CN102491479A - Neutralization method for treating alkali wastewater containing uranium - Google Patents
Neutralization method for treating alkali wastewater containing uranium Download PDFInfo
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- CN102491479A CN102491479A CN2011103937455A CN201110393745A CN102491479A CN 102491479 A CN102491479 A CN 102491479A CN 2011103937455 A CN2011103937455 A CN 2011103937455A CN 201110393745 A CN201110393745 A CN 201110393745A CN 102491479 A CN102491479 A CN 102491479A
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- uranium
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- radium
- containing waste
- alkaline
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Abstract
The invention provides a neutralization method for treating alkali wastewater containing uranium, which comprises the following steps: adding OH- in FeSO4 neutralized wastewater into the alkali wastewater containing uranium, wherein the molar weight of the added FeSO4 is 1/3-2/3 of that of the OH- in the alkali wastewater containing uranium, potential of hydrogen (pH) value of the wastewater is adjusted in a range of 7-9, the reaction temperature is 20-30 DEG C, and the reaction time is 1-3 hours; oxidizing and hydrolyzing Fe2+ under the action of air to produce Fe(OH)3 precipitation, wherein the Fe(OH)3 precipitation has positive electricity and can absorb uranium ions; 3 under the condition of ph 7-9, if the SO42- concentration is lowered than 1.0-2.0 grams per milliliter, adding Na2SO4 to supplement SO42- and enable the SO42- concentration to be 1.0-2.0 grams per milliliter; and adding BaCl2 to remove radium and co-precipitate and produce Ba(Ra)SO4, wherein added BaCl2 quantity is controlled in a range of 0.02-0.06 gram per milliliter. The neutralization method is an important process in the treatment technology of the alkali wastewater containing uranium, and simultaneously achieves functions including neutralization, adsorption carrying for removing the uranium deeply, supplement of SO42- for removing the radium, inhibiting of precipitation re-dissolution, coprecipitation for removing the radium and the like.
Description
Technical field
The present invention relates to the hydrometallurgy of uranium field, be specifically related to the removal of uranium radium in the uranium mine alkalescence uranium-containing waste water.
Background technology
The uranium ore alkaline process leaches with the acid system leaching and compares; Can optionally dissolve the uranium in the ore; Wherein iron, aluminium, titanium etc. are dissolved in the carbonate solution hardly, have only some a spot of molybdate, silicate, vannadate, phosphoric acid salt and some metal carbonate complex compound in the leach liquor.The radionuclide thorium soaks at alkali and is actually insoluble in the process, and radium then dissolves 1.5～3%, and other radionuclide is obviously all dumped mine tailing and suffered.Therefore the uranium mine of handling for alkaline process, the principal pollutant of waste water are radioactive nucleus uranium and radium.
See that from the explored uranium resources of China the ratio of alkaline ore resource amount reaches 30%, adopt alkaline process (carbonate) to leach usually, often use NaCl+NaHCO because uranium reclaims the drip washing operation of technology for this type ore
3, bring Cl to system
-, and progressively accumulation, cause the tail washings uranium concentration of absorption process to run height, influence the recovery of uranium.Therefore, need a part of waste water be effluxed, normally move to guarantee technology.CO in the alkalescence uranium-containing waste water
3 2-And Cl
-Coexistence, prior art remove uranium, remove the radium weak effect, are difficult to reach the highest allowable value of discharge of wastewater: uranium 0.3mg/L, radium 1.1Bq/L.This is the major cause that China's alkalescence ore uranium resources does not obtain large-scale development as yet.
Prior art is directly to adopt sulfuric acid that alkaline uranium-containing waste water is neutralized, its purpose: the one, and adjustment pH value makes it to be suitable for the desired best pH scope of sorbing material; The 2nd, reach the pH value that efflux wastewater allows.Because sulfuric acid belongs to strong acid, adopt sulfuric acid directly to neutralize, make the throw out of generation return molten; Do not replenish the carrier band metals ion in addition, throw out co-precipitation radium effect is relatively poor, does not reach the purpose that the degree of depth is removed uranium simultaneously, thereby causes water treatment effect not good.
Summary of the invention
The present invention provides a kind of neutralization method that alkaline uranium-containing waste water is handled that is used for, and it can realize neutralizing, the absorption carrier band degree of depth is molten except that uranium, inhibition throw out return, co-precipitation removes functions such as radium.
Realize the technical scheme of the object of the invention: a kind of neutralization method that is used for alkaline uranium-containing waste water processing adds FeSO in its alkalitropism uranium-containing waste water
4In with waste water in OH
-, FeSO
4The molar weight that adds is OH in the alkaline uranium-containing waste water
-1/3～2/3 of molar weight is regulated waste water ph 7～9,20～30 ℃ of temperature of reaction, reaction times 1～3h; Fe
2+Oxydrolysis generates Fe (OH) under air
3Deposition, Fe (OH)
3The adsorbable uranium ion of deposition positively charged; Under pH 7～9 situation, like SO
4 2-Concentration is lower than 1.0～2.0gL
-1, then add Na
2SO
4Replenish SO
4 2-, make SO
4 2-Concentration is 1.0～2.0gL
-1Add BaCl then
2Remove radium, co-precipitation generates Ba (Ra) SO
4, BaCl
2Add-on is controlled at 0.02～0.06gL
-1
Aforesaid a kind of neutralization method that alkaline uranium-containing waste water is handled that is used for, it is with adding FeSO in the pneumatic blending mode alkalitropism uranium-containing waste water
4
The aforesaid a kind of neutralization method that alkaline uranium-containing waste water is handled, its described alkaline uranium-containing waste water CO of being used for
3 2-Content is lower than 0.1mgL
-1, OH
-Content is 1.5～4.0gL
-1, pH value 12.0～13.0, uranium content 0.1～2.0mgL
-1, radium content 10～40BqL
-1, 20～30 ℃ of temperature of reaction, reaction times 1～3h.
Effect of the present invention is: the invention provides the neutralization method that a kind of alkaline uranium-containing waste water is handled, it is important procedure of alkaline uranium-containing waste water treatment process, realizes neutralizing, adsorbs the carrier band degree of depth simultaneously and remove uranium, replenish and remove the used SO of radium
4 2-, suppress throw out and return molten, co-precipitation and remove functions such as radium.Specific as follows:
(1) neutralization: add FeSO
4, Fe
2+Oxydrolysis generates Fe (OH) under air
3Deposition, and slowly disengage acid and the alkalization waste water that neutralizes, waste water is reached efflux pH value standard;
(2) the absorption carrier band degree of depth is removed uranium: newly-generated Fe (OH)
3The deposition positively charged has adsorption preferably to the uranyl complex anion, reaches the degree of depth and removes the uranium purpose;
(3) replenish except that the used SO of radium
4 2-: required FeSO neutralizes
47H
2O is approximately 5kg/m
3, replenish SO to waste water
4 2-, its concentration can reach about 1.8g/L, satisfies the follow-up needs that remove radium technology fully;
(4) suppressing throw out returns molten: Fe
2+The acid that oxydrolysis generates is called hydration acid, a little less than the acidity, only and OH
-Reaction, and lime carbonate that can not dissolve generation and diuranate deposition realize that inhibition N-process throw out returns molten;
(5) remove radium: add BaCl
2Carry out co-precipitation and remove radium.
Embodiment
Below in conjunction with specific embodiment a kind of neutralization method that is used for alkaline uranium-containing waste water processing of the present invention is further described.
Embodiment 1
Certain uranium ore alkaline waste water is formed U:0.97mgL
-1OH
-: 3.4gL
-1Cl
-: 7.54gL
-1Ra:18.2BqL
-1Ca:4.15gL
-1Mg:0.034gL
-1
A kind of neutralization method that alkaline uranium-containing waste water is handled that is used for of the present invention:
(1) adopt the pneumatic blending mode in above-mentioned alkaline uranium-containing waste water, to add FeSO
4In with waste water in OH
-, FeSO
47H
2O consumption 5kgm
-3, regulate waste water ph 8,25 ℃ of temperature of reaction, reaction times 2h; Fe
2+Oxydrolysis generates Fe (OH) under air
3Deposition, Fe (OH)
3The adsorbable uranium ion of deposition positively charged;
(2) be under 8.0 situation in the pH value, add Na
2SO
4Replenish SO
4 2-, make SO
4 2-Concentration is 1.7gL
-1Add BaCl then
2Remove radium, co-precipitation generates Ba (Ra) SO
4, BaCl
2Add-on is controlled at 0.04gL
-1, 25 ℃ of temperature of reaction, reaction times 2h.
The result: processed waste water U is lower than 0.05mgL
-1Ra is lower than 1.0BqL
-1
Embodiment 2
Certain uranium ore alkaline waste water is formed U:0.13mgL
-1OH
-: 4.0gL
-1Ra:15.2BqL
-1Cl
-: 3.92gL
-1Ca:4.30gL
-1Mg:0.042gL
-1PH value 13.
A kind of neutralization method that alkaline uranium-containing waste water is handled that is used for of the present invention:
(1) adopt the pneumatic blending mode in above-mentioned alkaline uranium-containing waste water, to add FeSO
4In with waste water in OH
-, FeSO
4The molar weight that adds is OH in the alkaline uranium-containing waste water
-2/3 of molar weight, 30 ℃ of temperature of reaction, reaction times 1h; Fe
2+Oxydrolysis generates Fe (OH) under air
3Deposition, Fe (OH)
3The adsorbable uranium ion of deposition positively charged;
(2) be under 9 situation in the pH value, add Na
2SO
4Replenish SO
4 2-, make SO
4 2-Concentration is 2.0gL
-1Add BaCl then
2Remove radium, co-precipitation generates Ba (Ra) SO
4, BaCl
2Add-on is controlled at 0.06gL
-1, 30 ℃ of temperature of reaction, reaction times 1h.
The result: processed waste water U is lower than 0.05mgL
-1Ra is lower than 1.1BqL
-1
Embodiment 3
Certain uranium ore alkaline waste water is formed U:1.64mgL
-1OH
-: 2.0gL
-1Ra:34.5BqL
-1Cl
-: 16.24gL
-1Ca:8.51gL
-1Mg＜0.005gL
-1PH value 12.
A kind of neutralization method that alkaline uranium-containing waste water is handled that is used for of the present invention:
(1) in above-mentioned alkaline uranium-containing waste water, adds FeSO
4In with waste water in OH
-, FeSO
4The molar weight that adds is OH in the alkaline uranium-containing waste water
-1/3 of molar weight, 20 ℃ of temperature of reaction, reaction times 3h; Fe
2+Oxydrolysis generates Fe (OH) under air
3Deposition, Fe (OH)
3The adsorbable uranium ion of deposition positively charged;
(2) be under 7 situation in the pH value, add Na
2SO
4Replenish SO
4 2-, make SO
4 2-Concentration is 1.0gL
-1Add BaCl then
2Remove radium, co-precipitation generates Ba (Ra) SO
4, BaCl
2Add-on is controlled at 0.02gL
-1, 20 ℃ of temperature of reaction, reaction times 3h.
The result: processed waste water U is lower than 0.05mgL
-1Ra is lower than 1.1BqL
-1
Claims (3)
1. one kind is used for the neutralization method that alkaline uranium-containing waste water is handled, and it is characterized in that:
Add FeSO in this method alkalitropism uranium-containing waste water
4In with waste water in OH
-, FeSO
4The molar weight that adds is OH in the alkaline uranium-containing waste water
-1/3～2/3 of molar weight is regulated waste water ph 7～9,20～30 ℃ of temperature of reaction, reaction times 1～3h; Fe
2+Oxydrolysis generates Fe (OH) under air
3Deposition, Fe (OH)
3The adsorbable uranium ion of deposition positively charged;
In the pH value under 7～9 situation, like SO
4 2-Concentration is lower than 1.0～2.0gL
-1, then add Na
2SO
4Replenish SO
4 2-, make SO
4 2-Concentration is 1.0～2.0gL
-1Add BaCl then
2Remove radium, co-precipitation generates Ba (Ra) SO
4, BaCl
2Add-on is controlled at 0.02～0.06gL
-1, 20～30 ℃ of temperature of reaction, reaction times 1～3h.
2. a kind of neutralization method that alkaline uranium-containing waste water is handled that is used for according to claim 1 is characterized in that: adopt in the pneumatic blending mode alkalitropism uranium-containing waste water to add FeSO
4
3. a kind of neutralization method that alkaline uranium-containing waste water is handled that is used for according to claim 1 is characterized in that: described alkaline uranium-containing waste water CO
3 2-Content is lower than 0.1mgL
-1, OH
-Content is 1.5～4.0gL
-1, pH value 12.0～13.0, uranium content 0.1～2.0mgL
-1, radium content 10～40BqL
-1
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|---|---|---|---|
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|---|---|---|---|
| CN2011103937455A CN102491479B (en) | 2011-12-01 | 2011-12-01 | Neutralization method for treating alkali wastewater containing uranium |
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| CN102491479B CN102491479B (en) | 2013-06-26 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173617A (en) * | 2013-03-05 | 2013-06-26 | 广州有色金属研究院 | Method for removing radium from south ionic rare earth leachate |
| CN104741084A (en) * | 2015-03-03 | 2015-07-01 | 清华大学 | Uranium adsorbent applicable to alkaline environment and preparation method of uranium adsorbent |
| CN106448790A (en) * | 2016-11-11 | 2017-02-22 | 东华理工大学 | Electrochemical treatment method for uranium containing wastewater |
| CN108046400A (en) * | 2017-12-18 | 2018-05-18 | 江西晶安新资源有限公司 | A kind of neutralization method of acidity uranium-containing waste water |
| CN111170474A (en) * | 2020-01-21 | 2020-05-19 | 西南科技大学 | Method for removing uranium in ryegrass-enriched degradation residual liquid by microorganisms under aerobic condition |
| CN111204880A (en) * | 2020-01-21 | 2020-05-29 | 西南科技大学 | Method for removing uranium in ryegrass-enriched degradation residual liquid by microorganisms under anaerobic condition |
| CN114014463A (en) * | 2021-11-08 | 2022-02-08 | 核工业北京化工冶金研究院 | Underground water surface treatment method and ex-service treatment method of in-situ leaching uranium mining base |
| CN114853208A (en) * | 2022-04-27 | 2022-08-05 | 中陕核工业集团综合分析测试有限公司 | Method for harmless treatment and resource utilization of associated mine radioactive acidic wastewater |
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2011
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173617A (en) * | 2013-03-05 | 2013-06-26 | 广州有色金属研究院 | Method for removing radium from south ionic rare earth leachate |
| CN103173617B (en) * | 2013-03-05 | 2014-07-09 | 广州有色金属研究院 | Method for removing radium from south ionic rare earth leachate |
| CN104741084A (en) * | 2015-03-03 | 2015-07-01 | 清华大学 | Uranium adsorbent applicable to alkaline environment and preparation method of uranium adsorbent |
| CN106448790A (en) * | 2016-11-11 | 2017-02-22 | 东华理工大学 | Electrochemical treatment method for uranium containing wastewater |
| 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 |
| CN108046400A (en) * | 2017-12-18 | 2018-05-18 | 江西晶安新资源有限公司 | A kind of neutralization method of acidity uranium-containing waste water |
| CN111170474A (en) * | 2020-01-21 | 2020-05-19 | 西南科技大学 | Method for removing uranium in ryegrass-enriched degradation residual liquid by microorganisms under aerobic condition |
| CN111204880A (en) * | 2020-01-21 | 2020-05-29 | 西南科技大学 | Method for removing uranium in ryegrass-enriched degradation residual liquid by microorganisms under anaerobic condition |
| CN114014463A (en) * | 2021-11-08 | 2022-02-08 | 核工业北京化工冶金研究院 | Underground water surface treatment method and ex-service treatment method of in-situ leaching uranium mining base |
| CN114853208A (en) * | 2022-04-27 | 2022-08-05 | 中陕核工业集团综合分析测试有限公司 | Method for harmless treatment and resource utilization of associated mine radioactive acidic wastewater |
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| CN102491479B (en) | 2013-06-26 |
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