GB1577383A - Process for treating radioactive ion-exchange resins - Google Patents
Process for treating radioactive ion-exchange resins Download PDFInfo
- Publication number
- GB1577383A GB1577383A GB7032/78A GB703278A GB1577383A GB 1577383 A GB1577383 A GB 1577383A GB 7032/78 A GB7032/78 A GB 7032/78A GB 703278 A GB703278 A GB 703278A GB 1577383 A GB1577383 A GB 1577383A
- Authority
- GB
- United Kingdom
- Prior art keywords
- exchange resins
- ion exchange
- resins
- reaction
- acid
- 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
Links
- 239000003456 ion exchange resin Substances 0.000 title claims description 44
- 229920003303 ion-exchange polymer Polymers 0.000 title claims description 44
- 230000002285 radioactive effect Effects 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 24
- 230000008569 process Effects 0.000 title claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- 238000003763 carbonization Methods 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 9
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 238000009434 installation Methods 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000498 cooling water Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052778 Plutonium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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
- G21F9/32—Processing by incineration
Description
(54) PROCESS FOR TREATING RADIOACTIVE ION-EXCHANGE RESINS
(71) We, NUKEM GmbH, a body corporate organised under the laws of
Germany, of 6450 Hanau 1, Germany do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to a process for treating radioactive ion-exchange resins, and is an improvement on out prior patent
Application No. 38111/77 (Serial No.
1558135).
In nuclear engineering, there accumulate a variety of contaminated organic waste materials (paper, cloths, plastics, gloves, etc) which are bulky and contain relatively little radioactive substance, but which nevertheless cannot be treated by conventional methods.
This applies in particular to waste containing the highly toxic plutonium or artificial radionuclides. The object of all processes for treating waste of the type in question is to reduce the volume by incineration and to treat the incineration residues or rather the plutonium without producing contaminated waste gases or active effluent.
According to our prior patent Application
No. 38111/77 (Serial No 1558135) the radioactive organic waste is treated by converting the organic constituents into gaseous products in countercurrent with excess steam in a closed furnace system at a temperature of from 600 to 1100"C, the exhaust gas passing through another temperature zone, on this occasion of 800 to 1100"C, for the purposes of after-reaction.
In nuclear installations, such as nuclear power stations and reprocessing plants, there accumulate from the treatment of water, large quantities of radioactive ion exchange resins which are exhausted after single or repeated charging and which have to be delivered to final storage sites. They contain activity often in the form of radioactive heavy metal ions.
Radioactive resins of the type in question are not allowed to be stored in the form of loose materials. Instead, they have to be accommodated in casks in admixture with a fixing composition. The solid mass obtained in this way has to meet stringent requirements in regard to strength and insolubility.
On account of increasingly more rigorous storage conditions and the further increase in storage costs likely to be introduced in the future, a reduction in the quantities of waste is absolutely essential. This can only be achieved by reducing the volume of the waste material before it is introduced into the fixing composition.
In the case of radioactive ion exchange resins, this has been done in conventional processes by subjecting them to a drying process in the swollen water-enriched state in which they accumulate in the nuclear installation. The reduction in volume obtained in this way, however, only amounts to around 50% of the initial volume. Other known processes based on heat treatment also lead to reductions in volume of this order. At the same time, however, there arise exhaust gas problems which are difficult to solve.
Even the process according to our prior
Application No. 38111/77 (Serial No. 1558135 based on the complete pyrohydrolysis of the organic reactor waste is not optimal when it comes to the treatment of radioactive ion exchange resins because, in their case, complete pyrohydrolysis results in a considerable proportion of activity entering the waste gas or rather the waste gas filters which, as a result, also have to be pyrohydrolysed.
Accordingly, an object of the present invention is to find a process for reducing the volume of radioactive ion exchange resins which does not involve any problems with radioactive waste gases.
According to the present invention, this object is achieved by converting the ion exchange resins into gaseous products in countercurrent with excess steam in a closed furnace system at a temperature of from 400 to 800"C until only from 4 to 10% by volume of the initial volume of the ion exchange resins used is present, the exhaust gas passing through another temperature zone of from 800 to 1100 C, for the purposes of after-reaction (as hereinafter defined). As used herein, the term "after-reaction" means thermal afterburning of the reaction gases.
Accordingly, the pyrohydrolytic treatment is terminated when from 4 to 10% of the initial volume is still present in the apparatus.
This may either be determined purely optically or, alternatively, tests may be conducted to determine the duration at certain temperatures and with certain types of resin.
The process according to the present invention has a significant advantage in that the activity remains in the carbonised resin, entering any condensate formed to a minimal extent only, whereas the exhaust gas is substantially free from activity.
The residue left after any condensate has been evaporated may advantageously be remixed and solidified with the carbonised resins. Since the resins lose their swelling power as a result of carbonisation, admixture with the evaporation residue is not accompanied by any increase in volume with the result that, in this case, too, the final volume always amounts to less than 10% of the initial volume of the ion exchange resins used.
In one embodiment of the process according to the present invention, the gaseous products from the ion exchange resins are neutralised either during or after the reaction.
An installation for the treatment of radioactive ion exchange resins in accordance with the present invention is diagrammatically illustrated in the accompanying drawings.
The installation consists, for example, of a fluidised-bed reactor (2) which is provided with a heating system (1) and in which the active ion exchange resins are contacted in countercurrent with superheated steam. The steam is produced in an evaporator (3) and is heated to the reaction temperature in a superheater (4). After leaving the fluidised bed reactor (1), the steam is delivered together with condensible and non-condensible reaction products to an injection-type condenser (5) where the steam and condensible reaction products are condensed. Non-condensible reaction products are delivered through an adsorption filter (6) to an exhaust-gas system for after-treatment.
The condensate is returned to and reevaporated in the evaporator (3). The steam generated in the evaporator (3) is returned to the process. A first component stream of the steam flows through the superheater (4) back into the fluidised-bed reactor, whilst a second component stream is condensed in a condenser (7) pumped off by means of a pump (8) and subsequently sprayed by sprayer (9) into the injection type condenser (5), thereby establishing a closed circuit for the water or steam used as process medium.
The residue product of the evaporator (3) consists of the condensible active reaction products formed during carbonisation of the exchanger resins. It is drained off at intervals into a storage tank (10) from which it is pumped off by means of the pump (I1) for admixture with the carbonised ion exchange resins.
The process according to the present invention is illustrated by the following
Examples. In all of the Examples, the ion exchange resins treated are converted into gaseous products in countercurrent with excess steam, and the exhaust gas produced is passed through another temperature zone of from 800 to 11000C for the purposes of after-reaction.
EXAMPLE I
A radioactive ion exchange resin filling is introduced into a fixed bed reactor which is then closed. The reactor is heated to a temperature of 150"C by direct jacket heating.
Thereafter steam superheated to 650"C is introduced. The carbonisation reaction lasts about 3 hours, after which 8% of the initial volume are still present. The reactor is then cooled by way of its outer jacket. The cold reaction product can be removed.
EXAMPLE 2
Radioactive ion exchange resins are introduced into a fluidised bed reactor. The reactor is heated to a temperature of 180"C by direct jacket heating. Once the temperature of the reactor is high enough, steam superheated to 700"C is introduced. The steam serves both as the fluidising gas for the ion exchange resins and also as the reaction gas.
The intimate contact between the reactants shortens the carbonisation time to around 1 hour for a residual volume of 7%. The solid particles remain intact as individual grains. This structure facilitates admixture with the active condensate and incorporation into fixing compositions.
On completion of carbonisation, the reaction products are cooled in the gas stream and may then be removed from the reactor.
EXAMPLE 3
A revolving tubular furnace is used as the reactor. The furnace is loaded with radioactive ion exchange resins continuously. It is heated beyond the condensation temperature of steam by direct jacket heating. The carbonisation reaction is carried out in the flowing steam superheated to 500"C. Steam and ion exchange resins flow in counter current. The constant movement of the ion exchange resins enables effective admixture of the resins, and reduces the danger of agglomeration. On completion of the carbonisation reaction, the solid residue is cooled by cooling the reactor jacket, and is subsequently delivered to the solidification stage.
In the carbonisation of acid or alkaline ion exchange resins, the reaction gases have to be neutralised, preferably in the injection condenser (5) or the exchange resins mixed in such a way that neutral reaction gases are formed.
EXAMPLE 4
Radioactive ion exchange resins differing in their characteristics, for example acid resins and alkaline resins, are mixed together.
The mixture is carbonised in installations and under reaction conditions corresponding to those of Examples 1 to 3. With acid resins,
SO3, for example, is liberated, whereas with alkaline resins, amines are liberated. Providing the ion exchange resins are mixed appropriately, chemically neutral reaction products are formed.
EXAMPLE 5
Radioactive acid ion exchange resins or a mixture of acid and alkaline ion exchange resins with an acid reaction are introduced into a reactor and carbonised as described in Examples 1 to 3.
Milk of lime, CaO in powder form, or
Ca(OH)2 in the form of an aqueous solution is added to the process steam before it enters the reactor in order to neutralise the reaction products.
EXAMPLE 6
Radioactive acid ion exchange resins or a mixture of acid and alkaline ion exchange resins with an acid reaction are initially introduced into the reactor. The carbonisation treatment takes place as described in Examples 1 to 3. Neutralisation solutions are added via the nozzle (9) and the acidic gaseous reaction product is neutralized in the injection condenser (5). Milk of lime or
Ca(OH)2 is also added to the cooling water upstream of the injection nozzle by a suitable dosing device.
WHAT WE CLAIM IS:
1. A process for the treatment of radioactive ion exchange resins which comprises converting the resins into gaseous products in countercurrent with excess steam in a closed furnace system at a temperature of from 400 to 8000C until only from 4 to 10% by volume of the initial volume of the active ion exchange resins used is present, the exhaust gas passing through another temperature zone of from 800 to 1100 C, for the purposes of afterreaction (as hereinbefore defined).
2. A process as claimed in claim 1, wherein the radioactive residue obtained in the closed circuit by evaporation of any condensate formed is mixed with the carbonised resins and the resulting mixture delivered to the final storage site.
3. A process as claimed in claims 1 and 2, wherein that the gaseous products from the ion exchange resins are neutralised either during or after the reaction.
4. A process for the treatment of radioactive ion exchange resins substantially as described with particular reference to any of the Examples.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (4)
1. A process for the treatment of radioactive ion exchange resins which comprises converting the resins into gaseous products in countercurrent with excess steam in a closed furnace system at a temperature of from 400 to 8000C until only from 4 to 10% by volume of the initial volume of the active ion exchange resins used is present, the exhaust gas passing through another temperature zone of from 800 to 1100 C, for the purposes of afterreaction (as hereinbefore defined).
2. A process as claimed in claim 1, wherein the radioactive residue obtained in the closed circuit by evaporation of any condensate formed is mixed with the carbonised resins and the resulting mixture delivered to the final storage site.
3. A process as claimed in claims 1 and 2, wherein that the gaseous products from the ion exchange resins are neutralised either during or after the reaction.
4. A process for the treatment of radioactive ion exchange resins substantially as described with particular reference to any of the Examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2708492A DE2708492C2 (en) | 1977-02-26 | 1977-02-26 | Process for the treatment of radioactively contaminated ion exchange resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1577383A true GB1577383A (en) | 1980-10-22 |
Family
ID=6002301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7032/78A Expired GB1577383A (en) | 1977-02-26 | 1978-02-22 | Process for treating radioactive ion-exchange resins |
Country Status (7)
| Country | Link |
|---|---|
| JP (2) | JPS53107600A (en) |
| BR (1) | BR7800508A (en) |
| DE (1) | DE2708492C2 (en) |
| ES (1) | ES465452A2 (en) |
| FR (1) | FR2382076A2 (en) |
| GB (1) | GB1577383A (en) |
| IT (1) | IT1156446B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2488524A1 (en) * | 1980-08-12 | 1982-02-19 | British Nuclear Fuels Ltd | WASTE TREATMENT PLANT, SUCH AS EFFLUENTS OF NUCLEAR PLANTS |
| WO2020089265A1 (en) | 2018-10-31 | 2020-05-07 | Montair Process Technology | System for thermally oxidising a waste gas with hydrocarbon compounds into an oxidised gas and use thereof |
| WO2020089341A1 (en) | 2018-10-31 | 2020-05-07 | Montair Process Technology | System and method for pyrolysing organic waste |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410126A (en) * | 1978-10-12 | 1983-10-18 | Cooper Industries, Inc. | Mass soldering system |
| CA1163431A (en) * | 1982-08-20 | 1984-03-13 | Atomic Energy Of Canada Limited - Energie Atomique Du Canada, Limitee | Method of reducing the volume of radioactive waste |
| JPS6417589U (en) * | 1987-07-20 | 1989-01-27 | ||
| JPH027693U (en) * | 1988-06-27 | 1990-01-18 | ||
| JP5961044B2 (en) * | 2012-06-01 | 2016-08-02 | 日本碍子株式会社 | Volume reduction treatment method and volume reduction treatment apparatus for persistent degradable waste |
| EP3246924A4 (en) * | 2015-01-15 | 2018-09-05 | Hankook Technology Inc. | System for reducing volume of low-level radioactive wastes by using superheated vapor |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1958464A1 (en) * | 1969-11-21 | 1971-06-03 | Alkem Gmbh | Process for wet chemical combustion of organic material |
| DE2251007C2 (en) * | 1972-10-18 | 1984-09-27 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe | Incineration furnace for radioactive waste |
| AT338388B (en) * | 1975-06-26 | 1977-08-25 | Oesterr Studien Atomenergie | METHOD AND DEVICE FOR TRANSFERRING RADIOACTIVE ION EXCHANGE RESINS INTO A STORAGE FORM |
-
1977
- 1977-02-26 DE DE2708492A patent/DE2708492C2/en not_active Expired
- 1977-12-27 ES ES465452A patent/ES465452A2/en not_active Expired
-
1978
- 1978-01-09 FR FR7800465A patent/FR2382076A2/en active Granted
- 1978-01-27 BR BR7800508A patent/BR7800508A/en unknown
- 1978-02-16 IT IT7867323A patent/IT1156446B/en active
- 1978-02-22 GB GB7032/78A patent/GB1577383A/en not_active Expired
- 1978-02-24 JP JP2080378A patent/JPS53107600A/en active Pending
-
1985
- 1985-02-21 JP JP60031686A patent/JPS60233598A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2488524A1 (en) * | 1980-08-12 | 1982-02-19 | British Nuclear Fuels Ltd | WASTE TREATMENT PLANT, SUCH AS EFFLUENTS OF NUCLEAR PLANTS |
| WO2020089265A1 (en) | 2018-10-31 | 2020-05-07 | Montair Process Technology | System for thermally oxidising a waste gas with hydrocarbon compounds into an oxidised gas and use thereof |
| WO2020089341A1 (en) | 2018-10-31 | 2020-05-07 | Montair Process Technology | System and method for pyrolysing organic waste |
| BE1026747A1 (en) | 2018-10-31 | 2020-05-28 | Montair Process Tech | System for the thermal oxidation of a waste gas with hydrocarbon compounds to an oxidized gas and the use thereof |
| BE1026748A1 (en) | 2018-10-31 | 2020-05-28 | Montair Process Tech | System and method for pyrolysing organic waste |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60233598A (en) | 1985-11-20 |
| DE2708492C2 (en) | 1983-01-20 |
| FR2382076A2 (en) | 1978-09-22 |
| ES465452A2 (en) | 1979-05-16 |
| IT1156446B (en) | 1987-02-04 |
| FR2382076B2 (en) | 1983-05-27 |
| JPS53107600A (en) | 1978-09-19 |
| IT7867323A0 (en) | 1978-02-16 |
| DE2708492A1 (en) | 1978-08-31 |
| BR7800508A (en) | 1978-10-03 |
| JPS6337360B2 (en) | 1988-07-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |