JPH01285899A - Quantity measuring method of deteriorating constituent in deterioration solvent - Google Patents
Quantity measuring method of deteriorating constituent in deterioration solventInfo
- Publication number
- JPH01285899A JPH01285899A JP63113535A JP11353588A JPH01285899A JP H01285899 A JPH01285899 A JP H01285899A JP 63113535 A JP63113535 A JP 63113535A JP 11353588 A JP11353588 A JP 11353588A JP H01285899 A JPH01285899 A JP H01285899A
- Authority
- JP
- Japan
- Prior art keywords
- degraded
- solvent
- solution
- standard solution
- mbp
- 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.)
- Pending
Links
- 239000002904 solvent Substances 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 19
- 230000002542 deteriorative effect Effects 0.000 title abstract description 7
- 230000006866 deterioration Effects 0.000 title description 5
- 239000000470 constituent Substances 0.000 title 1
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract 6
- 238000004255 ion exchange chromatography Methods 0.000 claims abstract 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract 2
- 239000003480 eluent Substances 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- 238000012958 reprocessing Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000003758 nuclear fuel Substances 0.000 claims description 2
- 239000012086 standard solution Substances 0.000 abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- 238000004458 analytical method Methods 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000010828 elution Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 abstract description 3
- 238000004445 quantitative analysis Methods 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 abstract 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 abstract 1
- 238000005259 measurement Methods 0.000 abstract 1
- 150000007524 organic acids Chemical class 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 13
- 238000001514 detection method Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- -1 sodium helium hydroxide Chemical compound 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000257465 Echinoidea Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 2
- NZCFITBCFLGDFN-JEDGRRCBSA-N (2S)-2-[[(2S)-2-[[(2S)-2-[[(2S)-2-[[(2S)-2-[[(2S)-5-amino-2-[[(2S)-2-[[(2S)-2,6-diaminohexanoyl]amino]propanoyl]amino]-5-oxopentanoyl]amino]-4-methylpentanoyl]amino]-5-(diaminomethylideneamino)pentanoyl]amino]-5-(diaminomethylideneamino)pentanoyl]amino]-4-methylpentanoyl]amino]-3-hydroxypropanoic acid Chemical compound C[C@@H](C(=O)N[C@@H](CCC(=O)N)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CO)C(=O)O)NC(=O)[C@H](CCCCN)N NZCFITBCFLGDFN-JEDGRRCBSA-N 0.000 description 1
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- WYKYKTKDBLFHCY-UHFFFAOYSA-N chloridazon Chemical compound O=C1C(Cl)=C(N)C=NN1C1=CC=CC=C1 WYKYKTKDBLFHCY-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- UTLZBWAGLRNNAY-UHFFFAOYSA-J thorium(4+);dicarbonate Chemical compound [Th+4].[O-]C([O-])=O.[O-]C([O-])=O UTLZBWAGLRNNAY-UHFFFAOYSA-J 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
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的」
（産業上の利用分野）
本梵明は、核燃利再望理工程で使用（）で劣化した溶媒
中のトリブチルリン酸（以下Ｔ Ｂ Ｐと記す）劣化成
分を定量する方法に関する。[Detailed Description of the Invention] [Objective of the Invention] (Industrial Application Field) The present invention relates to the use of tributyl phosphoric acid (hereinafter referred to as T B P) in a solvent that has been degraded during use in the nuclear refueling process. This invention relates to a method for quantifying degraded components.
（従来の技術）
原子力発電用燃料のウランやプル１〜ニウムの再処理プ
ロセスには、ビューレックス法とよばれる金属イオンの
溶媒抽出・精製方法が導入されている。この方法は使用
済燃料を硝酸で分解し、この分解液からウランまたはプ
ル１ヘニウムを有機溶媒で抽出するものである。この抽
出溶媒には〜Ｉ−Ｂ Ｐと希釈用ドデカンの混合溶媒を
使用するが、−１−ＢＰは硝酸や放射性金属と接触する
と分解して、抽出効果を低下させるジブデルリン酸（Ｄ
ＢＰ）。(Prior Art) A metal ion solvent extraction and purification method called the Burex method has been introduced into the reprocessing process of uranium and plu-1 to nium as fuel for nuclear power generation. In this method, spent fuel is decomposed with nitric acid, and uranium or pluhenium is extracted from the decomposed liquid using an organic solvent. A mixed solvent of ~IBP and dodecane for dilution is used as the extraction solvent, but -1-BP is mixed with dibderphosphate (D), which decomposes when it comes into contact with nitric acid or radioactive metals, reducing the extraction effect
BP).
モツプデルリン酸（ＭＢＰ）、リン酸、ブチルアルコー
ル等を生成し、いわゆる劣化溶媒となる。It produces mozupdel phosphoric acid (MBP), phosphoric acid, butyl alcohol, etc., and becomes a so-called degraded solvent.
この劣化溶媒の劣化の程度は上記各劣化成分を定量する
ことに」；って知ることかできる１、この定量法として
従来知られているのは、劣化溶媒をアルカリ性水溶液で
抽出処理し−で溶媒中の劣化物を水相側に移行させ、こ
れを定量分析する方法であり、この定量分析法として、
例えば、水相中の劣化各成分をリンモリブデン酸により
発色させて吸光！■測測定る方法や、水相中の劣化物を
イオンク［１ζ７１〜グラフイーにか（すて定量分析す
る方法などかある３゜
を記のイＡンク［１ン１〜グラフイーによる分析の場合
、溶離液としては炭酸すトリウムと炭酸水素−）−１〜
１戸ンムの混合液が使用されているが、このブ）Ｗ＜−
＜Ｊは劣化成分であるＤＢＰ、ＭＢＰ、リン酸等がぞれ
ぞ゛れ別々に定量分析に付されるの（”、時間と手間か
かかる上、分析精度も充分ではない。特に、リン酸の分
析ではピークが出るのに時間がかかかり、そのため試料
中の不純物である硝酸に干渉されて分析か実質−ト困難
であるという問題かある、。The degree of deterioration of this degraded solvent can be determined by quantifying each of the above-mentioned degraded components1.The conventional method for this quantitative determination is to extract the degraded solvent with an alkaline aqueous solution. This is a method of quantitatively analyzing degraded substances in the solvent by transferring them to the aqueous phase side.As this quantitative analysis method,
For example, each degraded component in the aqueous phase is colored with phosphomolybdic acid and absorbed! ■Is there a method to measure or quantitatively analyze degraded substances in the aqueous phase using an ion probe [1ζ71~Graphie?] As the eluent, thorium carbonate and hydrogen carbonate-)-1~
A mixed solution of 1 mm is used, but this B)W<-
<J is the deterioration components DBP, MBP, phosphoric acid, etc., which are each subjected to quantitative analysis separately (", it takes time and effort, and the analysis precision is not sufficient. In particular, phosphoric acid In this analysis, it takes a long time for a peak to appear, and the problem is that nitric acid, an impurity in the sample, interferes with the analysis, making analysis difficult.
（発明か解決しようとする課題）
本発明（よ上記情況に鑑みてなされたもので、上記劣化
溶媒中の王Ｂ Ｐ劣化各成分を同時に短時間で、かつ１
６度よく定接リ−ることを目的と１−るものである１、
［発明の構成１
（課題を解決するための手段）
上記目的はイオンク［１７１〜グラフイーの溶離液を改
良しかつ分析に供される試１′４のアルカリ濃度を調整
（〕て最最適量を見出したことによって達成された。(Problems to be Solved by the Invention) The present invention has been made in view of the above-mentioned circumstances, and is capable of simultaneously treating each of the BP deteriorating components in the deteriorating solvent in a short period of time, and
The purpose of the invention is to improve the eluent of Ionque [171~graphie] and analyze it. This was achieved by adjusting the alkali concentration of Test 1'4 to find the optimum amount.
すく【わら、本発明は、核燃料再処理玉押−Ｃ使用して
劣化した硝酸、１〜リブデルリン酸４３よび炭化水素系
希釈剤を主成分と１−る溶媒をアルカリ性水溶液で処理
して前記溶媒中のｌ、 １ノ１チル１ノン酸劣化物を水
相に移行させ、この水相中の１−記劣化物成分をイオン
クロマ１へグラノィーにより定量する劣化溶媒中の劣化
成分の定量方法において、イΔンク［−１７１〜グラフ
イーに供する試料水溶液のアルカリ濃度を２０ｍＭ以下
とし、かつイオンク［１７１〜グラフイーの溶離液とし
て炭酸）−１ヘリウムと炭酸水素す１〜リウムを含有す
る［１ｌＨ１０，４５へ、１１．０の範囲の液を使用寸
−ることを特徴とする溶媒中劣化成分の定量方法に関す
る。In the present invention, a solvent mainly composed of nitric acid, 1-Lybdell phosphoric acid 43 and a hydrocarbon diluent, which has been degraded by using nuclear fuel reprocessing condensation-C, is treated with an alkaline aqueous solution to obtain the solvent. In a method for quantifying degraded components in a degraded solvent, in which the 1-1-thyl 1-non acid degraded product is transferred to an aqueous phase, and the 1-1 degraded product component in this aqueous phase is quantified by Granoy to Ion Chroma 1. , Ink [-171 ~ The alkali concentration of the sample aqueous solution to be subjected to Graphie is 20 mM or less, and Ionk [171 ~ Carbonic acid as an eluent for Graphie] -1 Helium and hydrogen carbonate 1 to 1 Lithium [1lH10,45 The present invention relates to a method for quantifying degraded components in a solvent, characterized in that a liquid having a working size in the range of 11.0 is used.
（実施例）
本弁明の実施例を以下に説明づる。なｄ３実施例は模擬
劣化溶媒を作成し・−で行ったが、これに先専ら、濃度
既知の劣化成分溶液を用いて溶離液および試料液の条件
を検討した実験を示す。(Example) An example of the present defense will be described below. In Example d3, a simulated degraded solvent was prepared and carried out in -. However, an experiment in which the conditions of the eluent and sample solution were examined exclusively using a degraded component solution with a known concentration will be shown.
■−ｒ−１３ Ｐ劣化物各成分の標準溶液の調製Ｄ Ｂ
Ｐ特級試薬（ＤＢＰ９５％）、ＭＢＰ試桑（ＭＢＰ７
３％、ＤＢＰ２２％、リン酸５％）を、各々０．１Ｍ水
酸化す１ヘリウム（以下Ｎａ０Ｈ）水溶液で希釈して超
音波洗浄器で攪拌し、１０００ ｐｐｍのＤＢ［）標準
溶液、Ｍ Ｂ Ｐ標準溶液を調製する。さらに各標準液
を純水または１０ｎ＋ＭのＮａ０１１水溶液で希釈して
１暗波洗浄器で攪拌） 、２〜２００ｐｐｍのＩＣ（イ
寸ンク■マドグラフィー）分析用ＤＢＰおよびＭＢＰ各
標準標準溶液媒： １０ｍＭ ＮａＯＨ）を調製覆る。■-r-13 Preparation of standard solutions of each component of P-degraded product D B
P special grade reagent (DBP95%), MBP reagent (MBP7
3% DBP, 22% DBP, 5% phosphoric acid) were each diluted with 0.1M sodium helium hydroxide (hereinafter referred to as NaOH) aqueous solution and stirred in an ultrasonic cleaner to prepare 1000 ppm DB[) standard solution, M B Prepare P standard solution. Furthermore, each standard solution was diluted with pure water or 10n+M Na011 aqueous solution and stirred in a dark wave washer), 2-200ppm IC (Isunku Madography) analysis DBP and MBP standard standard solution medium: 10mM Prepare NaOH) and cover.
ここてＭ Ｂ Ｐ標準溶液の正確なＭ Ｂ Ｐ濃度は［
Ｍ Ｂ ｆ−）溌１ｆ ｌ ＝ ｆ標準液８磨］ Ｘｏ
、７：Ｗ）Ｉテある。１ノンＭ標準溶液は、リン酸三す
１〜リウム（以下Ｎａ ３ ＰＯ４）特級試薬をリン酸
イオンで４〜２（１（ｌ ｐｐｍになるＪ、う１０ｎ＋
ＨのＮａ１ｌ水溶液に溶かして調製する、。Here, the exact MBP concentration of the MBP standard solution is [
M B f-) 溌1fl = f standard solution 8 polish] Xo
, 7:W) I have it. The 1-Non M standard solution is made by adding trisium phosphate (hereinafter referred to as Na 3 PO 4 ) special grade reagent to 4 to 2 (1 (l ppm) J, 10 n+
Prepared by dissolving H in Na1 aqueous solution.
（ζ Ｉ（、、＋、Ｚ、Ｊφ炙化−聞分逝四の最適ｉＷ
ｌ液組成の−５〜
抜足
次にＩＣの分離カラムを、一般陰イオン・有機酸イオン
分析仕様とし、溶離液組成は炭酸すｉ〜リウム（Ｎａ２
ＣＯ３） ト、１ｍ Ｗ水Ｍ ｆ Ｉ〜’） ラム（Ｎ
ａＨＣＯ３）またはＮａ０１１を、温度と混合比を変化
させて設定する。(ζ I(, , +, Z, Jφ roasted − monbunjoshi's optimal iW
Next, the IC separation column was set to general anion/organic acid ion analysis specifications, and the eluent composition was -5 to 20% of the liquid composition.
CO3) g, 1 m W water M f I~') Ram (N
aHCO3) or Na011 by changing the temperature and mixing ratio.
これら種々の溶離液組成で、はじめに１６０ ＤＩ）ｍ
ＭＢＰ標準溶液をＩＣで分析し、次に４０ ｐｐｍ１つ
ＢＰ標準溶液と６０ ｐｐｍリン酸標準溶液の順に分析
して、それぞれのピークの検出時間とピーク高さを求め
、それぞれを比較して最適な溶離液組成を求めた。なお
、この分析には旧ｏｎｅｘ社製のＩＣ−４０００ｉを使
用した。ここで分離カラムは陰イオン用１１ＰＩｃ−Ａ
ｓ−１を、除去カラムは中空膜状のフフイバーサブレッ
リ−−を使用し、検出方法は電気電導率によった。結束
を第１図に示す。With these various eluent compositions, initially 160 DI) m
Analyze the MBP standard solution with IC, then analyze one 40 ppm BP standard solution and 60 ppm phosphoric acid standard solution in that order to find the detection time and peak height of each peak, compare each and find the optimal one. The eluent composition was determined. Note that IC-4000i manufactured by the former Onex Corporation was used for this analysis. Here, the separation column is 11PIc-A for anions.
In s-1, a hollow membrane-like fiber sabrelli was used as the removal column, and the detection method was based on electrical conductivity. The binding is shown in Figure 1.
これによると、ＤＢＩ）、ＭＢＰ、リン酸が最短時間で
検出され、ピーク検出高さ（すなわら感度）が良好な組
成は、Ｎｏ、 ９の［Ｎａ２ Ｃ０３７４ｍＭ＋Ｎａｔ
ｌＣＯ３１、５…Ｈ１であることがわかった。According to this, the composition that allows DBI), MBP, and phosphoric acid to be detected in the shortest time and has a good peak detection height (i.e., sensitivity) is No. 9 [Na2C0374mM+Nat
It turned out to be lCO31,5...H1.
−〇 −
検出時間４Ｊ１、ｉｆｆ ｔｔＳＩｔ液の１）１」とイ
オン強１宴、目的イΔンの分離カラム内の陰−ｒオン交
換樹脂に対する親１１カどの相関関係で決まってくる。-〇- It is determined by the correlation between the detection time 4J1, the 1)1'' of the if ttSIt solution, the ionic strength 1, and the parent 11 of the target ion against the anion-r ion exchange resin in the separation column.
ＮＯ９の場合ｐ Ｌ−１＜ｒ口０．４５ ”Ｃ゛あった
。また、ＤＢＰについて感度か良好なＮｏ、 ３へ−９
，１１の場合の旧旧よ１０．４５＝−１１、０の範囲に
あった。In the case of No. 9, p L-1 < r mouth 0.45 "C". Also, for No. 3, which has good sensitivity for DBP, -9
, 11, the old and old cases were in the range of 10.45=-11,0.
−１記〜０５）の）容離液を用いてｔｌＮＯｘ＋ ０．
０５Ｍの劣化物水浴液を分析し、１ｌＮＯ３の干渉がこ
の溶離液によるｉ Ｃ８（斤にとのＪ、うに影響するか
調べｌこ。このＩ ＣＵ−） ｆ（＝−ｔ”を第２図に
不眠、この図かられかるように、従来（ｉｌ′１Ｍに干
渉され−（出なかったリン酸イ、インのピークかこの実
験では明瞭に認められる６゜
次に、■Ｃ調製り、た各標準溶液を分析して、検量線を
作成りると共に、検出限界値と繰り返し分析（、二おＶ
Ｊる精度を調べてみた。その結果、第３図に７Ｊｋず番
犬化成分の検量線か得られた。tlNOx+0.
Analyze the degraded product water bath solution of 05M and investigate whether the interference of 1lNO3 affects the iC8 (J, sea urchin) caused by this eluent. As can be seen from this figure, the peaks of phosphoric acid and in, which did not appear due to interference with IL'1M, were clearly observed in this experiment. Analyze each standard solution and create a calibration curve, as well as determine the detection limit value and repeat analysis (2
I investigated the accuracy of J. As a result, a calibration curve for the 7Jk Zundog component was obtained as shown in FIG.
この検量線は、同−標ＱＬ ？Ｈ液の２へ一３回の繰り
返し５′Ｉ）＋、１１における平均値をｉｍ度に対して
ブ１］ツ１〜Ｌ、、 ／、−らの−Ｃある１３検出限界
値【よ、Ｄ Ｂ Ｐの場合溶約２ｐｐｍから１５０ｐｐ
ｍ程度、ＭＢＰではベースラインのドリフＩ〜に影響さ
れ２〜３ｐｐｍから２００ｐｐｍ、リン酸は検出時間が
遅くなだらかなピークとなるために低濃縮域では検出さ
れにくいという理由から、３ｐｐｍから２５０ｐｐｍ前
後までが確認された。また分析値の再現性は高濃度域は
ど高く、４０〜２００ｐｐｍまでの誤差範囲が１〜５％
である。This calibration curve is based on the same standard QL? Repeat 13 times for 2 to 5'I) +, 11 of H solution to the im degree, and calculate the -C detection limit value of -C for im degrees. In the case of D B P, melting range is from 2 ppm to 150 ppm.
For MBP, the range is from 2 to 3 ppm to 200 ppm due to the influence of the baseline drift I, and from 3 ppm to around 250 ppm because phosphoric acid is difficult to detect in the low concentration range due to the slow detection time and a gentle peak. was confirmed. In addition, the reproducibility of analytical values is very high in the high concentration range, with an error range of 1 to 5% from 40 to 200 ppm.
It is.
次に模擬劣化溶媒を作成し、前記Ｎｏ、 ９の溶離液を
使用して抽出条件ヤ）ＩＣ分析に供する試料のアルカリ
ａ度について検討した。その実験を次に示す。Next, a simulated degraded solvent was prepared, and using the eluent No. 9, the extraction conditions and a) alkalinity of the sample to be subjected to IC analysis were examined. The experiment is shown below.
まず、ＴＢＰ３０％、ｎ−１−’デカン７０％の組成の
有機溶媒に、濃度既知量のＤＢＰ、ＭＢＰおよびリン酸
を加えた模擬劣化溶媒を作り、アルカリ水で抽出および
定量する。これを劣化物のうち一番抽出され難いＤＢＰ
についてまず行なった。First, a simulated degraded solvent is prepared by adding known concentrations of DBP, MBP, and phosphoric acid to an organic solvent having a composition of 30% TBP and 70% n-1-'decane, and is extracted and quantified with alkaline water. This is DBP, which is the most difficult to extract among degraded substances.
I did it first.
すなわち、上記有機溶媒中で１０００１’ｌｌ）ｍとな
るようにＤＢＰ特級試薬を添加して模擬劣化溶媒とし、
これを ＮａＯＨ水溶液で抽出した。Ｎａ０１１水溶液
の濃度、該水溶液とイｊ機浴媒との混合比（有機溶媒／
″アルカリ水、振盪時間の３つのパラメーターの標／％
Ｉ条件を第１表の大枠内のにうに（ＮａＯＨＯ，５１（
、体積比１．・１、」辰盛時間５分）設定じ、そのうち
１つのパラメーターを変化させた条件て゛それぞれ抽出
分離実験を１１なった３、分離後、得られた水相を純水
−（−第１表に示す゛希釈イ８率に希釈し、ＩＣ（上記
■で設定した仕様）て定量分析し・た。この希釈ｔＪ１
アルカリ水溶液の０＋＋がＤＢＰ検出ピークに干渉して
し、ようためで、実験の結果アルカリ濃度２Ｏｎ＋Ｈ以
−Ｆ、好ましくは１０ｍＨで好結果が得られた。That is, DBP special grade reagent is added to the above organic solvent to give a concentration of 10001'll)m to simulate degraded solvent,
This was extracted with an aqueous NaOH solution. The concentration of the Na011 aqueous solution, the mixing ratio of the aqueous solution and the Ij bath medium (organic solvent/
``Standards/% of three parameters: alkaline water, shaking time
I conditions were set to sea urchin (NaOHO, 51 (
, volume ratio 1.・1. Extraction and separation experiments were conducted under the conditions of 11 minutes with one parameter changed. 3. After separation, the resulting aqueous phase was mixed with pure water (Table 1). It was diluted to the dilution ratio of 8 shown in ゛Dilution I and quantitatively analyzed using IC (specifications set in ① above).This dilution tJ1
Because the 0++ of the alkaline aqueous solution interferes with the DBP detection peak, good results were obtained in experiments at an alkali concentration of 2 On+H or more, preferably 10 mH.
但し、あＪ、り希釈リ−ると劣化成分濃度も低下するの
（、検出誤差が出やすくなる。ここではすべて１０ｍｆ
（とじた。分析した結果を第１表のθＢＰ讃度の欄（３
二示す。However, if it is diluted further, the concentration of degraded components will also decrease (and detection errors will occur easily.Here, all 10mf
(I closed it. The results of the analysis are shown in the θBP praise column (3) in Table 1.
Show two.
（以下 余白）
第 １ 表
これによると、Ｎａ０ｆｌ水溶液濃度が０．１）１．該
水溶液と有機溶媒との混合比（Ｏ／Ａ比）が１／２、振
盪時間が５分のとき、ＤＢＰの検出値が最も高くなると
考えられる。(Hereinafter in the margin) Table 1 According to this, the concentration of Na0fl aqueous solution is 0.1)1. It is considered that the detected value of DBP is highest when the mixing ratio (O/A ratio) of the aqueous solution and the organic solvent is 1/2 and the shaking time is 5 minutes.
ＭＢＰおよびリン酸についても同様の条件で充分抽出さ
れていること（９５〜９９％）が確認された。It was confirmed that MBP and phosphoric acid were also sufficiently extracted under the same conditions (95 to 99%).
以上の各実験により選定した溶離液条件（Ｎｏ、 ９
）、抽出条件および試料アルカリ濃度で、下記の劣化溶
媒をＩＣ分析した。Eluent conditions selected from the above experiments (No. 9)
), the following degraded solvent was subjected to IC analysis under the extraction conditions and sample alkali concentration.
硝酸接触後にＴ線を照射して劣化させた溶媒への適用
硝ＭＭｔ牛の王１’３ｐ３０％およびｎ−ドデ゛カンフ
０％の組成のイ書幾溶媒に放射線を当ててＴ−Ｂ Ｐを
劣化さ−け、この劣化溶媒を前記条件で抽出処理し、こ
れを萌記条イ′１て分析（）た。ブｌ析（ユ、まず抽出
された水相に苅し−Ｃその含有劣化成分を定量し、次に
既λ［１濶度の劣化成分を添７Ｊ［］ した後、再び劣
化成分を定量して行なった。結果を第２表に示づ。第２
表中、添叩後の検出濃度の欄の（）内の数値は先に検出
した濃度と添加ａ度とを加算したＳ１ｎ値であり、各成
分とも実測値と大きな隔りはない。このことから、照射
劣化溶媒についても精度のよい分析かＣ′さることがわ
かる。Application to solvents degraded by irradiation with T-rays after contact with nitric acid. The degraded solvent was extracted under the conditions described above and analyzed using Moeki. First, the extracted aqueous phase was soaked with C to quantify the contained deteriorating components, and then 7J of deteriorating components were added to the extracted aqueous phase, and the deteriorating components were again quantified. The results are shown in Table 2.
In the table, the numerical value in parentheses in the column of detected concentration after additional beating is the S1n value obtained by adding the previously detected concentration and the addition a degree, and there is no large difference from the actual measured value for each component. From this, it can be seen that C' is a highly accurate analysis even for irradiation-degraded solvents.
（以下 余白）
第 ２ 表
なお、本発明において、水相中の＋１ＮＯ３ｍ！ＳＬか
０．５１４を越える場合には、ＮＯ３−イオンを選択的
に除去して劣化物の検出を妨害し・ないようイ【前処理
を施すことかで−きる。前処理としＣは、ｒｉｎ酸−イ
Ａンの特うタ試薬である二１へロン（１，４〜ジフェニ
ル−−■−ンドアニリノジヒドロ１〜リアゾール）をエ
タノールに溶解したものを加える方法等がある。次にこ
のＩｊ法を示す。(Hereinafter, blank space) Table 2 In addition, in the present invention, +1NO3m in the aqueous phase! If the SL exceeds 0.514, pretreatment can be performed to selectively remove NO3- ions and prevent them from interfering with the detection of degraded products. Pretreatment C is a method of adding a solution of 21-heron (1,4-diphenyl--■-ndanilinodihydro-1-lyazole), which is a special reagent for phosphoric acid, in ethanol. etc. Next, this Ij method will be shown.
１０ｐｐｍのニド［］ンのエタノール溶液を作り、この
１ｍｌを１１０００ｐｐの硝酸イオンを含むρトイ８以
下の水２５威に加えてよく振りまぜると、水溶液か薄い
黄色８１ｆして、その中に白い針状結晶が生じる。Make an ethanol solution of 10 ppm Nidon [], add 1 ml of this to 25 ml of water of ρ toy 8 or less containing 11,000 ppm of nitrate ions, and shake well. crystals are formed.
この結晶をガラスフィルターでン濾過し、ン戸液にＮａ
０ｆｌを加えて１）１」調製（）たものを分析すると、
ＮＯ３−イオンが７５０〜８００ｐｐｍ程度検出された
ので、二）〜ｌンによって硝酸イオンか約２００ｐｐｍ
除去されたことがわかった。同様にＮＯ３−″イオン量
が同じで１００１）［）ｍ（７） Ｄ Ｂ Ｐを含む水
に対してニトロン溶液を加え、ン）１過おＪ、びｐｌ−
１込理を施した場合も、Ｄ ［３Ｆ’ Ｇま八−１算通
りの分析値となり、ＮＯ３−イオンの除去効果ら確かめ
られた。The crystals were filtered through a glass filter, and the Na solution was added to the solution.
When 1) 1'' was prepared by adding 0fl and analyzed,
Since NO3- ions were detected at about 750 to 800 ppm, nitrate ions were detected at about 200 ppm.
Turns out it was removed. Similarly, when the amount of NO3-'' ions is the same, 1001) [) m (7) Add a nitrone solution to water containing D B P,
Even when the 1-inclusive treatment was applied, the analysis value was as calculated as D[3F'Gm8-1, and the effect of removing NO3- ions was confirmed.
なお、２Ｌ１〜Ｏンはベンセン、り［１０ボルムにも溶
（Ｊるので、これらの溶液とＮＯ３−イオンを含む水と
を接触し−Ｃ二１〜ロンを水側に移行させる方法もある
。また、二１〜［１ンと同様の効果をもつ試桑にジシク
ロへキシルフタル酸塩等がある。イ１！２にデバルタ合
金と硝酸を作用させてアンモニアを生成させても、劣化
物の定量に（よ問題ない。Note that 2L1~O is also soluble in benzene and RI [10 vol, so there is also a method of bringing these solutions into contact with water containing NO3- ions and transferring -C21~ to the water side. In addition, dicyclohexyl phthalate is a test sample that has the same effect as 21-[1. Quantitatively (no problem.
［発明の効果］
以上説明したように、本発明にＪ、れば、従来個別に定
量していたＴＢＰ劣化成分を、同時に、短時間で、かつ
精度よく定量分析することかできる。。[Effects of the Invention] As explained above, according to the present invention, TBP deterioration components, which were conventionally quantified individually, can be quantitatively analyzed simultaneously, in a short time, and with high precision. .
第１図は溶離液組成ど溶離時間との関係を示１図、第２
図は本発明の一実施例にＪ３けるＩｃｆｔ□−トを示寸
図、第３図は各劣化成分の検量線を示す図である。
（８７３３）代理人 弁理士 猪 股 祥 晃（ほか
１名）
第２図
素 農（ｐｐｍ）
第３図Figure 1 shows the relationship between eluent composition and elution time.
The figure is a dimensional diagram of Icft□-t in J3 in one embodiment of the present invention, and FIG. 3 is a diagram showing calibration curves of each deterioration component. (8733) Agent: Yoshiaki Inomata, patent attorney (and others)
1 person) Figure 2: Agriculture (ppm) Figure 3
Claims (1)
ブチルリン酸および炭化水素系希釈剤を主成分とする溶
媒をアルカリ性水溶液で処理して前記溶媒中のトリブチ
ルリン酸劣化物を水相に移行させ、この水相中の上記劣
化物成分をイオンクロマトグラフィーにより定量する劣
化溶媒中の劣化成分の定量方法において、イオンクロマ
トグラフィーに供する試料水溶液のアルカリ濃度を２０
ｍＭ以下とし、かつイオンクロマトグラフィーの溶離液
として炭酸ナトリウムと炭酸水素ナトリウムを含有する
ｐＨ１０．４５〜１１．０の範囲の液を使用することを
特徴とする劣化溶媒中の劣化成分の定量方法。(1) A solvent mainly composed of nitric acid, tributyl phosphate, and a hydrocarbon diluent that has deteriorated during the nuclear fuel reprocessing process is treated with an alkaline aqueous solution to convert the degraded tributyl phosphate in the solvent into the aqueous phase. In a method for quantifying degraded components in a degraded solvent in which the degraded components in the aqueous phase are determined by ion chromatography, the alkali concentration of the sample aqueous solution to be subjected to ion chromatography is
1. A method for quantifying degraded components in a degraded solvent, the method comprising using a solution containing sodium carbonate and sodium hydrogen carbonate and having a pH range of 10.45 to 11.0 as an eluent for ion chromatography.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63113535A JPH01285899A (en) | 1988-05-12 | 1988-05-12 | Quantity measuring method of deteriorating constituent in deterioration solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63113535A JPH01285899A (en) | 1988-05-12 | 1988-05-12 | Quantity measuring method of deteriorating constituent in deterioration solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01285899A true JPH01285899A (en) | 1989-11-16 |
Family
ID=14614786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63113535A Pending JPH01285899A (en) | 1988-05-12 | 1988-05-12 | Quantity measuring method of deteriorating constituent in deterioration solvent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01285899A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03214100A (en) * | 1990-01-18 | 1991-09-19 | Shimadzu Corp | Managing method of nuclear fuel reprocessing process |
| EP0631290A1 (en) * | 1993-06-24 | 1994-12-28 | Hitachi, Ltd. | Reprocessing plant and method of operating the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS618204A (en) * | 1984-05-14 | 1986-01-14 | サントレ−ド リミテイド | Cutting tool |
-
1988
- 1988-05-12 JP JP63113535A patent/JPH01285899A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS618204A (en) * | 1984-05-14 | 1986-01-14 | サントレ−ド リミテイド | Cutting tool |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03214100A (en) * | 1990-01-18 | 1991-09-19 | Shimadzu Corp | Managing method of nuclear fuel reprocessing process |
| EP0631290A1 (en) * | 1993-06-24 | 1994-12-28 | Hitachi, Ltd. | Reprocessing plant and method of operating the same |
| EP0817207A1 (en) * | 1993-06-24 | 1998-01-07 | Hitachi, Ltd. | Reprocessing plant and method for operating the same |
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