CN105931692A - Method for stabilizing U(IV) valence state in TBP - Google Patents
Method for stabilizing U(IV) valence state in TBP Download PDFInfo
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- CN105931692A CN105931692A CN201610244630.2A CN201610244630A CN105931692A CN 105931692 A CN105931692 A CN 105931692A CN 201610244630 A CN201610244630 A CN 201610244630A CN 105931692 A CN105931692 A CN 105931692A
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- tbp
- acetaldehyde oxime
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000000087 stabilizing effect Effects 0.000 title abstract description 7
- 238000000605 extraction Methods 0.000 claims abstract description 4
- 239000003758 nuclear fuel Substances 0.000 claims abstract description 4
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 208000035126 Facies Diseases 0.000 claims 4
- FZENGILVLUJGJX-IHWYPQMZSA-N (Z)-acetaldehyde oxime Chemical compound C\C=N/O FZENGILVLUJGJX-IHWYPQMZSA-N 0.000 abstract description 35
- 239000012074 organic phase Substances 0.000 abstract description 21
- 239000012071 phase Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000012958 reprocessing Methods 0.000 abstract description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052770 Uranium Inorganic materials 0.000 description 2
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 2
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- 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
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
- G21F9/125—Processing by absorption; by adsorption; by ion-exchange by solvent extraction
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
本发明属于核燃料后处理技术领域，公开了一种稳定TBP中U(IV)价态的方法。该方法是向TBP有机相中引入乙醛肟；或者向水相中引入乙醛肟，再通过萃取的方式将乙醛肟萃取至TBP有机相中；其中向TBP有机相中引入的乙醛肟的浓度是2～100mmol/L；向水相中引入的乙醛肟的浓度是20～1000mmol/L。该方法具有方法简单且能够使TBP中U(IV)价态稳定时间长的优点。
The invention belongs to the technical field of nuclear fuel reprocessing and discloses a method for stabilizing the valence state of U(IV) in TBP. The method is to introduce acetaldehyde oxime into the TBP organic phase; or introduce acetaldehyde oxime into the water phase, and then extract the acetaldehyde oxime into the TBP organic phase by extraction; wherein the acetaldehyde oxime introduced into the TBP organic phase The concentration of the acetaldehyde oxime is 2-100mmol/L; the concentration of the acetaldehyde oxime introduced into the water phase is 20-1000mmol/L. The method has the advantages of being simple and capable of stabilizing the valence state of U(IV) in TBP for a long time.
Description
技术领域technical field
本发明属于核燃料后处理技术领域，具体涉及一种稳定TBP中U(IV)价态的方法。The invention belongs to the technical field of nuclear fuel reprocessing, and in particular relates to a method for stabilizing the valence state of U(IV) in TBP.
背景技术Background technique
在后处理Purex流程中，通常采用U(IV)为还原剂将易被TBP萃取的Pu(IV)还原到难萃取的Pu(III)，但是U(IV)会逐渐被料液中的硝酸及亚硝酸氧化成U(VI)，其中亚硝酸的氧化作用尤其明显，这主要是由于亚硝酸可自催化加速U(IV)的氧化。U(IV)被氧化成U(VI)会造成U(IV)试剂使用量的增加，同时U(IV)使用量的增加也会降低钚中除铀的效果。为了解决这一问题，传统的做法是采用肼作为支持还原剂清除亚硝酸，以稳定U(IV)价态，却存在以下问题：U(IV)可部分萃取到TBP中，而亚硝酸较U(IV)易萃取到TBP中，但肼难以被TBP萃取，因此肼作为支持还原剂时只能稳定水相中的U(IV)价态，有机相中的U(IV)容易被萃取到TBP中的亚硝酸氧化。In the post-treatment Purex process, U(IV) is usually used as a reducing agent to reduce Pu(IV) which is easy to be extracted by TBP to Pu(III) which is difficult to extract, but U(IV) will be gradually absorbed by nitric acid and Nitrous acid is oxidized to U(VI), and the oxidation of nitrous acid is particularly obvious, which is mainly due to the fact that nitrous acid can accelerate the oxidation of U(IV) by autocatalysis. The oxidation of U(IV) to U(VI) will increase the usage of U(IV) reagent, and the increase of U(IV) usage will also reduce the effect of removing uranium from plutonium. In order to solve this problem, the traditional method is to use hydrazine as a supporting reducing agent to scavenge nitrous acid to stabilize the valence state of U(IV), but there are the following problems: U(IV) can be partially extracted into TBP, and nitrous acid is more effective than U (IV) is easily extracted into TBP, but hydrazine is difficult to be extracted by TBP, so when hydrazine is used as a supporting reducing agent, it can only stabilize the valence state of U(IV) in the aqueous phase, and U(IV) in the organic phase is easily extracted into TBP Oxidation of nitrous acid in.
目前公开的文献中，还没有关于如何稳定TBP萃取剂中U(IV)价态的报道，因此，急需一种解决此问题的方法。In the current published literature, there is no report on how to stabilize the U(IV) valence state in the TBP extractant. Therefore, a method to solve this problem is urgently needed.
发明内容Contents of the invention
(一)发明目的(1) Purpose of the invention
根据现有技术所存在的问题，本发明提供了一种方法简单且能够使TBP中U(IV)价态稳定时间长的方法。According to the problems existing in the prior art, the present invention provides a method which is simple and can stabilize the valence state of U(IV) in TBP for a long time.
(二)技术方案(2) Technical solution
为了解决现有技术所存在的问题，本发明提供的技术方案如下：In order to solve the existing problems of the prior art, the technical solutions provided by the invention are as follows:
一种稳定TBP中U(IV)价态的方法，该方法属于核燃料后处理技术领域，关键在于，该方法是向TBP有机相中引入乙醛肟；或者向水相中引入乙醛肟，再通过萃取的方式将乙醛肟萃取至TBP有机相中；A method for stabilizing the valence state of U(IV) in TBP, the method belongs to the technical field of nuclear fuel reprocessing, the key is that the method is to introduce acetaldehyde oxime into the organic phase of TBP; or to introduce acetaldehyde oxime into the water phase, and then Acetaldoxime is extracted into the TBP organic phase by means of extraction;
其中向TBP有机相中引入的乙醛肟的浓度是2～100mmol/L；向水相中引入的乙醛肟的浓度是20～1000mmol/L。The concentration of the acetaldehyde oxime introduced into the TBP organic phase is 2-100mmol/L; the concentration of the acetaldehyde oxime introduced into the water phase is 20-1000mmol/L.
优选地，该方法是向TBP有机相中引入乙醛肟，其中乙醛肟的浓度为2～100mmol/L。Preferably, the method is to introduce acetaldehyde oxime into the TBP organic phase, wherein the concentration of acetaldehyde oxime is 2-100mmol/L.
优选地，该方法是在5～40℃条件下进行的。Preferably, the method is carried out at 5-40°C.
(三)有益效果(3) Beneficial effects
本发明提供的后处理流程中TBP中U(IV)价态稳定的方法，该方法通过向TBP有机相中引入乙醛肟或者向水相中引入乙醛肟达到清除亚硝酸的目的。通过测定U(IV)的吸光光度值，得知该方法可使U(IV)价态稳定时间达5小时以上。其原理是：The method for stabilizing the valence state of U(IV) in TBP in the post-treatment process provided by the present invention, the method achieves the purpose of removing nitrous acid by introducing acetaldehyde oxime into the organic phase of TBP or introducing acetaldehyde oxime into the water phase. By measuring the absorbance value of U(IV), it is known that the method can stabilize the valence state of U(IV) for more than 5 hours. The principle is:
在硝酸介质中，以20℃温度条件下为例，乙醛肟与亚硝酸的反应速率常数为k＝(921.6±7.4)(mol/L)-1 . 5·min-1；且乙醛肟可少量萃入有机相TBP中，如果直接将乙醛肟加入有机相中，乙醛肟在TBP中也有一定的溶解度，与有机相中亚硝酸反应。In nitric acid medium, taking 20°C as an example, the reaction rate constant of acetaldehyde oxime and nitrous acid is k=(921.6±7.4)(mol/L) -1 . 5 ·min -1 ; and acetaldehyde oxime A small amount can be extracted into the organic phase TBP. If the acetaldehyde oxime is directly added into the organic phase, the acetaldehyde oxime also has a certain solubility in the TBP and reacts with the nitrous acid in the organic phase.
附图说明Description of drawings
图1是无乙醛肟存在时，TBP萃取剂中U(IV)吸光度值随时间变化图；Fig. 1 is when there is no acetaldehyde oxime, U (IV) absorbance value changes with time in the TBP extractant;
图2是乙醛肟存在条件下，TBP萃取剂中U(IV)吸光度值随时间变化图。Figure 2 is a graph showing the change of U(IV) absorbance value in the TBP extractant over time under the condition of the presence of acetaldehyde oxime.
具体实施方式detailed description
下面将结合说明书附图和具体实施例对本发明作进一步阐述。The present invention will be further elaborated below in conjunction with the accompanying drawings and specific embodiments.
实施例1Example 1
用两份含TBP体积分数10％的TBP-二甲苯溶液按相比1:1分别萃取纯化后的U(IV)溶液(铀总浓度3.09g/L，其中U(IV)浓度3.07g/L，纯度≥99.2％，硝酸浓度均为1mol/L)，分为两组，且均在25℃条件下，其中一组的水相中加入浓度为20mmol/L的乙醛肟，另一组水相中不含乙醛肟。萃取后取出有机相，每隔一定时间测定有机相在450～700nm区间的吸光度值，可通过U(IV)在该区域的特征吸收峰考察U(IV)的价态稳定性。Use two parts of TBP-xylene solutions containing TBP volume fraction 10% to extract the purified U(IV) solution (total uranium concentration 3.09g/L, wherein U(IV) concentration 3.07g/L , purity ≥ 99.2%, nitric acid concentration is 1mol/L), divided into two groups, and all under the condition of 25 ℃, wherein the concentration of adding acetaldehyde oxime to the water phase of one group is 20mmol/L, another group of water The phase does not contain acetaldehyde oxime. After extraction, take out the organic phase, and measure the absorbance value of the organic phase in the range of 450-700 nm at regular intervals, and the valence stability of U(IV) can be investigated through the characteristic absorption peak of U(IV) in this region.
实验结果如图1、2所示，由以上结果可知，无乙醛肟存时，2小时后，有机相中U(IV)的峰值已出现明显降低，即U(IV)发生了氧化；而有乙醛肟存在下，经过5小时，U(IV)的峰值仍比较稳定。所以实验中加入乙醛肟能明显提高有机相中U(IV)的稳定性。The experimental results are shown in Figures 1 and 2. From the above results, it can be seen that when there is no acetaldehyde oxime, after 2 hours, the peak value of U(IV) in the organic phase has been significantly reduced, that is, U(IV) has been oxidized; In the presence of acetaldehyde oxime, after 5 hours, the peak value of U(IV) is still relatively stable. Therefore, the addition of acetaldehyde oxime can significantly improve the stability of U(IV) in the organic phase.
实验中水相乙醛肟浓度很低，仅为20mmol/L，萃取到有机相的乙醛肟更少，如提高有机相乙醛肟浓度，U(IV)价态的稳定时间将更长，因此乙醛肟适用于稳定TBP中U(IV)的价态。In the experiment, the concentration of acetaldehyde oxime in the aqueous phase was very low, only 20mmol/L, and the acetaldehyde oxime extracted into the organic phase was less. If the concentration of acetaldehyde oxime in the organic phase was increased, the stable time of the U(IV) valence state would be longer. So acetaldehyde oxime is suitable for stabilizing the valence state of U(IV) in TBP.
实施例2Example 2
与实施例1不同的是，加入乙醛肟至有机相中，浓度为2mmol/L。该实施例的温度条件是40℃。The difference from Example 1 is that acetaldehyde oxime is added to the organic phase at a concentration of 2 mmol/L. The temperature condition in this example was 40°C.
实施例3Example 3
与实施例1不同的是，加入乙醛肟至有机相中，浓度为50mmol/L。该实施例的温度条件是5℃。The difference from Example 1 is that acetaldehyde oxime is added to the organic phase at a concentration of 50 mmol/L. The temperature condition in this example was 5°C.
实施例4Example 4
与实施例1不同的是，加入乙醛肟至有机相中，浓度为100mmol/L。The difference from Example 1 is that acetaldehyde oxime is added to the organic phase at a concentration of 100 mmol/L.
实施例5Example 5
与实施例1不同的是，加入乙醛肟至水相中，浓度为100mmol/L。The difference from Example 1 is that acetaldehyde oxime is added to the water phase at a concentration of 100 mmol/L.
实施例6Example 6
与实施例1不同的是，加入乙醛肟至水相中，浓度为500mmol/L。The difference from Example 1 is that acetaldehyde oxime is added to the water phase at a concentration of 500 mmol/L.
实施例7Example 7
与实施例1不同的是，加入乙醛肟至水相中，浓度为1000mmol/L。The difference from Example 1 is that acetaldehyde oxime is added to the water phase at a concentration of 1000 mmol/L.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6413482B1 (en) * | 1998-08-28 | 2002-07-02 | British Nuclear Fuels Plc | Method for reprocessing nuclear fuel by employing oximes |
| CN101765890A (en) * | 2007-06-07 | 2010-06-30 | 法国原子能委员会 | Use of butyraldehyde oxime as anti-nitrous agent in an operation for the reducing back-extraction of plutonium |
| CN102352436A (en) * | 2011-07-21 | 2012-02-15 | 中国原子能科学研究院 | Method for separating U (uranium) from Pu (plutonium) in Purex process |
| CN103820656A (en) * | 2014-01-28 | 2014-05-28 | 中国原子能科学研究院 | Uranium and plutonium separation technology in Purex process |
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- 2016-04-19 CN CN201610244630.2A patent/CN105931692A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6413482B1 (en) * | 1998-08-28 | 2002-07-02 | British Nuclear Fuels Plc | Method for reprocessing nuclear fuel by employing oximes |
| CN101765890A (en) * | 2007-06-07 | 2010-06-30 | 法国原子能委员会 | Use of butyraldehyde oxime as anti-nitrous agent in an operation for the reducing back-extraction of plutonium |
| CN102352436A (en) * | 2011-07-21 | 2012-02-15 | 中国原子能科学研究院 | Method for separating U (uranium) from Pu (plutonium) in Purex process |
| CN103820656A (en) * | 2014-01-28 | 2014-05-28 | 中国原子能科学研究院 | Uranium and plutonium separation technology in Purex process |
Non-Patent Citations (2)
| Title |
|---|
| 叶国安: "Purex流程中有机无盐试剂的应用分析", 《原子能科学技术》 * |
| 韩清珍 等: "乙醛肟还原钚的动力学及其在Purex流程铀钚分离中的应用", 《原子能科学技术》 * |
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