EP1564188A1 - Procédé de traitement de résines échangeuses d'ions usées - Google Patents
Procédé de traitement de résines échangeuses d'ions usées Download PDFInfo
- Publication number
- EP1564188A1 EP1564188A1 EP04003230A EP04003230A EP1564188A1 EP 1564188 A1 EP1564188 A1 EP 1564188A1 EP 04003230 A EP04003230 A EP 04003230A EP 04003230 A EP04003230 A EP 04003230A EP 1564188 A1 EP1564188 A1 EP 1564188A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- ion exchange
- exchange resin
- exchange resins
- wet oxidation
- 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
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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
- G21F9/28—Treating solids
-
- 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
- G21F9/301—Processing by fixation in stable solid media
- G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
- G21F9/304—Cement or cement-like matrix
Definitions
- the invention relates to a method for processing spent ion-exchange resins, and in particular, to a method for processing spent ion-exchange resins by reducing the volume of the spent ion-exchange resins through a wet oxidation process and using barium hydroxide to adjust pH of the wet oxidation reaction solution.
- the method of the invention is applicable mainly to various cleaning treatments in nuclear power plants and in other relative fields.
- ion-exchange resins had been used extensively in the nuclear power plant, including, for example, cleaning treatment of reactor water for supplying de-mineralized reactor water; removing from the reactor water contaminants such as neutron activation products and fission products that are escaped from nuclear fuel elements; lowering the oxygen content in the coolant; controlling contents of the corrosion inhibitor and chemical additives, and the like. Further, ion exchange resins are useful as well in the treatment of wastewater from the nuclear power plant.
- powdery ion exchange resins other than bead resins are also used in the nuclear power plant.
- the specific surface area of the powdery ion exchange resin is approximately 100 times than that of the bead ion exchange resin, and it is a kind of very fine powder. They are used usually for coating the filter elements where, in addition to the function of ion exchange, they can remove small solid beads suspended in the water.
- the bead ion exchange resin After declining of the ion exchange capability of the ion exchange resins or increasing of the radioactivity due to contamination of nuclides in the ion exchange resins, the bead ion exchange resin must be regenerated. After being regenerated and re-used for allowable times, the bead ion exchange resin should be discarded as a radioactive waste. On the contrary, since the powdery ion exchange resin will retrain a great amount of solid impurities therein once in use, it is no more subjected to regeneration and is discarded as waste after being used once.
- the spent ion exchange resin needs to be stabilized for the safety of final disposal.
- agent such as cement, polymers, pitch and the like.
- the performance of the solidification is characterized differently by the kind of agent used.
- solidification with high polymers or pitch could result in less volume of the solidified products.
- polymers are expensive.
- the operation cost with polymers is eventually very expensive.
- pitch gives lower strength of solidified product and the product is combustible.
- March 1997 a fire accident in Japan had been arisen due to solidification operation with pitch, which resulted in a severe nuclear accident. Solidification with cement is a simple and cheap operation.
- the spent ion exchange resin after solidification still has ion exchange ability such that it can exchange with the calcium ion and the like in the solidified product to the extent of affecting its quality. Further, the solidified resin can absorb or release moisture and hence undergoes swelling or contraction. These phenomena will occur particularly in the bead ion exchange resin that, to the severe extent, might result in the swelling or cracking of the solidified product. All of these will limit greatly the loading rate of the spent ion exchange resin in the cement-solidified product such that a bulky solidified product might be yielded after solidification. In view of the increment of the final disposal cost, the direct solidification of spent ion exchange resin is no more economical.
- Processes for treating spent ion exchange resins may be classified into two types, i.e., the dry process and the wet process.
- the dry process includes incineration, vitrification and pyrolysis, while the wet process includes acid hydrolysis, oxidative hydrolysis and supercritical water oxidation etc.
- incineration process is the earliest developed one and had been implemented commercially in some countries. For incineration, it is done typically in a manner of mixing the spent bead ion exchange resins with other combustible waste in order to control the release concentration of SO x , NO x or other hazardous gas.
- Radioactive nuclides Release control of radioactive nuclides is also a critical problem to be solved in incineration process. Unless the discharge of volatile nuclides such as, for example, carbon-14, tritium, cesium-137 and the like can be avoided, nuclides must be removed at first from the spent resin to lower its radioactivity before incineration.
- volatile nuclides such as, for example, carbon-14, tritium, cesium-137 and the like
- the final solidified product in that process is a high active iron block containing sulfur, silicon, sodium and the like, and a special container is required for containing the same.
- the construction cost of the Q-CEP system is very high and it is not economic to construct a process plant with small capacity system. Further, the treatment left of the considerable amount of gaseous byproducts such as hydrogen sulfide and the like produced by that process could be a difficult problem.
- ThermoChem Inc. of USA had developed a steam reforming process, comprising pyrolysis of ion exchange resins under elevated temperature and, meanwhile, generating a combustible gas useful as a fuel through reforming.
- This process has also a severe problem of materials corrosion, and its future needs to be demonstrated further.
- a process at its starting step of development is the SuperCritical Water Oxidation (SCWO) process.
- SCWO SuperCritical Water Oxidation
- the British AEA Industry had developed successfully a wet oxidation process that is comprised of carrying out an oxidative decomposition of bead type spent ion exchange resins by using ferrous sulfate as the catalyst, aqueous hydrogen peroxide as the oxidant and lime hydrate as pH regulator at a temperature of about 100° C and pH of 3-4 to decompose organic components into CO 2 and H 2 O. It is reported that, for treating 40 kg of ion exchange resins, this process would consumed 160 kg of 50 wt% aqueous hydrogen peroxide, 1 kg of concentrated sulfuric acid, 6 kg of slime hydrate, and less than 0.5 kg of de-foaming agent.
- Spent ion exchange resins generated in nuclear power plant includes the cation exchange resin of strong acid type and the anion exchange resin of strong basic type, each possessing different chemical properties.
- the over-all reaction can be represented as eq. (1) and (2) respectively: C 8 H 8 SO 3 + 20H 2 O 2 ⁇ 8CO 2 + 23H 2 O + H 2 SO 4 C 12 H 19 NO + 31H 2 O 2 ⁇ NH 4 OH + 12CO 2 + 38H 2 O
- the ion exchange resin is oxidized, hydrogen carbon constituents are oxidized into CO 2 and H 2 O.
- one mole each of sulfonate group and quaternary amino group contained respectively in cation and anion exchange resins will be oxidized into one mole each of sulfuric acid and ammonium hydroxide, respectively.
- Sulfuric acid generated from the oxidation of cation exchange resins may, other than increasing the acidity of the solution, impart high corrosive property on the wet oxidation solution due to the presence of both sulfuric acid and hydrogen peroxide. This corrosive property may increase as the progress of the wet oxidation of the cation exchange resin.
- the mole ratio of sulfuric acid to ammonium hydroxide in the waste solution of the wet oxidation will vary depending on the mole ratio of the cation exchange resin to the anion exchange resin that have undergone the wet oxidation.
- the mole ratio of anion /cation exchange resin is equal to 2
- the ammonium hydroxide and sulfuric acid produced will form into ammonium sulfate exactly corresponding to that ratio, and the pH of the solution will increase slightly at the end of the reaction.
- the mole ratio > 2 there will be excess of ammonium hydroxide; the pH of the waste wet oxidation solution will increase significantly.
- the mole ratio ⁇ 2 there will remain excess sulfuric acid and, accordingly, the pH will lower considerably.
- one object of the invention is to provide a process for processing spent ion exchange resins on the purpose of reducing the volume of the ion exchange resins by wet oxidation.
- Another object of the invention is to provide a process for processing spent ion exchange resins, characterized in that, after reducing the volume of the ion exchange resin via wet oxidation, the wet oxidation residue and the waste liquor slurry are solidified with high efficiency.
- the process for processing spent ion exchange resins comprises of carrying out the decomposition and oxidation of the ion exchange resin by using aqueous hydrogen peroxide as the oxidant, and increasing pH of the reaction solution with barium hydroxide, or lowering pH of the reaction solution with sulfuric acid.
- a preferred embodiment of the invention comprises the following steps:
- sulfuric acid is specifically selected as the acid
- barium hydroxide is specifically selected as the base for regulating pH
- barium hydroxide is employed as the neutralization agent.
- pH of the wet oxidation solution is preferably controlled at 0.5 to 4 and more preferably at 1 to 3 for cation exchange resins; preferably at 1.5 to 4 and more preferably at 2 to 3.5 for anion exchange resins; and preferably at 1 to 4, and more preferably at 1.5 to 3 for anion-cation mixed ion exchange resins.
- Controlling pH of the reaction solution in an appropriate range can decrease the consumption of the aqueous hydrogen peroxide.
- the experimental results of the invention indicated that, the wet oxidation of a resin mixture containing equal volume ratio of anion and cation exchange resins, and controlling of pH at about 2 consumes about 3.2 to 5 liter of 50% aqueous per liter of the mixed ion exchange resins. The lower is the addition rate of the aqueous hydrogen peroxide, the less the consumption rate of hydrogen peroxide will be.
- the amount of the cation exchange resin added into the reaction solution may yield corresponding amount of sulfate as H 2 SO 4 and/or (NH 4 ) 2 SO 4 .
- They can be converted to BaSO 4 also through addition of barium hydroxide as shown in following reaction equations: ( NH 4 ) 2 SO 4 + Ba ( OH ) 2 ⁇ 2 NH 4 OH + BaSO 4 H 2 SO 4 + Ba ( OH ) 2 ⁇ 2 H 2 O + BaSO 4
- Ammonium hydroxide generated in the above reaction will escape from the solution at pH of more than 8.5, and its escaping rate will be faster as the temperature and pH are higher. Since the conversion is an exothermic reaction, addition of barium hydroxide will increase the temperature and hence favor the escape of ammonia. Based on the experimental results of the invention, it is found that it is more favor for the escape of ammonia as the temperature and pH are higher. In conversion, by adding the amount of barium hydroxide required should be calculated based on the concentration of the barium sulfate to the extent to convert sulfate ion properly into barium sulfate.
- barium hydroxide will increase the amount of wastes, and besides, will give a too high alkalinity of the waste solution, and will consequently result in an adverse effect on the quality of the solidified product.
- an insufficient addition amount of barium hydroxide can not convert adequately sulfate salt into barium sulfate and expel ammonia completely such that not only might affect the quality of the solidified product, but also may generate and evolve ammonia gas in the course of solidification or even after, producing adverse effect on the environmental hygiene.
- the process according to the invention encompasses a perfect and clean treatment on condensed water containing ammonia and organic carbon on the purpose of not incurring secondary pollution.
- ammonia gas upon generation of ammonia gas, it is introduced into an ammonia dissociator where it is decomposed into nitrogen and hydrogen by contacting with a catalyst at an elevated temperature.
- Hydrogen gas thus produced will be oxidized into H2O as it contacts with air at the outlet of the ammonia dissociator and then is discharged together with the nitrogen gas, wherein the reaction involved is as follows: 2 H 2 + O 2 ⁇ 2 H 2 O
- nickel base catalyst has a very good effect.
- nickel oxide loaded on SiO 2 or Al 2 O 3 supports is used as the catalyst, while nickel hydroxide that is converted to nickel oxide upon heating can be used as a catalyst precursor.
- Heating the catalyst bed to above 600° C can decompose highly ammonia gas passing it, and decomposes almost completely at temperature of 700° C.
- no ammonia could be detected in the dissociated gas and the concentration of NOx in it is below 50 ppm.
- Liquid condensate obtained by cooling vapor from the wet oxidation tank might entrain nuclides, and inevitably contains small amount of organic substances that will increase TOC (Total Organic Carbon) concentration if not subjected to any treatment. This might incur the condensed water not allow to be discharged or brings the difficulty of its recycling.
- TOC Total Organic Carbon
- the condensed water after being subjected to a TOC lowering treatment, the condensed water is allowed to pass a bed of ion exchange resins to remove any possible nuclides.
- the experimental result demonstrated that the condensed water generated according to the invention contains a TOC value between about several tens to several hundreds ppm.
- the TOC lowering treatment is accomplished by an advanced oxidation method or through addition of peroxide.
- the advanced oxidation method comprises of utilizing a combination of ozone with ultraviolet light, while the peroxide includes calcium peroxide, sodium persulfate, horseradish peroxidase and the like.
- the condensed water has an optionally lowered TOC concentration of below several tens or even several ppm, and therefore can be reused or discharged.
- the solidification agent used for solidifying wet oxidation liquid waste according to the process of the invention is specially formulated and is composed of cement and pozzolanic materials such as silica fume, fly ash, blast furnace slag powder, as well as, optionally, silicates, phosphates, and oxides or salts of calcium, silicon, magnesium, aluminum, iron, zircon and the like, for ensuring long-term stability and homogeneous quality as well as enhancing operability. Consequently, the solidified product produced by the invention not only exhibits good mechanical strength, freezing and thawing resistance, and water immersion resistance, but also has good long-term stability and homogeneous quality.
- the present invention can provide good solution to overcome disadvantages associated with the prior art techniques in that, in addition to eliminate severe corrosion problem, it demonstrates a high volume reducing effect and a quite stable control on operation.
- the experimental apparatus used in this example is composed of, as shown in Fig. 2, a 4,000 ml glass beaker 1 that can be covered with a three-hole glass lid. Of these three holes, the middle hole A is provided with a Teflon stirring blade 3 driven by a motor 2, another hole is used as a feeding port B, and another hole is used as an outlet C.
- the outlet C is communicated with a refluxing tube 4, a membrane demister 5, and a condenser 6. Gas mixture generated in the wet oxidation emits from the outlet C, and passes through the membrane demister 5 to have water mist contained in that gas mixture removed as large water drop by falling to the refluxing tube 4 and flowing into the reactor 7.
- a Teflon tube 9 is further provided for refluxing of the condensed water.
- the valve on the Teflon tube 9 can be opened as necessary for allowing the condensed water refluxing to the reaction beaker to adjust the liquid level therein.
- 10 denotes a conduct
- 11 an ammonia dissociator
- 12 a heater
- 13 a thermometer
- V1, V2 and V3 denote valves.
- a metering pump was used to metering 50% aqueous hydrogen peroxide into the beaker at a flow rate of 12.5 ml/min. As soon as the aqueous hydrogen peroxide was metered into the beaker, the temperature of the reaction solution was increased to boiling point. The temperature was then kept at the boiling point. If bubbles were evolved in the course, a proper amount of de-foaming agent (Dow Coming Q2-3447) was added timely to control them. At the same time, barium hydroxide monohydrate powder was added to adjust pH of the solution to 1.9 ⁇ 0.1.
- the valve on the Teflon tube 9 was opened to reflux the water condensate to keep a stable level.
- 40 ml of cation exchange resin and 60 ml of anion exchange resin as well as 375 ml of aqueous hydrogen peroxide were added every half hour.
- enough aqueous hydrogen peroxide was added to a predetermined consumption amount.
- the reaction solution was kept at a temperature between 98°C and the boiling point for 0.5 hour to allow the aqueous hydrogen peroxide reacted completely.
- PE polyethylene
- weight of calcium hydroxide consumed for adjusting pH of the wet oxidation solution was 68.2 g that was 2.5 times the amount when using barium hydroxide (27 g), and was 9 times in term of number of moles. This indicated that control of pH achieved by using barium hydroxide was more stable and effective than that achieved by using calcium hydroxide.
- compressive strength of the solidification products tested according the test method specified by USNRC after standing for 28 days and after freezing and thawing test indicated that solidification products did not possess considerable mechanical strength.
- the specific gravity of the solidification product was 1.86 that was 84% of the specific gravity (2.22) of the solidification product obtained when using barium hydroxide.
- the volume of the solidification product was 980 ml that was 1.1 times obtained when using barium hydroxide (885 ml). These indicated that process of the prior art was inferior to the process of the invention in aspects of pH control in operation of the wet oxidation, qualities of the solidification product and the effectiveness of volume reduction.
- the forgoing illustrates only part of embodiments according to the invention, and is not intended to limit the scope of the invention thereto.
- expected objects of the invention can be achieved.
- the invention thus provides a process for processing spent ion exchange resins, which can reduce the volume of the spent ion exchange resins by wet oxidation and can solidify the wet oxidation residue and slurry with high efficiency, and thus meets the requirement of commercial uses.
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE602004003464T DE602004003464T2 (de) | 2004-02-13 | 2004-02-13 | Verfahren zur Behandlung vor verbrauchten Ionenaustauschern |
AT04003230T ATE346827T1 (de) | 2004-02-13 | 2004-02-13 | Verfahren zur behandlung vor verbrauchten ionenaustauschern |
ES04003230T ES2278237T3 (es) | 2004-02-13 | 2004-02-13 | Metodo para procesar resinas de intercambio ionico usadas. |
EP04003230A EP1564188B1 (fr) | 2004-02-13 | 2004-02-13 | Procédé de traitement de résines échangeuses d'ions usées |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04003230A EP1564188B1 (fr) | 2004-02-13 | 2004-02-13 | Procédé de traitement de résines échangeuses d'ions usées |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1564188A1 true EP1564188A1 (fr) | 2005-08-17 |
EP1564188B1 EP1564188B1 (fr) | 2006-11-29 |
Family
ID=34684685
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04003230A Expired - Lifetime EP1564188B1 (fr) | 2004-02-13 | 2004-02-13 | Procédé de traitement de résines échangeuses d'ions usées |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1564188B1 (fr) |
AT (1) | ATE346827T1 (fr) |
DE (1) | DE602004003464T2 (fr) |
ES (1) | ES2278237T3 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110400648A (zh) * | 2019-06-20 | 2019-11-01 | 中国辐射防护研究院 | 一种核级放射性废树脂的高效氧化处理方法 |
CN110723799A (zh) * | 2019-11-18 | 2020-01-24 | 中核核电运行管理有限公司 | 一种核电机组常规岛含氨废水收集与排放装置及方法 |
TWI755071B (zh) * | 2020-09-23 | 2022-02-11 | 黃慶村 | 以廢離子交換樹脂的濕法降解廢液製備可硬化漿,並用以固化/固定其他廢棄物的方法,以及改良的廢離子交換樹脂與有機物的濕法氧化方法 |
RU2810633C1 (ru) * | 2023-03-23 | 2023-12-28 | Федеральное государственное автономное образовательное учреждение высшего образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" | Способ утилизации отработанных сульфокислотных ионообменных смол |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008005336A1 (de) * | 2008-01-17 | 2009-07-30 | Areva Np Gmbh | Verfahren zur Konditionierung radioaktiver Ionenaustauscherharze |
CN103288330A (zh) * | 2013-07-10 | 2013-09-11 | 江苏坤泽科技股份有限公司 | 一种淡水淤泥固化剂 |
DE102018131902B3 (de) | 2018-12-12 | 2020-02-27 | Framatome Gmbh | Verfahren zur Konditionierung von Ionenaustauscherharzen und Vorrichtung zur Durchführung des Verfahrens |
CN110510842A (zh) * | 2019-08-28 | 2019-11-29 | 中交一航局第三工程有限公司 | 一种淤泥固化和筑岛工艺 |
WO2023019563A1 (fr) * | 2021-08-20 | 2023-02-23 | 钰永科技有限公司 | Optimisation de l'oxydation humide d'une résine usagée et procédé de traitement de déchets avec un liquide résiduaire d'oxydation |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4686068A (en) * | 1984-07-10 | 1987-08-11 | Toyo Engineering Corporation | Method of batchwise treating radioactive organic wastes |
US4770783A (en) * | 1986-01-15 | 1988-09-13 | Aktiebolaget Asea-Atom | Method of processing waste from a nuclear power plant, said waste comprising ion-exchange resin containing radioactive metals |
US5545798A (en) * | 1992-09-28 | 1996-08-13 | Elliott; Guy R. B. | Preparation of radioactive ion-exchange resin for its storage or disposal |
-
2004
- 2004-02-13 ES ES04003230T patent/ES2278237T3/es not_active Expired - Lifetime
- 2004-02-13 AT AT04003230T patent/ATE346827T1/de not_active IP Right Cessation
- 2004-02-13 DE DE602004003464T patent/DE602004003464T2/de not_active Expired - Lifetime
- 2004-02-13 EP EP04003230A patent/EP1564188B1/fr not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4686068A (en) * | 1984-07-10 | 1987-08-11 | Toyo Engineering Corporation | Method of batchwise treating radioactive organic wastes |
US4770783A (en) * | 1986-01-15 | 1988-09-13 | Aktiebolaget Asea-Atom | Method of processing waste from a nuclear power plant, said waste comprising ion-exchange resin containing radioactive metals |
US5545798A (en) * | 1992-09-28 | 1996-08-13 | Elliott; Guy R. B. | Preparation of radioactive ion-exchange resin for its storage or disposal |
Non-Patent Citations (1)
Title |
---|
"Radioactive Waste Management and Environmental Remediation", 1995, ASME, XP009032908 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US12033766B2 (en) | 2018-12-12 | 2024-07-09 | Framatome Gmbh | Method for conditioning ion exchange resins and apparatus for carrying out the method |
CN110400648A (zh) * | 2019-06-20 | 2019-11-01 | 中国辐射防护研究院 | 一种核级放射性废树脂的高效氧化处理方法 |
CN110723799A (zh) * | 2019-11-18 | 2020-01-24 | 中核核电运行管理有限公司 | 一种核电机组常规岛含氨废水收集与排放装置及方法 |
TWI755071B (zh) * | 2020-09-23 | 2022-02-11 | 黃慶村 | 以廢離子交換樹脂的濕法降解廢液製備可硬化漿,並用以固化/固定其他廢棄物的方法,以及改良的廢離子交換樹脂與有機物的濕法氧化方法 |
RU2810633C1 (ru) * | 2023-03-23 | 2023-12-28 | Федеральное государственное автономное образовательное учреждение высшего образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" | Способ утилизации отработанных сульфокислотных ионообменных смол |
Also Published As
Publication number | Publication date |
---|---|
EP1564188B1 (fr) | 2006-11-29 |
ATE346827T1 (de) | 2006-12-15 |
ES2278237T3 (es) | 2007-08-01 |
DE602004003464T2 (de) | 2007-09-20 |
DE602004003464D1 (de) | 2007-01-11 |
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