichiometry of the reaction.
- metakaolin this is obtained by calcining kaolin at temperatures of 500 to 1200 ° C. The lower the calcination temperature, the more reactive the product. However, the drop in reactivity can be compensated for by grinding.
- the metakaolins obtained at temperatures of 800 to 1000 ° C. are preferred, having an average particle size of 1 to 50 ⁇ m, preferably from 1 to 10 ⁇ m.
- the treatment temperature used for reaction (3) can be from 15 to 100 ° C, under atmospheric pressure. One could also operate at higher temperatures under pressure. Indeed, moderate heating of the suspension makes it possible to activate the solidification of the suspension.
- the chemical species present in the starting aqueous solution may interfere with the reaction (3) for the formation of zeolite A. It is the case in particular of the N0 3 " and N0 2 ions present in the starting aqueous solution of the reference [1] which prevent the formation of the zeolite A phase and the solidification leading to the cancrinite phase. Also according to the invention , the total content of N0 3 ⁇ and N0 2 " ions in the starting aqueous solution is preferably 0 to 0.5 mol / l.
- the molded product obtained by this solidification is subjected to drying, then to a heat treatment to transform it into nepheline.
- Drying can be carried out after demolding the product at temperatures of 110 to 500 ° C.
- the heat treatment is then carried out on the dried product at temperatures of 1000 to 1500 ° C, to obtain the transformation into nepheline (between 500 and 850 ° C), then the densification of the products by removing the open porosity.
- the figure is a diagram representing the different stages of the process of the invention.
- the first step of the process is to add to the starting soda solution (waste) the desired amount of metakaolin powder, and knead the whole to obtain a homogeneous paste.
- the average particle size of the metakaolin powder is less than 10 ⁇ m and this metakaolin was obtained by calcination of a powdered kaolin at a temperature of 800 ° C., for 1 hour.
- the shaping step is carried out by casting or spinning.
- the dough can be poured into a sealed mold to obtain a product of the desired shape.
- the mixture crystallizes and solidifies in the minutes or hours that follow.
- the setting time depends on the temperature used. To activate the plug very strongly, you can operate at a temperature of 40 to 70 ° C by moderate heating. It would also be possible to promote the growth of the zeolite grains by inoculating the suspension with crystals of zeolite A to obtain a homogeneous germination or with crystals of Nepheline leading to heterogeneous germination.
- hardened products After solidification, hardened products are obtained which have acquired sufficient mechanical strength to be handled by automated means. They can therefore be removed from the mold before subjecting them to drying and the final heat treatment.
- the molded products can also be stored in the mold, if the latter consists of a completely incinerable and ashless material, for example made of polymer material or cellulose.
- the molded products are then dried, which is carried out slowly to evacuate the residual water, avoiding cracking of the products.
- the duration of the drying step obviously depends on the amount of water to be evaporated, as well as on the geometry of the molded products. We can operate at a temperature of 110 to 550 ° C, not exceeding the temperature of 100 ° C at first, to avoid cracking of the molded products, by a too violent departure of water vapor.
- This drying step corresponds to the following reaction equation:
- the dried products are then subjected to the final heat treatment, at least 1000 ° C.
- the purpose of this treatment is: 1) convert the zeolite phase to a nepheline type phase, conversion which typically takes place between 500 and 850 ° C; and
- a densified nepheline phase is thus obtained in which the salts or radioactive elements which were liable to be present in the aqueous sodium hydroxide solution are trapped.
- the products obtained can then be sent to a storage site, possibly after baking.
- Example 2 Packaging of a 5N sodium hydroxide solution
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Fertilizers (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0000985 | 2000-01-26 | ||
FR0000985A FR2804103B1 (en) | 2000-01-26 | 2000-01-26 | PROCESS FOR THE CONDITIONING OF NEPHELINE SODIUM EFFLUENTS |
PCT/FR2001/000233 WO2001056040A2 (en) | 2000-01-26 | 2001-01-25 | Method for conditioning soda effluents in the form of nepheline |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1252635A2 true EP1252635A2 (en) | 2002-10-30 |
EP1252635B1 EP1252635B1 (en) | 2004-04-21 |
Family
ID=8846327
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01907692A Expired - Lifetime EP1252635B1 (en) | 2000-01-26 | 2001-01-25 | Method for conditioning soda effluents in the form of nepheline |
Country Status (6)
Country | Link |
---|---|
US (1) | US6676915B2 (en) |
EP (1) | EP1252635B1 (en) |
JP (1) | JP2003520975A (en) |
FR (1) | FR2804103B1 (en) |
RU (1) | RU2257627C2 (en) |
WO (1) | WO2001056040A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10673660B2 (en) * | 2017-09-26 | 2020-06-02 | International Business Machines Corporation | Continuous time linear equalizer |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9926674D0 (en) * | 1999-11-12 | 2000-01-12 | British Nuclear Fuels Plc | Encapsulation of waste |
US7309339B2 (en) * | 2003-02-04 | 2007-12-18 | Howmedica Osteonics Corp. | Apparatus for aligning an instrument during a surgical procedure |
JP6067497B2 (en) * | 2013-07-05 | 2017-01-25 | 株式会社東芝 | Production method of solidified radioactive waste |
FR3009550A1 (en) * | 2013-08-08 | 2015-02-13 | Commissariat Energie Atomique | PROCESS FOR TREATING AND / OR INERTING A HIGHLY SALTED SOLUTION POSSIBLY CONTAMINATED |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4028265A (en) * | 1974-04-02 | 1977-06-07 | The United States Of America As Represented By The United States Energy Research And Development Administration | Process for converting sodium nitrate-containing, caustic liquid radioactive wastes to solid insoluble products |
DE2533614C2 (en) | 1975-07-26 | 1985-10-31 | Degussa Ag, 6000 Frankfurt | Process for the production of zeolitic alkali aluminum silicates |
DE2852674A1 (en) * | 1978-12-06 | 1980-06-19 | Bayer Ag | METHOD FOR PRODUCING ZEOLITH A FROM KAOLIN |
LU84743A1 (en) * | 1983-04-11 | 1984-11-28 | Sipac | PROCESS FOR PRODUCING ZEOLITE A AND PRODUCTS OBTAINED |
US4859367A (en) * | 1987-10-02 | 1989-08-22 | Joseph Davidovits | Waste solidification and disposal method |
DD292432A5 (en) * | 1989-04-10 | 1991-08-01 | ������@������������k�� | METHOD FOR PRODUCING A FINE-PARTICULAR TYPE 4A CRYSTALLINE ZEOLITE POWDER WITH PREDETERMINABLE GRAIN SIZE DISTRIBUTION |
FR2688223B1 (en) * | 1992-03-05 | 1994-05-20 | Institut Francais Petrole | NEW PROCESS FOR SOFTENING OIL CUTS WITHOUT REGULAR ADDITION OF AQUEOUS ALKALINE SOLUTION, USING A BASIC SOLID CATALYST. |
-
2000
- 2000-01-26 FR FR0000985A patent/FR2804103B1/en not_active Expired - Fee Related
-
2001
- 2001-01-25 EP EP01907692A patent/EP1252635B1/en not_active Expired - Lifetime
- 2001-01-25 WO PCT/FR2001/000233 patent/WO2001056040A2/en active IP Right Grant
- 2001-01-25 RU RU2002122769/06A patent/RU2257627C2/en not_active IP Right Cessation
- 2001-01-25 US US10/149,958 patent/US6676915B2/en not_active Expired - Lifetime
- 2001-01-25 JP JP2001555103A patent/JP2003520975A/en active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO0156040A3 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10673660B2 (en) * | 2017-09-26 | 2020-06-02 | International Business Machines Corporation | Continuous time linear equalizer |
Also Published As
Publication number | Publication date |
---|---|
WO2001056040A3 (en) | 2002-02-28 |
US20020198431A1 (en) | 2002-12-26 |
RU2257627C2 (en) | 2005-07-27 |
JP2003520975A (en) | 2003-07-08 |
FR2804103A1 (en) | 2001-07-27 |
US6676915B2 (en) | 2004-01-13 |
RU2002122769A (en) | 2004-02-27 |
WO2001056040A2 (en) | 2001-08-02 |
EP1252635B1 (en) | 2004-04-21 |
FR2804103B1 (en) | 2002-03-01 |
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