JPS63208798A - Method of processing radioactive waste liquor - Google Patents
Method of processing radioactive waste liquorInfo
- Publication number
- JPS63208798A JPS63208798A JP62041191A JP4119187A JPS63208798A JP S63208798 A JPS63208798 A JP S63208798A JP 62041191 A JP62041191 A JP 62041191A JP 4119187 A JP4119187 A JP 4119187A JP S63208798 A JPS63208798 A JP S63208798A
- Authority
- JP
- Japan
- Prior art keywords
- waste liquid
- radioactive waste
- column
- cmp
- solid support
- 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
- 239000002901 radioactive waste Substances 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 18
- 239000007788 liquid Substances 0.000 claims description 48
- 239000002699 waste material Substances 0.000 claims description 27
- 229910052778 Plutonium Inorganic materials 0.000 claims description 11
- 229910052770 Uranium Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 4
- -1 carbamoyl methylene pho sph-onate Chemical compound 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 238000000605 extraction Methods 0.000 description 15
- 229910017604 nitric acid Inorganic materials 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 11
- 238000011282 treatment Methods 0.000 description 8
- SGZRFMMIONYDQU-UHFFFAOYSA-N n,n-bis(2-methylpropyl)-2-[octyl(phenyl)phosphoryl]acetamide Chemical compound CCCCCCCCP(=O)(CC(=O)N(CC(C)C)CC(C)C)C1=CC=CC=C1 SGZRFMMIONYDQU-UHFFFAOYSA-N 0.000 description 7
- 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 5
- 239000003463 adsorbent Substances 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002915 spent fuel radioactive waste Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
- 150000001255 actinides Chemical class 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002927 high level radioactive waste Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052695 Americium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- LXQXZNRPTYVCNG-UHFFFAOYSA-N americium atom Chemical compound [Am] LXQXZNRPTYVCNG-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100001252 long-term toxicity Toxicity 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002914 transuranic radioactive waste Substances 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
「産業上の利用分野」
この発明は、超ウラン元素（ＴＲＵ）を含む放射性廃液
を容易かつ経済的に処理する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a method for easily and economically treating radioactive waste liquid containing transuranic elements (TRU).
「従来の技術」
周知のように、使用済み核燃料に対しては、再処理によ
りＵ−Ｐｕを回収し、残りの高レベル放射性廃液をガラ
ス固化する方法が我が国において採択されている。廃棄
物の処理処分という点から、高レベル放射性廃液中に含
まれる長寿命α放射体である超ウラン元素（’ｒｎＵ）
を分離し、これを効果的に貯蔵管理または消滅処理する
のがもつとら妥当な考え方であり、従来、再処理は、使
用済み燃料を硝酸に溶解して種々の酸化還元処理を行な
い、Ｔ １１１） （リン酸トリブチル）を用いた溶媒
抽出でＵとＰｕとを分離する、いわゆるＰｕｒｅｘ法が
用いられている。"Prior Art" As is well known, Japan has adopted a method for recovering U-Pu from spent nuclear fuel through reprocessing and vitrifying the remaining high-level radioactive waste liquid. From the point of view of waste treatment and disposal, transuranium elements ('rnU), which are long-lived alpha emitters contained in high-level radioactive waste liquids, are important.
It is a reasonable idea to separate the spent fuel and effectively store it or dispose of it. Conventionally, reprocessing involves dissolving spent fuel in nitric acid and performing various redox treatments. The so-called Purex method is used in which U and Pu are separated by solvent extraction using (tributyl phosphate).
「発明が解決しようとする問題点」
ところで、前記従来の放射性廃液の処理方法において、
Ｕ、Ｐｕ除去後のＴＲＵを含む放射性廃液は、長期的に
毒性を持つので、これをガラス固化して貯蔵管理してい
るが、長寿命のα放射体が放射性廃液から分離されてい
ないため、放射性廃棄物（ガラス固化物）の貯蔵期間が
極めて長いらのとなり、貯蔵管理に膨大なコストを要し
ている。"Problems to be Solved by the Invention" By the way, in the conventional radioactive waste liquid treatment method,
The radioactive waste liquid containing TRU after U and Pu removal has long-term toxicity, so it is stored and managed by vitrification, but the long-lived alpha emitters have not been separated from the radioactive waste liquid. The storage period of radioactive waste (vitrified waste) is extremely long, and storage management requires enormous costs.
このように、従来の放射性廃液の処理方法では、溶液中
からＴ ＲＵを効率良（分離除去しないかぎり、放射性
廃棄物の処分や管理方法か困難になり、膨大なコストを
要することになる。As described above, in conventional radioactive waste treatment methods, unless TRU is efficiently separated and removed from the solution, it becomes difficult to dispose and manage the radioactive waste, and it requires a huge amount of cost.
この発明は上記事情に鑑みてなされた乙ので、その目的
はＴＲＵを含む放射性廃液からＴ ＲＵを容易かつ経済
的に分離除去し、長期にわたる管理を要する廃液固化体
を低減することができる一放射性廃液の処理方法を提供
することにある。This invention was made in view of the above circumstances, and its purpose is to easily and economically separate and remove TRU from radioactive waste liquid containing TRU, and to reduce the amount of solidified waste liquid that requires long-term management. The object of the present invention is to provide a method for treating waste liquid.
「問題点を解決するための手段」
この発明に係る放射性廃液の処理方法は、まず、高酸濃
度にした放射性廃液から陰イオン交換等によりＵ、Ｐｕ
を分離除去し、Ｕ、Ｐｕ除去後の’ｒ ｔｔＵを含む放
射性廃液をＣＭ Ｐ （ｃａｒｂａ（ｌｌｏｙｌ ｍｅ
ｔｈｙｌｅｎｅ ｐｈｏｓｐｈｏｎａＬｅ）またはＣＭ
Ｐ Ｏ（ｃａｒｂａｍｏｙｌ ｍｅ−ｔｈｙｌｅｎｅ
ｐｈｏｓｐｈｉｎｅ ｏｘｉｄｅ）を含浸させた固体
支持体（カラム）中を通過させることによりこの固体支
持体に液中のＴＲＵを吸着させて前記廃液からＴＲｕを
除去するとともに、前記固体支持体に吸着した’ｌ’
ＲＵを溶離して回収することを特徴とする方法である。"Means for Solving the Problems" The method for treating radioactive waste liquid according to the present invention is to first remove U, Pu, etc. from radioactive waste liquid with a high acid concentration by anion exchange or the like.
After removing U and Pu, the radioactive waste solution containing 'r ttU was treated with CMP (carba(lloyl me)).
thylene phosphonaLe) or CM
P O (carbamoyl me-thylene
TRU in the liquid is adsorbed on this solid support by passing it through a solid support (column) impregnated with phosphine oxide), and the TRU is removed from the waste liquid. '
This method is characterized by eluting and recovering RU.
「作用 」
前記構成におけるＣ Ｍ Ｐ （ｃａｒｂａｍｏｙｌ
ｍｅｔｈｙｌｅｎｅｐｔｉｏｓｐｈｏｎａｔｅ）または
ＣＭ Ｐ Ｏ（ｃａｒｂａｍｏｙｌ ｍｅｔｈｙ−１ｅ
ｎｅ ｐｈｏｓｐｈｉｎｅ ｏｘｉｄｅ）は、３価、４
価、６価のアクチノイド元素の抽出、特に３価のアクチ
ノイド元素の抽出が可能な化合物（二座配位系有機リン
化合物）として最近注目され始めた抽出剤である。本発
明においては、このＣＭＰＳＣＭＰＯをイオン交換樹脂
等の固体支持体に含浸させることによって、比較的高価
なＣＭＰ、ＣＭＰＯの流損失を防止するとともに、ＣＭ
ＰＸＣＭＰＯに抽出させたＴＲＵの固定を容易にしてい
る。"Action" CMP (carbamoyl
methyleneptiosphonate) or CM PO (carbamoyl methyl-1e
ne phosphine oxide) are trivalent and 4-valent
It is an extractant that has recently begun to attract attention as a compound (bidentate organic phosphorus compound) capable of extracting valent and hexavalent actinide elements, especially trivalent actinide elements. In the present invention, by impregnating this CMPSCMPO into a solid support such as an ion exchange resin, flow loss of relatively expensive CMP and CMPO is prevented, and CMPS
This facilitates the fixation of TRU extracted by PXCMPO.
前記ＣＭＰの硝酸溶液中でのウラン；Ｕ（ＶＩ）および
１’ ＲＵの抽出反応式は次のように表すことができる
。なお、ＴＲＵとしては、プルトニウム；Ｐｕ（［Ｖ）
と、廃液中に比較的多量に含まれるアメリシウム；Ａｍ
（Ｉｎ）とを例に挙げた。The extraction reaction formula of uranium; U(VI) and 1' RU in the CMP nitric acid solution can be expressed as follows. In addition, as TRU, plutonium; Pu([V)
and americium contained in relatively large amounts in the waste liquid; Am
(In) was given as an example.
口Ｑ、２＋＋ ２ＮＯ３−＋ ２ＣＭＰ＝ ＵＯｘ
（ＮＯ３）ｔ・２ＣＭＰＰｕ”＋ ４ＮＯ３−＋ ２Ｃ
ＭＰ ” ＰＬＩ（ＮＯ３）４”２ＣＭＰＡｍ” ＋３
ＮＯｚ−＋ ３ＣＭＰ＝ Ａ１１ｌ（ＮＯ３）３ ・３
ＣＭＰまた、高酸性度では、硝酸の付加反応が生じ（塩
基性のより強いＣＭ Ｐ Ｏにおいては一層顕著に生じ
ろ）、Ａｍ（ＩＩＩ）の抽出は次式のようになると考え
られる。Mouth Q, 2++ 2NO3-+ 2CMP= UOx
(NO3)t・2CMPPu"+ 4NO3-+ 2C
MP” PLI(NO3)4”2CMPAm” +3
NOz-+ 3CMP= A11l(NO3)3 ・3
CMP Also, at high acidity, an addition reaction of nitric acid occurs (even more prominently in the more basic CMPO), and the extraction of Am(III) is thought to be as shown in the following equation.
Ａｍ”＋ ４ＮＯ３−＋ｌＩ”＋ ３ＣＭＰ＝ Ａｍ（
ＮＯ３）３・３ＣＭＰ−ＨＮＯ３一般に塩基性の強い抽
出剤においては、高硝酸濃度では金属錯体の抽出よりら
酸の付加反応が優先するので、抽出能力が低下する。し
かし、塩基性の弱いＣＭＰでは、アミド基がバッファー
となり、金属錯体が配位するフォスホリル基が１−ビの
アタックを受けないため、高酸性度でも抽出能力か低下
しない。ただし、抽出能力自体については、第５図に示
すように、ＣＭＰＯの方が強い。また、他の元素との分
離性では、ＣＭＰの方が優れている。なお、この第５図
においては、ＣＭＰとして゛ はＤ １１１） Ｅ Ｃ
Ｍ Ｐ （ｄｉｈｅｘｙ−Ｎ、Ｎ−ｄｉｅｔｈｙｌ ｃ
ａｒｂａｍｏ−ｙｉ ｍｅｔｈｙｌｅｎｅ ｐｈｏｓｐ
ｈｏｎａｔｅ）を用い、ＣＭ Ｐ ＯとしてはＤ ＨＤ
Ｅ ＣＭ Ｐ Ｏ（ｄｉｈｅｘｙ−Ｎ、Ｎ−ｄｉｅｔ
ｈｙｌｃａｒｂａｍｏｙｌ ｍｅｔｈｙｌｅｎｅ ｐｈ
ｏｓｐｈｉｎｅ ｏｘｉｄｅ）を用いた。Am"+ 4NO3-+lI"+ 3CMP= Am(
NO3)3.3CMP-HNO3 In general, in highly basic extractants, at high nitric acid concentrations, the acid addition reaction takes precedence over the extraction of metal complexes, resulting in a decrease in extraction ability. However, in weakly basic CMP, the amide group acts as a buffer and the phosphoryl group to which the metal complex is coordinated is not attacked by 1-bi, so the extraction ability does not decrease even at high acidity. However, as for the extraction ability itself, as shown in FIG. 5, CMPO is stronger. Furthermore, CMP is superior in terms of separation from other elements. In addition, in this Fig. 5, as CMP, ゛ is D 111) E C
M P (dihexy-N, N-diethyl c
arbamo-yi methylene phosp
honate), and CM PO is D HD.
E CM P O (dihexy-N, N-diet
hylcarbamoyl methylene ph
osphine oxide) was used.
各構造式は同図中に示した。Each structural formula is shown in the figure.
また、前記ＣＭＰまたはＣＭＰＯの含浸固体支持体には
、ＣＭＰまたはＣＭＰＯの含浸量が多く、ＣＭＰまたは
ＣＭＰＯが溶出しにくい樹脂を使用する。例えば、Ａｍ
ｂｅｒｌｉｔｅ ＸＡＤ−４（商品名；非極性のポリス
チレン−ＤＶＢ樹脂、巨大網状構造）が好適である。こ
のような固体支持体にＣＭＰまたはＣＭ Ｐ Ｏ（抽出
剤）を含浸させて構成する吸着剤は、まず前記樹脂をア
セトンで洗浄して不純物を除去し、これを減圧乾燥した
ものに抽出剤を含浸させて調製する。含浸時間は数時間
で充分である。Further, for the solid support impregnated with CMP or CMPO, a resin is used that has a large amount of CMP or CMPO impregnated and that CMP or CMPO is difficult to elute. For example, Am
berlite XAD-4 (trade name; non-polar polystyrene-DVB resin, giant network structure) is preferred. An adsorbent made by impregnating such a solid support with CMP or CMPO (extractant) is first washed with acetone to remove impurities, and then dried under reduced pressure, followed by adding the extractant. Prepare by impregnating. A few hours is sufficient for the impregnation time.
前記のようにして支持体に含浸された抽出剤は前記支持
体のカラムに通水することにより、その溶解度（〜５０
０ｐｐｍ）に応じて溶出されていく。調製した吸着カラ
ムに蒸留水を通すと、通水初期に多量の抽出剤が流出し
、その後は一定濃度（４２０ｐｐｍ）での溶出となる。The extractant impregnated into the support as described above is passed through a column of the support to improve its solubility (~50
0 ppm). When distilled water is passed through the prepared adsorption column, a large amount of extractant flows out at the beginning of the water flow, and thereafter elutes at a constant concentration (420 ppm).
一定濃度での溶出は抽出剤の水に対する溶解度によるも
のであるが、初期の多量の流出は抽出剤の含浸工程で余
剰抽出剤として除去しきれないものが流出したことによ
るものである。したがって、抽出液をカラムから抜いた
後、カラムをカラムボリュームの１０倍程度で洗浄し、
この洗浄液を抽出剤を含浸していないＡｍｂｅｒｌｉｔ
ｅＸＡＤ−４のカラムに通して、抽出剤を吸着回収する
。Elution at a constant concentration is due to the solubility of the extractant in water, but the initial large amount of outflow is due to the outflow of excess extractant that could not be removed during the extractant impregnation process. Therefore, after removing the extract from the column, wash the column with approximately 10 times the column volume.
Amberlit, which is not impregnated with an extractant, is used as the cleaning solution.
The extractant is adsorbed and collected through an eXAD-4 column.
このように抽出剤を固体支持体に含浸させるので、抽出
剤の溶解度に見合うだけの少量しか流失しないので、高
価な抽出剤を使用してもコスト高になるのを抑えること
ができる。Since the solid support is impregnated with the extractant in this way, only a small amount commensurate with the solubility of the extractant is washed away, so even if an expensive extractant is used, the cost increase can be suppressed.
このようにして調製した吸着剤を塔内に充填してカラム
を形成し、このカラム中にＵ、Ｐｕ除去後のＴＲＵを含
む放射性廃液を通過させれば、液中の′Ｉ″Ｉｔ Ｕを
カラムに吸着さ仕ることができ、これによって容易にＴ
ＲＵの除去を行なうことができる。カラムに吸着させた
ＴＲＵは希酸溶液の洗浄により容易に溶離することがで
き、ＴＲＵ廃液を分離、回収することができる。If the adsorbent prepared in this way is packed into a column to form a column, and a radioactive waste liquid containing U and TRU after removing Pu is passed through this column, 'I'' It U in the liquid can be removed. It can be adsorbed onto the column, which makes T
RU removal can be performed. The TRU adsorbed on the column can be easily eluted by washing with a dilute acid solution, and the TRU waste liquid can be separated and recovered.
以下、この発明を実施例によりさらに詳しく説明する。Hereinafter, this invention will be explained in more detail with reference to Examples.
「実施例」
第１図に本発明方法を実施するに好適な装置の概略構成
図を示す。"Example" FIG. 1 shows a schematic diagram of an apparatus suitable for carrying out the method of the present invention.
周知のように、放射性廃液は、多量のアメリンラム；Ａ
ｍを含んでいる。この放射性廃液は、通常、前記Ａｍの
他にＵ（Ｖｌ）、Ｐｕ（ＩＶ）を含んでおり、これらの
濃度が高い場合にはＡｌ１１の吸着容量に影響を及ばず
ことが考えられる。そこで、まず、図に示すように、一
旦、廃液供給槽１に貯えた廃液をポンプ２により濃硝酸
溶液とともに陰イオン交換樹脂塔３に流して、Ｕ、Ｐｕ
元素を除去する。除去したＵ、Ｐｕ成分は希硝酸溶液に
よる逆洗により塔３内のイオン交換樹脂から溶離し、Ｕ
−Ｐｕ貯留槽４に貯えて適宜リサイクルする。As is well known, radioactive waste liquid contains a large amount of amerine rum;
Contains m. This radioactive waste liquid usually contains U (Vl) and Pu (IV) in addition to the above-mentioned Am, and when the concentrations of these are high, it is considered that they do not affect the adsorption capacity of Al11. Therefore, first, as shown in the figure, the waste liquid once stored in the waste liquid supply tank 1 is sent to the anion exchange resin column 3 together with the concentrated nitric acid solution by the pump 2, and the U, Pu,
Remove elements. The removed U and Pu components are eluted from the ion exchange resin in column 3 by backwashing with dilute nitric acid solution, and the U and Pu components are eluted from the ion exchange resin in column 3.
- Store in the Pu storage tank 4 and recycle as appropriate.
Ｕ、Ｐｕ除去後の流出液（Ａｍ廃液）は、廃液貯留槽５
に一時貯留し、この貯留槽５からポンプ６により抽出部
７に供給する。抽出部７は、ｌバッチあたりの廃液処理
量を増すために７ａ（７ａ）、７ｂの２段とし、前段の
塔７ａ、７ａにはＣＭＰ含浸イオン交換樹脂またはＣＭ
ＰＯ含浸イオン交換樹脂を充填し、後段の塔７ｂに溶出
した抽出剤を回収・保持するためのバックアップカラム
を設ける。このバックアップカラムにより前段の塔７ａ
、７ａから溶出した抽出剤を吸着し、抽出剤の溶出によ
るコストの損失を大きく低減化することができる。The effluent after removing U and Pu (Am waste liquid) is transferred to the waste liquid storage tank 5.
It is temporarily stored in the storage tank 5 and supplied to the extraction section 7 by a pump 6. The extraction section 7 has two stages, 7a (7a) and 7b, in order to increase the amount of waste liquid treated per 1 batch, and the former columns 7a, 7a are equipped with CMP-impregnated ion exchange resin or CM
A backup column filled with PO-impregnated ion exchange resin and for collecting and retaining the extractant eluted into the latter column 7b is provided. With this backup column, the former column 7a
, 7a can be adsorbed, and the cost loss due to elution of the extractant can be greatly reduced.
前記抽出部７からのＡｍが分離除去された流出液は、一
旦ＦＰ廃液貯留槽８へ送り、たとえば、硝酸ナトリウム
に対する処理を施して、暫定固化処理を行なうことがで
きる。The effluent from the extraction section 7 from which Am has been separated and removed can be temporarily sent to the FP waste liquid storage tank 8 and subjected to a treatment with sodium nitrate, for example, to perform a temporary solidification treatment.
一方、抽出塔７ａ、？ａ内のカラムに吸着されているＡ
ｍ等のＴＲＵは希硝酸溶液による順先により溶離し、こ
のＡｍを含む廃液は、一時廃液貯留槽９に貯え、ガラス
固化処理を行ない処分するか、あるいは必要な場合には
、シュウ酸沈澱法等によりＡｍを回収することが可能で
ある。On the other hand, extraction tower 7a, ? A adsorbed on the column in a
TRUs such as m are eluted by dilute nitric acid solution, and this waste liquid containing Am is temporarily stored in the waste liquid storage tank 9 and disposed of by vitrification treatment, or if necessary, oxalic acid precipitation method. It is possible to recover Am by etc.
次に、この発明方法の効果を定量的に確認するために行
なった実験例を示す。この実験例では抽出剤としてＣＭ
Ｐを用いた。Next, an example of an experiment conducted to quantitatively confirm the effect of the method of this invention will be shown. In this experimental example, CM was used as the extractant.
P was used.
「実験例」
（ｉ） 吸着剤の調製
ｃ Ｍ ｐの含浸支持体には、ＣＭＰの含浸量が多く、
ＣＭＰが溶出しにくいとされるＡｍｂｅｒｌｉｔｅ Ｘ
ＡＤ−４（商品名；非極性のポリスチレン−ＤＶＢ樹脂
、巨大網状構造）を用いた。吸着剤は、樹脂をアセトン
で洗浄して不純物を除去し、これを減圧乾燥したしのに
ＣＭＰを含浸させて調製した。"Experimental example" (i) Preparation of adsorbent The impregnated support of cMp has a large amount of CMP impregnated,
Amberlite X, which is said to be difficult for CMP to elute
AD-4 (trade name; non-polar polystyrene-DVB resin, giant network structure) was used. The adsorbent was prepared by washing the resin with acetone to remove impurities, drying it under reduced pressure, and impregnating it with CMP.
（１１）放射性廃液
この実験例では実際の放射性廃液のかイつりにランタノ
イド（Ｃｅ、 Ｎｄ、 Ｅｕ）を用いた模擬廃液により
ＯＭＰ含浸支持体カラムの廃液中からの’Ｉ” ＲＵ分
離・回収特性を評価した。使用した模擬廃液の組成を表
１に示す。他元素との分離性を評価するために■価金属
の代表としてＰｅを、１価金属の代表としてＳｒを添加
した。(11) Radioactive waste liquid In this experimental example, we used a simulated waste liquid using lanthanoids (Ce, Nd, Eu) to recover the actual radioactive waste liquid, and evaluated the characteristics of 'I' RU separation and recovery from the waste liquid of an OMP impregnated support column. The composition of the simulated waste liquid used is shown in Table 1. In order to evaluate the separability from other elements, Pe was added as a representative of valent metals, and Sr was added as a representative of monovalent metals.
（以下、余白）
［表］
（ｉｉｉ） 模擬廃液を用いた分離・回収特性第２図
はこの実験例に用いた装置を示すらのである。図中符号
ＩＯは前記模擬廃液を入れたビー力を示すもので、この
ビー力１０内の廃液は定量ポンプ１１によって第１段目
の抽出カラム１２、第２段目のバックアップカラム１３
中に順次に供給され、カラムからの流出液はサンプル容
器１４中に滴下されるようになっている。前記抽出カラ
ム１２内には前記した吸着剤が充填されており、バック
アップカラム１３内にはＡｍｂｅｒｌｉＬｅ ＸＡＤ−
４が充填されている。(Hereinafter, blank spaces) [Table] (iii) Separation and recovery characteristics using simulated waste liquid Figure 2 shows the apparatus used in this experimental example. The symbol IO in the figure indicates the bee force in which the simulated waste liquid was added.
The effluent from the column is dripped into the sample container 14. The extraction column 12 is filled with the adsorbent described above, and the backup column 13 is filled with AmberliLe XAD-
4 is filled.
模擬廃液や溶離液（希硝酸溶液）は、定量ポンプ１１を
用いてカラム１２−１３に供給し、流出液、溶離液はカ
ラムボリューム単位でフラクションをとった。各フラク
ションからサンプリングし、ランタノイド（Ｃｅ）につ
いては高周波プラズマ発光分析で、Ｆｅ、Ｓｒについて
は原子吸光度分析で、それぞれ流出液中の濃度を分析し
た。The simulated waste liquid and eluent (dilute nitric acid solution) were supplied to columns 12-13 using a metering pump 11, and the effluent and eluate were fractionated in column volume units. Each fraction was sampled, and the concentrations in the effluent were analyzed using high-frequency plasma emission spectrometry for lanthanoids (Ce) and atomic absorption spectrometry for Fe and Sr.
分析の結果得られた流出液のブレークスルーカーブを第
３図に示す。図に見られるように、６×（カラムボリュ
ームの６倍）までの模擬液に対して良好な分離か得られ
ている。なお、ブレークスルーのしきい値は、流速の調
整、吸着カラムの多段化により大きくすることが可能で
ある。The breakthrough curve of the effluent obtained as a result of the analysis is shown in FIG. As seen in the figure, good separation was obtained for simulated liquids up to 6x (6 times the column volume). Note that the breakthrough threshold can be increased by adjusting the flow rate and increasing the number of adsorption columns.
また、第４図に希硝酸溶液を用いた吸着カラムの溶離曲
線を示す。図に見るように、ｔＯＸまでにほぼ全量のセ
リウムが溶出される。Further, FIG. 4 shows an elution curve of an adsorption column using a dilute nitric acid solution. As shown in the figure, almost all of the cerium is eluted by tOX.
「発明の効果」
以上説明したように、この発明に係る放射性廃液の処理
方法によれば、’ｒ ＲＵを含む放射性廃液からＴＲＵ
を容易かつ経済的に分離除去し、長期にわたる管理を要
する廃液固化体を大幅に低減することかでき、放射性廃
棄物（ガラス固化物）の貯蔵管理コストの低減に大きく
寄与することができる。"Effects of the Invention" As explained above, according to the radioactive waste liquid treatment method according to the present invention, TRU is removed from radioactive waste liquid containing 'rRU.
can be easily and economically separated and removed, and the amount of solidified waste liquid that requires long-term management can be significantly reduced, making it possible to greatly contribute to reducing the cost of storage and management of radioactive waste (vitrified waste).
第１図はこの発明方法に用いて好適な装置の一例を示す
もので、同装置の概略構成図で、第２図ないし第４図は
本発明方法の実験例を説明するためのらので、第２図は
用いた装置の概略構成図、第３図は分析の結果得られた
流出液のブレークスルーカーブ、第４図は希硝酸溶液を
用いた吸着カラムの溶離曲線、第５図は本発明方法に用
いるＣＭＰおよびＣＭ Ｉ：）０のよる硝酸溶液からの
Ａｍの抽出分離性能を示す曲線である。
！・・・・・・廃液供給槽、
２．６・・・・・・ポンプ、
３・・・・・・陰イオン交換樹脂塔、
４・・・・・・Ｕ−Ｐｕ貯留槽、
５・・・・・・廃液貯留槽、
７・・・・・・抽出部、
７ａ・・・・・・抽出塔、
７ｂ・・・・・・バックアップカラム、８・・・・・・
ＦＰ廃液貯留槽、
９・・・・・・廃液貯留槽、
ｌＯ・・・・・・ビー力、
１１・・・・・・定量ポンプ、
１２・・・・・・抽出カラム、
１３・・・・・・バックアップカラム、１４・・・・・
・サンプル容器。
カフムボリー−ム
１７八ｘ ｌ ｔFIG. 1 shows an example of a device suitable for use in the method of the present invention, and is a schematic diagram of the device, and FIGS. 2 to 4 are for explaining experimental examples of the method of the present invention. Figure 2 is a schematic diagram of the equipment used, Figure 3 is the breakthrough curve of the effluent obtained as a result of analysis, Figure 4 is the elution curve of the adsorption column using dilute nitric acid solution, and Figure 5 is the book. 1 is a curve showing the extraction and separation performance of Am from a nitric acid solution by CMP and CM I:)0 used in the invention method. ! ...... Waste liquid supply tank, 2.6 ... Pump, 3 ... Anion exchange resin tower, 4 ... U-Pu storage tank, 5 ... ... Waste liquid storage tank, 7 ... Extraction section, 7a ... Extraction tower, 7b ... Backup column, 8 ...
FP waste liquid storage tank, 9... Waste liquid storage tank, 1O... Bee force, 11... Metering pump, 12... Extraction column, 13... ...Backup column, 14...
・Sample container. Kahum volume 178 x l t
Claims (1)
Ｕ、Ｐｕ除去後の超ウラン元素を含む放射性廃液をＣＭ
Ｐ（ｃａｒｂａｍｏｙｌ ｍｅｔｈｙｌｅｎｅ ｐｈｏ
ｓｐｈ−ｏｎａｔｅ）またはＣＭＰＯ（ｃａｒｂａｍｏ
ｙｌ ｍｅｔｈｙｌｅｎｅ ｐｈ−ｏｓｐｈｉｎｅ ｏ
ｘｉｄｅ）を含浸させた固体支持体中を通過させること
によりこの固体支持体に超ウラン元素を吸着させて前記
廃液から超ウラン元素を除去するとともに、前記固体支
持体に吸着した超ウラン元素を溶離して回収することを
特徴とする放射性廃液の処理方法。Separate and remove U and Pu from radioactive waste liquid with high acid concentration,
CM radioactive waste liquid containing transuranic elements after U and Pu removal
P (carbamoyl methylene pho
sph-onate) or CMPO (carbamo
yl methylene ph-osphine o
xide) is passed through a solid support impregnated with the solid support to adsorb the transuranic element to the solid support, thereby removing the transuranic element from the waste liquid, and eluting the transuranic element adsorbed on the solid support. 1. A method for treating radioactive waste liquid, which comprises recovering the radioactive waste liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4119187A JPH0797155B2 (en) | 1987-02-24 | 1987-02-24 | Treatment method of radioactive waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4119187A JPH0797155B2 (en) | 1987-02-24 | 1987-02-24 | Treatment method of radioactive waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63208798A true JPS63208798A (en) | 1988-08-30 |
| JPH0797155B2 JPH0797155B2 (en) | 1995-10-18 |
Family
ID=12601531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4119187A Expired - Fee Related JPH0797155B2 (en) | 1987-02-24 | 1987-02-24 | Treatment method of radioactive waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0797155B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008304280A (en) * | 2007-06-06 | 2008-12-18 | Hitachi-Ge Nuclear Energy Ltd | Actinoid adsorption material and method for treating radioactive waste liquid |
| JP2014126544A (en) * | 2012-12-27 | 2014-07-07 | Kobelco Eco-Solutions Co Ltd | Exchange method for adsorption towers for radioactive cesium containing water |
-
1987
- 1987-02-24 JP JP4119187A patent/JPH0797155B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008304280A (en) * | 2007-06-06 | 2008-12-18 | Hitachi-Ge Nuclear Energy Ltd | Actinoid adsorption material and method for treating radioactive waste liquid |
| JP2014126544A (en) * | 2012-12-27 | 2014-07-07 | Kobelco Eco-Solutions Co Ltd | Exchange method for adsorption towers for radioactive cesium containing water |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0797155B2 (en) | 1995-10-18 |
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