CN105274363A - Method for destructing oxalic acid in plutonium oxalate sediment mother solution - Google Patents

Method for destructing oxalic acid in plutonium oxalate sediment mother solution Download PDF

Info

Publication number
CN105274363A
CN105274363A CN201510697776.8A CN201510697776A CN105274363A CN 105274363 A CN105274363 A CN 105274363A CN 201510697776 A CN201510697776 A CN 201510697776A CN 105274363 A CN105274363 A CN 105274363A
Authority
CN
China
Prior art keywords
precipitation
ammonium
mother liquor
plutonium oxalate
anode
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
Application number
CN201510697776.8A
Other languages
Chinese (zh)
Inventor
李辉波
何喜红
谢书宝
曹智
苏哲
袁洁琼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Institute of Atomic of Energy
Original Assignee
China Institute of Atomic of Energy
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Institute of Atomic of Energy filed Critical China Institute of Atomic of Energy
Priority to CN201510697776.8A priority Critical patent/CN105274363A/en
Publication of CN105274363A publication Critical patent/CN105274363A/en
Pending legal-status Critical Current

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Landscapes

  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The invention belongs to the technical field of spent fuel postprocessing, and discloses a method for destructing oxalic acid in a plutonium oxalate sediment mother solution. The method comprises the following steps that a direct-current power source capable of achieving periodic reverse is utilized for electrolyzing the plutonium oxalate sediment mother solution under the constant-voltage condition, and platinum electrodes or titanium-plated platinum electrodes are adopted as a cathode and an anode, wherein the reverse period of the direct-current power source is the time spent when the anode is passivated, and the constant voltage is an electrolytic oxidation decomposition peak potential value of the oxalic acid in the plutonium oxalate sediment mother solution. The method has the beneficial effects of being capable of effectively avoiding anode passivation and anode oxidation, and being high in electrolytic efficiency and high in electrolysis speed.

Description

A kind of method destroying plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid
Technical field
The invention belongs to spent fuel post-processing technology field, be specifically related to a kind of method destroying plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid.
Background technology
In spent fuel reprocessing process flow process, plutonium product tail end technique normally adds oxalic acid in plutonium nitrate solution makes plutonium become the sedimentary form of plutonium oxalate as the precipitation agent of plutonium, and will the throw out of acquisition be filtered through high-temperature calcination, form final plutonium dioxide product, the solution wherein after the filtration of plutonium oxalate throw out is referred to as plutonium oxalate mother liquor of precipitation of ammonium.Except containing having an appointment except 0.05 ~ 0.1mol/L oxalic acid and 2 ~ 3mol/L nitric acid in plutonium oxalate mother liquor of precipitation of ammonium, also contain the micro-plutonium of 50 ~ 200mg/L.Maximization is reclaimed in order to realize plutonium in aftertreatment flow process, further extraction and recovery plutonium in extraction procedure is back to after oxalic acid in plutonium oxalate mother liquor of precipitation of ammonium need being destroyed, because the amount of oxalic acid has considerable influence to the recovery of plutonium in aftertreatment extraction procedure, the destructive rate of the plutonium oxalate mother liquor mesoxalic acid that general requirement returns reaches more than 99.5%.At present, spent fuel last handling process mainly adopts potassium permanganate boiling oxidation style to the destruction of mother liquor of precipitation of ammonium mesoxalic acid, this method have operation under high temperature can cause equipment corrosion serious, introduce new impurity element and the shortcoming such as waste liquid saltiness is high, thus reduce its its usage economy.Some research structure external also once have studied by adding concentrated nitric acid, hydrogen peroxide or pass into ozone or by method oxygenolysis oxalic acid such as uviolizings in plutonium oxalate mother liquor in plutonium oxalate mother liquor, but all have that oxalic acid destructive rate is low, reagent consumption and the shortcoming such as waste liquid generation is large.
Along with the development of electrochemical techniques in recent years, electrochemical techniques have also been obtained extensive concern and research in nuclear chemistry field, electrochemical oxidation destroy method can realize the destruction of oxalic acid when adding other reagent in normal temperature, normal pressure, nothing, it has simple to operate, easy to control, has a good application prospect.The electrolyte destruction behavior of the glad grade of China Qiao Ji to simulation plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid is studied, and result of study all shows, electrochemical oxidation process can realize the oxalic acid destructive rate of more than 98%, but the CO produced due to anode destruction oxalic acid process 2and O 2anode is made to occur serious reversible passivation, current efficiency and electrolytic speed decline thereupon, at this moment usual by improve electrolytic current density guarantee stable electrolytic speed, but after current density improves, except increasing the weight of anode passivation, yin, yang the two poles of the earth also can produce a large amount of hydrogen, oxygen and other side reaction, whole process current efficiency and processing safety are all reduced, and industrial applications is restricted.Therefore set up and a kind ofly avoid anode passivation and electrolytic efficiency is high, electrolytic speed is fast and the electrolysis process of avoiding anode oxygen to generate is very important.
Summary of the invention
(1) goal of the invention
Problem existing for prior art, the invention provides a kind of anode passivation and anode oxygen can avoided and generates and the method for the destruction plutonium oxalate solution mesoxalic acid that electrolytic efficiency is high, electrolytic speed is fast.
(2) technical scheme
In order to solve prior art Problems existing, the present invention is achieved by the following technical solutions:
Destroy a method for plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid, the method comprises the following steps:
Utilization can periodic reverse direct supply and under constant voltage condition, electrolysis is carried out to plutonium oxalate mother liquor of precipitation of ammonium, negative electrode used and anode are platinum electrode or titanium platinized electrode (titanium sheet or titanium are coated with platinum film on the net); The cycle that wherein this direct supply is reverse is the time that anode produces passivation, and constant voltage used is plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid electrolytic oxidation decomposition peak potential value;
Preferably, due in last handling process, plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid electrolytic oxidation decomposition peak current potential is 1.0 ~ 1.4V, Oxygen anodic evolution current potential is 1.5V, therefore constant voltage used is 1.0 ~ 1.4V, the generation of anode oxygen can be avoided, also can reduce cathode hydrogen evolution amount simultaneously, improve processing safety.
Preferably, direct supply reverse cycle utilizes cyclic voltammetry to determine, the cycle that in plutonium oxalate mother liquor of precipitation of ammonium electrolytic process, direct supply is reverse is 7 ~ 10s.
Preferably, agitator is utilized to stir in electrolytic process.
Preferably, negative electrode used and anode are titanium platinized electrode.
(3) beneficial effect
Adopt the method for destruction plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid provided by the invention, the method effectively can avoid anode passivation and anode oxygen generates and electrolytic efficiency is high, electrolytic speed fast, and specific explanations is:
1) in electrolytic decomposition oxalic acid process, anode can produce reversible passivation.The method of the periodic reverse power supply electrolysis provided by the application, makes the anode of generation slight deactivation be activated when oppositely becoming negative electrode, avoids anode passivation continuity, makes it be in active state all the time, avoid the generation of anode passivation phenomenon.Compared with direct current one-way electric power electrolytic process, average current efficiency is made to be increased to about 85% from original less than 20%.
2) avoid the generation of anode oxygen, reduce cathodic hydrogen generation, improve its processing safety.
3) improve oxalic acid electrolytic oxidation electrolytic speed, in order to reach the oxalic acid destructive rate of more than 99.5%, utilize can the direct supply of periodic reverse compared with direct current one-way electric power electrolytic process, the former required time is 2.5h, and the latter's required time is 7h.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated.
Embodiment 1
Destroy a method for plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid, the method comprises the following steps:
By the plutonium oxalate mother liquor of precipitation of ammonium in the 100ml mixing solutions of the solution composition by 0.05mol/L oxalic acid, 2mol/L nitric acid and 100mgPu/L simulation aftertreatment feed liquid, and this mother liquor of precipitation of ammonium to be added to volume be in the electrolyzer of 130ml, in electrolyzer, add two areas is 4cm 2titanium platinized electrode as negative electrode and anode, and these two electrodes with can the direct supply of periodic reverse be connected; Power settings operating voltage is 1.4V, periodic reverse is spaced apart 10 seconds cycling time.In electrolytic process, adopt magnetic stirring apparatus to carry out solution stirring.
Every the concentration of 20min sampling analysis solution oxalate, and calculate its destructive rate and current efficiency.In addition, also by its with utilize direct current one-way electric power oxygenolysis plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid to compare, as following table:
The current efficiency of table 1 direct current unidirectional electrolysis oxygenolysis oxalic acid and electrolytic speed
(continuous current 0.1A, electrode current density 0.025A/cm 2, service temperature is 25 DEG C)
Table 2 can the current efficiency of direct supply electrolytic oxidation decomposing oxalic acid of periodic reverse and electrolytic speed
(constant voltage 1.4V, electrode current density 3.75*10 -3~ 0.025A/cm 2, service temperature is 25 DEG C)
Can find out from table 1 and table 2, what utilize the application to provide the direct supply of periodic reverse can carry out electrolysis to the oxalic acid in plutonium oxalate mother liquor of precipitation of ammonium under constant voltage condition, current efficiency can be made to significantly improve, and electrode surface avoids the generation of oxygen.
Embodiment 2
As different from Example 1, power settings operating voltage is 1.0V, and direct supply reverse cycle is 7s, and negative electrode and anode are platinum electrode.
Embodiment 3
As different from Example 1, power settings operating voltage is 1.2V, and direct supply reverse cycle is 8s, and negative electrode is platinum electrode, and anode is titanium platinized electrode.

Claims (5)

1. destroy a method for plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid, it is characterized in that, the method comprises the following steps:
Utilization can periodic reverse direct supply and under constant voltage condition, electrolysis is carried out to plutonium oxalate mother liquor of precipitation of ammonium, negative electrode used and anode are platinum electrode or titanium platinized electrode; The cycle that wherein this direct supply is reverse is the time that anode produces passivation, and constant voltage used is plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid electrolytic oxidation decomposition peak potential value.
2. a kind of method destroying plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid according to claim 1, is characterized in that, the magnitude of voltage of described constant voltage is 1.0 ~ 1.4V.
3. a kind of method destroying plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid according to claim 1, it is characterized in that, direct supply reverse cycle utilizes cyclic voltammetry to determine, the cycle that in plutonium oxalate mother liquor of precipitation of ammonium electrolytic process, direct supply is reverse is 7 ~ 10s.
4. a kind of method destroying plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid according to claim 1, is characterized in that, utilize agitator to stir in electrolytic process.
5. a kind of method destroying plutonium oxalate mother liquor of precipitation of ammonium mesoxalic acid according to claim 1, it is characterized in that, negative electrode used and anode are titanium platinized electrode.
CN201510697776.8A 2015-10-23 2015-10-23 Method for destructing oxalic acid in plutonium oxalate sediment mother solution Pending CN105274363A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510697776.8A CN105274363A (en) 2015-10-23 2015-10-23 Method for destructing oxalic acid in plutonium oxalate sediment mother solution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510697776.8A CN105274363A (en) 2015-10-23 2015-10-23 Method for destructing oxalic acid in plutonium oxalate sediment mother solution

Publications (1)

Publication Number Publication Date
CN105274363A true CN105274363A (en) 2016-01-27

Family

ID=55144183

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510697776.8A Pending CN105274363A (en) 2015-10-23 2015-10-23 Method for destructing oxalic acid in plutonium oxalate sediment mother solution

Country Status (1)

Country Link
CN (1) CN105274363A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106119578A (en) * 2016-06-27 2016-11-16 中国原子能科学研究院 In a kind of plutonium oxalate mother liquor of precipitation of ammonium, nitric acid oxalic acid concentrates and the integral method destroyed
CN108630332A (en) * 2018-03-26 2018-10-09 中国核电工程有限公司 A kind of breaking plant and destruction methods of oxalate precipitation filtrated stock oxalate
CN114420335A (en) * 2022-01-19 2022-04-29 中国原子能科学研究院 Method for continuously precipitating plutonium oxalate
CN114684879A (en) * 2020-12-25 2022-07-01 中核四0四有限公司 One-pass oxalic acid oxidation method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1064111A (en) * 1991-04-20 1992-09-02 张家口市宣化化工厂 Bipolar chamber paired electrolysis method is produced oxoethanoic acid
CN1219611A (en) * 1998-10-16 1999-06-16 化学工业部天津化工研究设计院 Electrolytic preparation method for glyoxalic acid
CN1281063A (en) * 2000-04-04 2001-01-24 华东理工大学 Process for preparing glyoxylic acid by electrolytic reduction of oxalic acid
CN1322860A (en) * 2001-04-17 2001-11-21 华东理工大学 Oxalic acid electroreduction process of preparing glyoxalic acid
CN101713026A (en) * 2009-12-16 2010-05-26 中国原子能科学研究院 Method for extracting palladium from high-level radioactive waste liquid
CN103335964A (en) * 2013-06-18 2013-10-02 中国原子能科学研究院 Carbonyl compound analysis method in after-treatment technique process
CN104112485A (en) * 2014-08-04 2014-10-22 中国原子能科学研究院 Device for continuously destructing radiative waste organic solvent

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1064111A (en) * 1991-04-20 1992-09-02 张家口市宣化化工厂 Bipolar chamber paired electrolysis method is produced oxoethanoic acid
CN1219611A (en) * 1998-10-16 1999-06-16 化学工业部天津化工研究设计院 Electrolytic preparation method for glyoxalic acid
CN1281063A (en) * 2000-04-04 2001-01-24 华东理工大学 Process for preparing glyoxylic acid by electrolytic reduction of oxalic acid
CN1322860A (en) * 2001-04-17 2001-11-21 华东理工大学 Oxalic acid electroreduction process of preparing glyoxalic acid
CN101713026A (en) * 2009-12-16 2010-05-26 中国原子能科学研究院 Method for extracting palladium from high-level radioactive waste liquid
CN103335964A (en) * 2013-06-18 2013-10-02 中国原子能科学研究院 Carbonyl compound analysis method in after-treatment technique process
CN104112485A (en) * 2014-08-04 2014-10-22 中国原子能科学研究院 Device for continuously destructing radiative waste organic solvent

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
乔继欣: "模拟草酸钚沉淀母液中草酸电解破坏研究", 《原子能科学技术》 *
陆振昌: "《中华人民共和国电力百科全书 第5卷》", 30 November 2001 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106119578A (en) * 2016-06-27 2016-11-16 中国原子能科学研究院 In a kind of plutonium oxalate mother liquor of precipitation of ammonium, nitric acid oxalic acid concentrates and the integral method destroyed
CN106119578B (en) * 2016-06-27 2018-10-09 中国原子能科学研究院 Nitric acid-oxalic acid concentration and the integral method that destroys in a kind of plutonium oxalate mother liquor of precipitation of ammonium
CN108630332A (en) * 2018-03-26 2018-10-09 中国核电工程有限公司 A kind of breaking plant and destruction methods of oxalate precipitation filtrated stock oxalate
CN108630332B (en) * 2018-03-26 2021-06-18 中国核电工程有限公司 Device and method for destroying oxalate in oxalate precipitation and filtration mother liquor
CN114684879A (en) * 2020-12-25 2022-07-01 中核四0四有限公司 One-pass oxalic acid oxidation method
CN114420335A (en) * 2022-01-19 2022-04-29 中国原子能科学研究院 Method for continuously precipitating plutonium oxalate
CN114420335B (en) * 2022-01-19 2024-02-20 中国原子能科学研究院 Method for continuously precipitating plutonium oxalate

Similar Documents

Publication Publication Date Title
CN102190573B (en) Method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide
Stucki et al. In situ production of ozone in water using a membrel electrolyzer
CN105274363A (en) Method for destructing oxalic acid in plutonium oxalate sediment mother solution
CN104846397A (en) Electrode for electrochemical reduction of CO2 and preparation of formic acid and preparation method and application thereof
Zhang et al. High-efficiency lithium isotope separation in an electrochemical system with 1-butyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, and diethyl carbonate as the solvents
CN107541744B (en) Nano-silver electrode formed by in-situ formation of flat silver and preparation method and application thereof
KR20140084640A (en) Method for reducing carbon dioxide and non-diaphragm reductor of carbon dioxide using the same
CN104313663A (en) Preparation method of N, Ti<3+> codoped visible light catalysis TiO2 nanotube array
Tehrani et al. Application of electrodeposited cobalt hexacyanoferrate film to extract energy from water salinity gradients
CN104638288A (en) Electrochemical preparation method of 3.5 valence vanadium electrolyte
CN106876767B (en) A kind of positive electrolyte for all-vanadiumredox flow battery containing additive
CN201981262U (en) Circular electrolysis reacting device for preparing electrolyte of vanadium batter
CN101634039B (en) Glassy carbon electrode (GCE) modified by conductive copolymer, preparation method thereof and method for removing dichromate from water
CN105112980A (en) High-activity TiO2-NTs/PbO2-Y-Co3O4 modified electrode and method for electrocatalytic oxidation treatment of pharmaceutical wastewater with same
US9435042B2 (en) System and method for selective electrochemical reduction of carbon dioxide employing an anodized silver electrode
CN204702546U (en) A kind of electrochemical treatment system processing nickel-containing waste water
CN106119578B (en) Nitric acid-oxalic acid concentration and the integral method that destroys in a kind of plutonium oxalate mother liquor of precipitation of ammonium
CN101864577B (en) Method for electrochemically preparing peroxysulfuric acid
CN114759285B (en) Treatment method of waste lithium ion battery leaching liquid
CN107620089B (en) One kind is in CuFeO2/CuInS2By CO on composite semiconductor films electrode2The method for being reduced to methanol
CN107574455B (en) It is a kind of in the CuFeO for mixing Li2By CO on semi-conducting electrode2The method of reduction
CN102011135A (en) Cyclic electrolysis reaction device and method for preparing vanadium battery electrolyte
CN109095688A (en) A kind of method of chloride ion in recycling waste water
CN110592608B (en) Device for electrolyzing seawater for tri-generation, method and application thereof
CN103290415A (en) Treatment process and system of acid etching solution

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20160127

RJ01 Rejection of invention patent application after publication