CN105280261B - A kind of method that electroreduction for uranium-containing waste water treatment precipitates uranium - Google Patents
A kind of method that electroreduction for uranium-containing waste water treatment precipitates uranium Download PDFInfo
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- CN105280261B CN105280261B CN201510636626.6A CN201510636626A CN105280261B CN 105280261 B CN105280261 B CN 105280261B CN 201510636626 A CN201510636626 A CN 201510636626A CN 105280261 B CN105280261 B CN 105280261B
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Abstract
The present invention provides a kind of method that electroreduction for uranium-containing waste water treatment precipitates uranium.First according to wastewater property using the pH value of sulfuric acid or NaOH regulation uranium-containing waste water to 24, then with metallic iron as anode, graphite is negative electrode, electroreduction is carried out using dc source, it is transformed into ferroso-ferric oxide by controlling technological parameter, iron ion, hexavalent uranium is reduced into uranous, and uranium is co-precipitated with ferroso-ferric oxide, so as to reach the purpose of removal Uranium in Waste Water.The present invention has the advantages that process is simple, non-secondary pollution, easy to control, removal efficiency is high, the uranium that is precipitated is recyclable.
Description
Technical field
The present invention relates to hydrometallurgy of uranium field, and in particular to the removal of uranium in uranium mine uranium-containing waste water.
Background technology
In order to alleviate the greenhouse effects in the whole world, it is contemplated that will expand more than 44% to the nuclear power scale in the whole world in 2035.Uranium is made
It is the main fuel of nuclear power, its demand inherently increases.And substantial amounts of uranium-containing waste water can be produced in the recovery process of uranium ore,
These uranium waste water will cause greatly harm to environment.Various uranium-containing waste water handling process are developed both at home and abroad, wherein main
Will be including absorption method, chemical precipitation method, membrane separation process, ion-exchange etc..Absorption method refers to uranium etc. between material and adsorbent
Reacted by physical absorption and ion exchange etc. and be attracted in porous material, then by the mode such as being centrifuged by adsorbent from useless
Separated in water, remove the purpose of uranium from waste water so as to reach.Although absorption method is economical in Spent Radioactive water process and is easy to
Operation, but because the adsorption capacity of adsorbent is limited, and discarded adsorbent needs to make specially treated, therefore absorption method is only fitted
Conjunction is applied to the uranium-containing waste water of low concentration.Chemical precipitation method is using the radioactive nucleus in flocculant and flocculation aid and uranium-containing waste water
Element is brought it about co-precipitation in the form of adsorption bridging or charge neutrality and forms the compound of some slightly solubilities and separate.Chemistry is heavy
Although shallow lake method process is simple, the chemical reagent added in processing procedure can form waste residue in the form of precipitating and cause secondary dirt
Dye, therefore, subsequent treatment cost is higher.Membrane separation process is to make the pollutants such as uranium by film using the selective penetrated property of film, and
Other materials can not reach the purpose for separating concentration by film, reach the purpose of purification waste water.Membrane separation process has separation
Efficiency high, energy consumption are low, simple to operate, be easily managed, effluent quality is good, strong adaptability the advantages of, but its price is costly, no
Easy large-scale use.Ion-exchange is, using the ion-exchanger with physical absorption ability, the uranium in waste water to be selected
The removal of selecting property purifies the purpose of uranium-containing waste water to reach.The advantage of ion-exchange is good removal effect, strong operability, sets
It is standby simple, produce it is few containing radioactive sludge, it is adaptable to suspension content is few and the low system of salt content.But for containing competition
The property high-concentration waste water of ion its treatment effect can be subject to strong influence.At present, electrodeposition process is because its equipment is simple, easily automatic
Change, progressively paid attention to by researcher the advantages of sensitivity is high, energy utilization rate is high, selectivity good, environment compatibility is high, at present
The treatment of the waste water such as chromate waste water, dyeing waste water, cyanide, percolate is carried out.However, uranium in general uranium-containing waste water
Concentration it is relatively low（About 0.5-50mg/L）, therefore be difficult to obtain uranium clearance higher using conventional electro-deposition method.
The content of the invention
It is an object of the invention to provide a kind of method that electroreduction for uranium-containing waste water treatment precipitates uranium, it has technique
Flow is simple, purification low cost, non-secondary pollution, the advantages of be capable of achieving the recovery of uranium.
Following characteristics must be included in electroreduction technical scheme, the purpose of the present invention is can be only achieved：
（1）Between the pH value of uranium-containing waste water necessarily be in 2-4 before electroreduction, pH is too low will to cause the quick dissolving of positive plate
And the quick rising of solution ph；PH is too high will to cause the rapid precipitation of iron ion in solution, the equal nothing of both the above situation
Method obtains the precipitation of ferroso-ferric oxide, is unfavorable for the separation of follow-up uranium.
（2）The positive plate of electroreduction is necessary for iron plate, and minus plate is necessary for inertia graphite, and it mainly uses appraising at the current rate for iron
Metallic character and redox characteristic, it is ensured that can form mixed containing ferrous iron, ferric iron and uranium ion in electro-reduction process
Solution environmental is closed, can just facilitate the crystallization of ferroso-ferric oxide and in the process to the capture of uranium, such as change other electrode materials into
Material cannot realize the purpose of the present invention.
（3）Electroreduction voltage is necessary for dc source, and magnitude of voltage will be controlled between 27-32V, and voltage is too low, reaction
Speed is too slow；Overtension, will cause reduction process pH value of waste water to rise very fast, it is impossible to which the formation to ferroso-ferric oxide crystal is carried
For the time, cause precipitated product for ferric hydroxide colloid, be unfavorable for that subsequent filter is separated.
（4）Need to be circulated waste water near anode agitation using circulating pump in electro-reduction process, its purpose one is
The ferrous ion produced near quickening anode diffusion in the solution, so as to improve uranic speed in its reducing waste water；
Two is to avoid a large amount of ferrous ions from being stopped near anode, prevents from being formed about hydroxide in anode in wastewater pH elevation process
Iron is precipitated, and weakens the removal effect of uranium.
（5）In electro-reduction process, can first occur yellowish-brown floccule near minus plate, little particle black then occur
Ferroso-ferric oxide is precipitated, and should now continue energization 10min, and the time is left to the crystallization of ferriferrous oxide particles, is otherwise produced
Ferroso-ferric oxide precipitation property is unstable, is unfavorable for subsequent treatment.
Therefore, the present invention is the characteristic for making full use of electrochemical principle and uranium ion, in specific electroreduction technique bar
Under part, the uranium in waste water is entered in ferroso-ferric oxide precipitation, lack conditions above, it is impossible to reach the purpose of the present invention.Its is excellent
Gesture is：（1）Ferroso-ferric oxide is crystalline solid, it is easy to be separated by filtration；（2）Ferroso-ferric oxide is stable in properties, is easy to after depositing
Storage；（3）Ferroso-ferric oxide can be recovered and as other industrial raw material.（4）Will not be produced in whole reduction process and appointed
What other secondary pollution.
Realize the technical scheme of the object of the invention：A kind of method that electroreduction for uranium-containing waste water treatment precipitates uranium, it is first
First with the pH value of dilute sulfuric acid or NaOH adjustment uranium-containing waste water between 2-4, then with monolithic metal as anode, inertia graphite
It is negative electrode, electroreduction is carried out using dc source, and control supply voltage between 27-32V, circulating pump is used in electro-reduction process
Waste water is stirred near anode iron plate, when starting to occur yellowish-brown floccule near minus plate, continue be powered until
It is transformed into after black particle shape sediment the holding 10min that is powered again, and electroreduction is filtered after terminating to sediment, and its is main
Composition is the crystal of ferroso-ferric oxide and uranium.
The method of the electroreduction precipitation uranium containing the uranium-containing waste water that uranium concentration is more than 0.5mg/L to can process.
General principle of the invention is as follows：
（1）With monolithic metal as anode, electrolytic process Anodic iron plate is gradually dissolved and produces ferrous ion, due to useless
Uranium in water is main with U（VI）Form is present, then ferrous iron serves as reducing agent by U（VI）It is reduced to U（IV）, while ferrous iron turns
Become ferric iron；
（2）In the presence of electric field, ferrous iron, ferric iron and U（IV）Moved to minus plate simultaneously, due in electrolytic process
Hydrogen ion is equally also reduced into hydrogen, causes the pH value of waste water slowly to rise, and moves closer to neutrality, now, ferrous iron, three
Valency iron and U（IV）It is co-precipitated near minus plate, forms with ferroso-ferric oxide and be mingled with the sediment of uranium crystallization.
It is of the invention compared with traditional uranium-containing waste water handling process, have the advantage that：
（1）Only need to carry out pH value regulation to uranium-containing waste water to the strong adaptability of waste water, before electroreduction；
（2）Any chemical reagent need not be added in electro-reduction process, it is to avoid secondary pollution；
（3）Electroreduction PROCESS FOR TREATMENT ability is big, and the uranium-containing waste water to more than 0.5mg/L can be processed；
（4）Electroreduction precipitated product amount is few, and predominantly ferroso-ferric oxide and the crystal of uranium, subsequently can be recovered profit
With.
Brief description of the drawings
Fig. 1 electroreduction devices,
Fig. 2 sediments form schematic diagram.
Specific embodiment
The present invention processes uranium-containing waste water using electrochemical reduction method, and its implementation range of application is wider, herein only by following implementation
The invention will be further described for case.
Embodiment 1
The concentration of uranium is 10mg/L in certain uranium-containing waste water, and pH value is 2.2.
The method that a kind of electroreduction for uranium-containing waste water treatment of the present invention precipitates uranium：
The uranium-containing waste water of 500ml is poured into electrolytic cell, with metallic iron as anode, inertia graphite is negative electrode, in the direct current of 27V
Electroreduction is carried out under the conditions of electricity, meanwhile, liquid is stirred near positive plate with internal circulation pump, after reaction 90min, negative electrode
Occur a large amount of black particle shape sediments near plate, powered off after continuing energization 10min, now the pH value of waste water is 6.7, in waste water
The concentration of uranium is reduced to 0.6mg/L, and the clearance of uranium is 94%.
Embodiment 2
The concentration of uranium is 30mg/L in certain uranium-containing waste water, and pH value is 4.6.
The method that a kind of electroreduction for uranium-containing waste water treatment of the present invention precipitates uranium：
The uranium-containing waste water of 500ml is poured into electrolytic cell, is nertralizer with 30% dilute sulfuric acid, pH value is adjusted to 2.6, with gold
Category iron is anode, and inertia graphite is negative electrode, and electroreduction is carried out under the conditions of the direct current of 30V, meanwhile, with internal circulation pump in anode
Plate is nearby stirred to liquid, after reaction 50min, occurs a large amount of black particle shape sediments near minus plate, continues to be powered
Powered off after 10min, now the pH value of waste water is 7.2, the concentration of Uranium in Waste Water is reduced to 1.2mg/L, and the clearance of uranium is 96%.
Embodiment 3
The concentration of uranium is 20mg/L in certain uranium-containing waste water, and pH value is 5.2.
The method that a kind of electroreduction for uranium-containing waste water treatment of the present invention precipitates uranium：
The uranium-containing waste water of 500ml is poured into electrolytic cell, is nertralizer with 30% dilute sulfuric acid, pH value is adjusted to 3.2, with gold
Category iron is anode, and inertia graphite is negative electrode, and electroreduction is carried out under the conditions of the direct current of 32V, meanwhile, with internal circulation pump in anode
Plate is nearby stirred to liquid, after reaction 70min, occurs a large amount of black particle shape sediments near minus plate, continues to be powered
Powered off after 10min, now the pH value of waste water is 6.5, the concentration of Uranium in Waste Water is reduced to 0.8mg/L, and the clearance of uranium is 96%.
Claims (3)
1. a kind of method that electroreduction for uranium-containing waste water treatment precipitates uranium, it is characterised in that control uranium-containing waste water first
Between 2-4, then with monolithic metal as anode, inertia graphite is negative electrode to pH value, and electroreduction is carried out using dc source, is passed through
Control electroreduction parameter, the uranium in waste water is produced in electro-reduction process and form sediment, electroreduction terminate after to sediment
Filtered, so as to reach the purpose of removal Uranium in Waste Water,
The control electroreduction parameter, specifically includes：Control supply voltage uses circulating pump between 27-32V in electro-reduction process
Waste water is stirred near anode iron plate, when starting to occur yellowish-brown floccule near minus plate, continue be powered until
Yellowish-brown floccule is transformed into after black particle shape sediment the holding 10min that is powered again；
The uranium is produced in electro-reduction process and forms sediment, and detailed process is：
（1）With monolithic metal as anode, electrolytic process Anodic iron plate is gradually dissolved and produces ferrous ion, the uranium in waste water
With U（VI）Form is present, then ferrous iron serves as reducing agent by U（VI）It is reduced to U（IV）, while ferrous iron is transformed into ferric iron；
（2）In the presence of electric field, ferrous iron, ferric iron and U（IV）Simultaneously to minus plate move, due in electrolytic process hydrogen from
Son is equally also reduced into hydrogen, causes the pH value of waste water slowly to rise, and moves closer to neutrality, now, ferrous iron, ferric iron
With U（IV）It is co-precipitated near minus plate, forms the sediment for being mingled with uranium crystallization with ferroso-ferric oxide.
2. the method that a kind of electroreduction for uranium-containing waste water treatment according to claim 1 precipitates uranium, it is characterised in that
The pH value of the control uranium-containing waste water specially adjusts the pH value of uranium-containing waste water between 2-4 using dilute sulfuric acid or NaOH
Between 2-4.
3. the method that a kind of electroreduction for uranium-containing waste water treatment according to claim 1 precipitates uranium, it is characterised in that
The uranium-containing waste water is the uranium-containing waste water of more than 0.5mg/L containing uranium concentration.
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| CN106448790B (en) * | 2016-11-11 | 2017-12-22 | 东华理工大学 | A kind of uranium-containing waste water electrochemical process for treating |
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| CN114134349B (en) * | 2021-12-06 | 2023-03-28 | 西北工业大学 | Process for recovering uranium in water through photocatalytic reduction fixation, electrooxidation enrichment and precipitation separation |
| CN115821080A (en) * | 2022-10-17 | 2023-03-21 | 西北工业大学 | Process for extracting uranium from uranium-containing wastewater and preparing yellow cake |
| CN117438124B (en) * | 2023-12-22 | 2024-04-09 | 中核第四研究设计工程有限公司 | Method for long-term stable treatment of uranium-containing waste residues |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108868A (en) * | 1984-07-06 | 1987-06-24 | 英国核子燃料公司 | The production of uranous tetrafluoride |
| US4769180A (en) * | 1986-04-04 | 1988-09-06 | Doryokuro Kakunenryo Kaihatsu Jigyodan | Process for separately recovering uranium and hydrofluoric acid from waste liquor containing uranium and fluorine |
| CN101597113A (en) * | 2009-06-27 | 2009-12-09 | 南华大学 | A kind of treatment process of uranium-containing waste water |
| CN101650980A (en) * | 2008-08-12 | 2010-02-17 | 株式会社东芝 | Method for reprocessing spent nuclear fuel and centrifugal extractor therefor |
| CN202201767U (en) * | 2011-08-25 | 2012-04-25 | 厦门市威士邦膜科技有限公司 | Comprehensive electroplating wastewater treatment device |
| CN103695956A (en) * | 2013-12-30 | 2014-04-02 | 中国原子能科学研究院 | Device for preparing tetravalent uranium by electrolytic reduction |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3144160B2 (en) * | 1993-07-02 | 2001-03-12 | 住友金属鉱山株式会社 | How to remove radioactive materials in water |
-
2015
- 2015-10-01 CN CN201510636626.6A patent/CN105280261B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108868A (en) * | 1984-07-06 | 1987-06-24 | 英国核子燃料公司 | The production of uranous tetrafluoride |
| US4769180A (en) * | 1986-04-04 | 1988-09-06 | Doryokuro Kakunenryo Kaihatsu Jigyodan | Process for separately recovering uranium and hydrofluoric acid from waste liquor containing uranium and fluorine |
| CN101650980A (en) * | 2008-08-12 | 2010-02-17 | 株式会社东芝 | Method for reprocessing spent nuclear fuel and centrifugal extractor therefor |
| CN101597113A (en) * | 2009-06-27 | 2009-12-09 | 南华大学 | A kind of treatment process of uranium-containing waste water |
| CN202201767U (en) * | 2011-08-25 | 2012-04-25 | 厦门市威士邦膜科技有限公司 | Comprehensive electroplating wastewater treatment device |
| CN103695956A (en) * | 2013-12-30 | 2014-04-02 | 中国原子能科学研究院 | Device for preparing tetravalent uranium by electrolytic reduction |
Non-Patent Citations (2)
| Title |
|---|
| 电解-微电解耦合处理重金属废水及机理分析;王刚;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20130115(第1期);B027-409-1-73 * |
| 零价铁和赤铁矿去除污染水体中U(VI)的试验研究;张纯;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20080115(第1期);B027-124-1-66 * |
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