RU2145451C1 - Method for immobilizing radioactive iodine in ceramic matrix - Google Patents
Method for immobilizing radioactive iodine in ceramic matrix Download PDFInfo
- Publication number
- RU2145451C1 RU2145451C1 RU97116857A RU97116857A RU2145451C1 RU 2145451 C1 RU2145451 C1 RU 2145451C1 RU 97116857 A RU97116857 A RU 97116857A RU 97116857 A RU97116857 A RU 97116857A RU 2145451 C1 RU2145451 C1 RU 2145451C1
- Authority
- RU
- Russia
- Prior art keywords
- iodine
- ceramic matrix
- zeolite
- radioactive iodine
- days
- Prior art date
Links
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 25
- 239000011630 iodine Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000003100 immobilizing effect Effects 0.000 title claims abstract description 4
- 239000000919 ceramic Substances 0.000 title claims description 11
- 230000002285 radioactive effect Effects 0.000 title claims description 7
- 239000011159 matrix material Substances 0.000 title claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010457 zeolite Substances 0.000 claims abstract description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 5
- 239000002901 radioactive waste Substances 0.000 claims abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims abstract description 4
- 238000000605 extraction Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- 238000007731 hot pressing Methods 0.000 claims description 5
- 239000000428 dust Substances 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- 238000002386 leaching Methods 0.000 description 6
- 229910052665 sodalite Inorganic materials 0.000 description 5
- 229910052849 andalusite Inorganic materials 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
Изобретение относится к области переработки и захоронения высокорадиоактивных отходов и может быть использовано в ядерной промышленности и энергетике для фиксации в устойчивой твердой фазе радиоактивного иода. The invention relates to the field of processing and disposal of highly radioactive waste and can be used in the nuclear industry and energy for fixing in a stable solid phase of radioactive iodine.
Известен способ удерживания радиоактивного иода, включающий перевод его в иодид свинца и последующее спекание с эпоксидной смолой (Калинин Н.Н., Елизарова А.Н."Исследование выщелачивания иода из композиций на основе эпоксидной смолы и иодида свинца". - Радиохимия, 1998, т.3, N 4, стр. 107-111). A known method of retaining radioactive iodine, including its transfer into lead iodide and subsequent sintering with epoxy resin (Kalinin NN, Elizarova AN "Study of the leaching of iodine from compositions based on epoxy resin and lead iodide." - Radiochemistry, 1998, t.3, N 4, p. 107-111).
Недостатками данного способа являются усложнение технологического процесса за счет предварительного перевода иода в иодид свинца, а также низкая прочность полимерного материала в условиях долговременного захоронения. The disadvantages of this method are the complexity of the process due to the preliminary transfer of iodine to lead iodide, as well as the low strength of the polymer material under long-term burial conditions.
Известен способ иммобилизации радиоактивного иода в керамическую матрицу (пат. США N 4229317, по кл МКИ G 21 F 9/16 1981 г.), включающий предварительный перевод радиоактивного иода в иодиды или иодаты щелочных металлов и добавление последних к раствору оксидов алюминия, кремния и щелочных металлов в стехиометрическом соотношении. Компоненты перемешивали в течении 16 ч до гомогенности, высушивали до получения порошка и прессовали под давлением 69-127 бар и температуре 800-1100oC до образования иодсодержащего алюмосиликата (иод-содалита).A known method of immobilization of radioactive iodine in a ceramic matrix (US Pat. US N 4229317, according to MKI G 21 F 9/16 1981), including the preliminary conversion of radioactive iodine into iodides or iodates of alkali metals and adding the latter to the solution of aluminum, silicon and alkali metals in a stoichiometric ratio. The components were mixed for 16 hours until homogeneous, dried to obtain a powder and pressed at a pressure of 69-127 bar and a temperature of 800-1100 o C to form an iodine-containing aluminosilicate (iodine-sodalite).
Однако этот способ достаточно трудоемок из-за многостадийности и необходимости приготовления в процессе иммобилизации ряда малоустойчивых реагентов, например, коллоидного кремния. However, this method is quite time-consuming due to the multi-stage nature and the need to prepare in the process of immobilization a number of unstable reagents, for example, colloidal silicon.
Способ, описанный в патенте США 4661291, хотя и наиболее близок к предлагаемому нами по числу совпадающих операций, однако из-за отличий в условиях их проведения (адсорбций только на Ag-замещенных цеолитах, горячее прессование в присутствии более чем 5% воды при относительно низких и широких интервалах температур и давлении) не позволяет решить поставленную задачу - керамизацию отходов как наиболее оптимальный способ их захоронения. Он, как и способ, описанный в ЕП 0379895, G 21 F 9/02, 1990, основан на использовании цеолита только как адсорбента иода. Однако параметры опытов по проведению фиксации сорбента иода по патенту США не соответствуют условиям получения плотной и низко пористой керамической матрицы. The method described in US patent 4661291, although it is closest to our proposed in the number of matching operations, however, due to differences in the conditions of their implementation (adsorption only on Ag-substituted zeolites, hot pressing in the presence of more than 5% water at relatively low and wide temperature and pressure ranges) does not allow us to solve the problem - the ceramicization of waste as the most optimal way of their disposal. He, like the method described in EP 0379895, G 21 F 9/02, 1990, is based on the use of zeolite only as an iodine adsorbent. However, the parameters of experiments on the fixation of the sorbent of iodine according to the US patent do not meet the conditions for obtaining a dense and low porous ceramic matrix.
Требуются именно те высокие параметры, которые патентуются нами. Способ, описанный в патенте 4661291, обеспечивает скорее компактирование сорбента и, таким образом, его удерживание, но не содержит гарантии удерживания радионуклида иода, которая характеризуется согласно требованиям МАГАТЭ скоростью выщелачивания - количеством вещества, теряемого с единицы поверхности в единицу времени. It is precisely those high parameters that are patented by us. The method described in patent 4661291, rather provides compaction of the sorbent and, therefore, its retention, but does not guarantee the retention of iodine radionuclide, which is characterized according to IAEA requirements by the leaching rate - the amount of substance lost from a surface unit per unit time.
Предлагаемое изобретение решает задачу повышения сохранности окружающей среды путем упрощения технологии иммобилизации иода, извлеченного из пылегазовых отходов ядерного производства, для его дальнейшего надежного захоронения. The present invention solves the problem of improving the preservation of the environment by simplifying the technology of immobilization of iodine extracted from dust and gas waste from nuclear production, for its further reliable disposal.
Поставленная задача решается тем, что в известном способе иммобилизации радиоактивного иода в керамическую матрицу, включающем извлечение иода и горячее прессование шихты, новым является то, что извлечение иода из радиоактивных отходов осуществляют методом химической адсорбции на цеолите NaX или его свежеприготовленных металлзамещенных формах, полученный материал высушивают, растирают до пудры, дегидратируют и осуществляют горячее прессование в присутствии 0,3 - 1% воды при температуре 500 - 1000oC и давлении 0,5 - 1,5 кбар в течение 3-5 суток.The problem is solved in that in the known method of immobilizing radioactive iodine in a ceramic matrix, including extracting iodine and hot pressing the mixture, it is new that the extraction of iodine from radioactive waste is carried out by chemical adsorption on zeolite NaX or its freshly prepared metal-substituted forms, the resulting material is dried , triturated to powder, dehydrated and hot pressed in the presence of 0.3 - 1% water at a temperature of 500 - 1000 o C and a pressure of 0.5 - 1.5 kbar for 3-5 days.
Пример 1. 0,326 г. цеолита NaX засыпали в ионнообменную колонку, сквозь которую пропускали поток воздуха, насыщенный парами иода. После чего цеолит высушили, растерли до пудры, дегитратировали при 300oC до постоянного веса и плотно запрессовали в платиновую ампулу, добавив 1 вес.% воды. Ампулу заварили и поместили в реактор установки высокого давления при 500oC и обжимающем давлении 1000 бар в течение 5 суток. Полученная керамика представляла собой иод-содалит с плотностью 2,34 г/см3 и пористостью 8%. Скорость выщелачивания иода на 22-е сутки составляла 1,8 г/м2 •сутки.Example 1. 0.326 g of zeolite NaX was poured into an ion-exchange column through which a stream of air saturated with iodine vapor was passed. After that, the zeolite was dried, ground to powder, degraded at 300 o C to constant weight and tightly pressed into a platinum ampoule, adding 1 wt.% Water. The ampoule was brewed and placed in a reactor of a high-pressure apparatus at 500 ° C and a compression pressure of 1000 bar for 5 days. The resulting ceramic was iodine-sodalite with a density of 2.34 g / cm 3 and porosity of 8%. The iodine leaching rate on the 22nd day was 1.8 g / m 2 • day.
Пример 2. То же, что и в примере один, только сквозь ионнообменную колонку пропускали водный раствор, содержащий иод в форме иодида. Горячее прессование проводили в присутствии 0,3% воды при 1000oC и обжимающем давлении 500 бар в течение 3 суток. Полученная керамика представляла собой иод-содалит с плотностью 2,45 г/см3 и пористостью 8% Скорость выщелачивания иода на 22-е сутки составляла 1,9 г/м2•сутки.Example 2. The same as in example one, only through an ion-exchange column was passed an aqueous solution containing iodine in the form of an iodide. Hot pressing was carried out in the presence of 0.3% water at 1000 ° C. and a compression pressure of 500 bar for 3 days. The obtained ceramic was iodine-sodalite with a density of 2.45 g / cm 3 and porosity of 8%. The rate of leaching of iodine on the 22nd day was 1.9 g / m 2 • day.
Пример 3. То же, что и в примере один, только ионнообменную колонку заполняли свежевосстановленным медьзамещенным цеолитом NaX. Example 3. The same as in example one, only the ion exchange column was filled with freshly restored copper-substituted zeolite NaX.
Полученная керамика представляла собой смесь иодида меди, окиси меди и андалузита - аналога природного андалузита и имела фазово-химическое соответствие с породой, в которую ее можно захоронить. Плотность полученной керамики 2,62 г/см3, пористость 0,5%. Скорость выщелачивания иода на 36-е сутки составляла 0,93 г/м2•сутки, что в 4 раза меньше, чем у иод-содалита, синтезированного по прототипу.The resulting ceramics was a mixture of copper iodide, copper oxide and andalusite - an analogue of natural andalusite and had a phase-chemical correspondence with the rock into which it could be buried. The density of the obtained ceramics is 2.62 g / cm 3 , the porosity is 0.5%. The iodine leaching rate on the 36th day was 0.93 g / m 2 • day, which is 4 times less than that of the sodalite iodine synthesized according to the prototype.
Пример 4. То же, что и в примере 1, только ионнообменную колонку заполняли свежевосстановленным свинецзамещенным цеолитом NaX. Полученная керамика представляла собой смесь иодида свинца, окиси свинца и андалузита - аналога природного андалузита и имела фазово-химическое соответствие с породой, в которую ее можно захоронить. Плотность полученной керамики 2,82 г/см3, пористость 0,95%. Скорость выщелачивания иода на 36-е сутки составляла 1,03 г/м2•сутки, что в 3 раза меньше чем у иод-содалита, синтезированного по прототипу.Example 4. The same as in example 1, only the ion exchange column was filled with freshly reduced lead-substituted zeolite NaX. The resulting ceramics was a mixture of lead iodide, lead oxide and andalusite - an analogue of natural andalusite and had a phase-chemical correspondence with the rock into which it could be buried. The density of the obtained ceramics is 2.82 g / cm 3 , the porosity is 0.95%. The iodine leaching rate on the 36th day was 1.03 g / m 2 • day, which is 3 times lower than that of the iodine-sodalite synthesized according to the prototype.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU97116857A RU2145451C1 (en) | 1997-10-09 | 1997-10-09 | Method for immobilizing radioactive iodine in ceramic matrix |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU97116857A RU2145451C1 (en) | 1997-10-09 | 1997-10-09 | Method for immobilizing radioactive iodine in ceramic matrix |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| RU97116857A RU97116857A (en) | 1999-07-20 |
| RU2145451C1 true RU2145451C1 (en) | 2000-02-10 |
Family
ID=20197928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| RU97116857A RU2145451C1 (en) | 1997-10-09 | 1997-10-09 | Method for immobilizing radioactive iodine in ceramic matrix |
Country Status (1)
| Country | Link |
|---|---|
| RU (1) | RU2145451C1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4229317A (en) * | 1978-12-04 | 1980-10-21 | The United States Of America As Represented By The United States Department Of Energy | Method for immobilizing radioactive iodine |
| US4661291A (en) * | 1984-09-25 | 1987-04-28 | Mitsui Engineering & Shipbuilding Co., Ltd. | Method for fixation of incinerator ash or iodine sorbent |
| US4913850A (en) * | 1988-03-16 | 1990-04-03 | Bayer Aktiengesellschaft | Process for the removal of iodine and organic iodine compounds from gases and vapors using silver-containing zeolite of the faujasite type |
| EP0379895A1 (en) * | 1989-01-21 | 1990-08-01 | Bayer Ag | Process for removal of iodine and iodine compounds from hydrogen containing gases and vapours |
| RU2035975C1 (en) * | 1989-01-21 | 1995-05-27 | Байер Аг | Method for purification of oxygen-containing gases against iodine impurities and sorbent for its realization |
-
1997
- 1997-10-09 RU RU97116857A patent/RU2145451C1/en not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4229317A (en) * | 1978-12-04 | 1980-10-21 | The United States Of America As Represented By The United States Department Of Energy | Method for immobilizing radioactive iodine |
| US4661291A (en) * | 1984-09-25 | 1987-04-28 | Mitsui Engineering & Shipbuilding Co., Ltd. | Method for fixation of incinerator ash or iodine sorbent |
| US4913850A (en) * | 1988-03-16 | 1990-04-03 | Bayer Aktiengesellschaft | Process for the removal of iodine and organic iodine compounds from gases and vapors using silver-containing zeolite of the faujasite type |
| EP0379895A1 (en) * | 1989-01-21 | 1990-08-01 | Bayer Ag | Process for removal of iodine and iodine compounds from hydrogen containing gases and vapours |
| RU2035975C1 (en) * | 1989-01-21 | 1995-05-27 | Байер Аг | Method for purification of oxygen-containing gases against iodine impurities and sorbent for its realization |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Couture | Steam rapidly reduces the swelling capacity of bentonite | |
| Yanagisawa et al. | Immobilization of cesium into pollucite structure by hydrothermal hot-pressing | |
| US4229317A (en) | Method for immobilizing radioactive iodine | |
| Daimon et al. | Morphological study on hydration of tricalcium silicate | |
| RU2145451C1 (en) | Method for immobilizing radioactive iodine in ceramic matrix | |
| Yamasaki et al. | Immobilization of radioactive wastes in hydrothermal synthetic rock: Lithification of silica powder | |
| JPH06138298A (en) | Manufacture of sintered solidified body containing cesium and/or strontium being radioisotope and method for using it as large-scale ri battery through processing | |
| Collepardi et al. | Low pressure steam curing of compacted lime-pozzolana mixtures | |
| Jing et al. | Hydrothermal synthesis of pollucite with soil and incineration ash for Cs immobilization and its immobilizing mechanism and leaching property | |
| Chen et al. | Cold reaction sintering of geopolymers for enhanced Cs+ immobilization: Synthesis, characterization, and leaching behavior | |
| US5875407A (en) | Method for synthesizing pollucite from chabazite and cesium chloride | |
| RU2197763C1 (en) | Method for solidifying liquid radioactive wastes and ceramic material used for the purpose | |
| RU2165110C2 (en) | Ceramic sponge for concentration and hardening of liquid extrahazardous waste and method for its production | |
| RU2068208C1 (en) | Method for recovering radioactive ion-exchange resins | |
| RU2428758C1 (en) | Processing method of liquid radioactive waste of low level | |
| Luca et al. | The immobilization of cesium and strontium in ceramic materials derived from tungstate sorbents | |
| Shrivastava et al. | Sr2+ Sorption and leach rate studies on synthetic calcium silicate hydroxy hydrate | |
| RU2127920C1 (en) | Method for treating very toxic inorganic wastes | |
| RU2257627C2 (en) | Method for treatment of caustic soda wastes to produce nepheline | |
| Varshney et al. | Radiation stability of some thermally stable inorganic ion exchangers | |
| CN108470594B (en) | Method for dropwise preparing simulated pollucite source core | |
| RU2439726C1 (en) | Method to immobilise radioactive wastes in mineral-like matrix | |
| Lan et al. | Synthesis of a new microporous indium sulphide and its capabilities to the separation of strontium | |
| Yanagisawa et al. | Leachability of waste form containing cesium produced by hydrothermal hot-pressing | |
| Sugiyama et al. | Sorption of radionuclides onto cement materials altered by hydrothermal reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | The patent is invalid due to non-payment of fees |
Effective date: 20091010 |