CN106205760B - A kind of waste water treatment process exempted in rare earth extraction waste water with slag radioactivity - Google Patents
A kind of waste water treatment process exempted in rare earth extraction waste water with slag radioactivity Download PDFInfo
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- CN106205760B CN106205760B CN201610669577.0A CN201610669577A CN106205760B CN 106205760 B CN106205760 B CN 106205760B CN 201610669577 A CN201610669577 A CN 201610669577A CN 106205760 B CN106205760 B CN 106205760B
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- waste water
- rare earth
- slag
- earth extraction
- radioactivity
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- 239000002351 wastewater Substances 0.000 title claims abstract description 63
- 239000002893 slag Substances 0.000 title claims abstract description 38
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 36
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 36
- 238000000605 extraction Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000008569 process Effects 0.000 title claims abstract description 18
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 13
- 230000002285 radioactive effect Effects 0.000 claims abstract description 26
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 4
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 4
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 3
- 210000000481 breast Anatomy 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000002474 experimental method Methods 0.000 description 15
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 12
- 229910052776 Thorium Inorganic materials 0.000 description 12
- 229910052770 Uranium Inorganic materials 0.000 description 12
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 12
- 239000013049 sediment Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000008394 flocculating agent Substances 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 231100000225 lethality Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003904 radioactive pollution Methods 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- G21F9/20—Disposal of liquid waste
-
- 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
-
- 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
- G21F9/10—Processing by flocculation
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The present invention provides the waste water treatment process exempted in a kind of rare earth extraction waste water with slag radioactivity, mainly including following steps：（1）The pH to 13 that alkali adjusts waste water is added in rare earth extraction waste water, radioactive element is made to form solid and is precipitated；（2）To step（1）Flocculant is added in the water of middle generation, is stirred, precipitation makes the solid to be formed be detached with waste water；（3）To step（2）It is added in the water of middle generation in milk of lime and acid waste water, adjusting pH to 7 10 forms neutralization slag, generated neutralization slag radioactivity is exempted.Radioactive element in rare earth extraction waste water of the present invention is removed when pH is acid.Remain in after radioactive element enrichment that radioactive element is extremely low in waste water, so as to make the radioactive element content in neutralization slag seldom, radioactive level reaches Wave gear pair, can be used as general solidification disposal of waste, greatly reduces in radioactivity and the processing cost of slag.
Description
Technical field
The present invention relates to field of industrial production, more particularly to controlling for extraction wastewater generated in being produced in rare-earth smelting
Reason, belongs to environment protection treating field.
Background technology
Uranium is usually associated in rare-earth mineral（U）, thorium（Th）Natural radionuclides are waited, during Rare Earth Production, this
A little radionuclides are often enriched in intermediate products and " three wastes ", so that there are radioactivity for most of process of Rare Earth Production
Pollution.Radioactive pollution has the characteristics that endanger that concealment is strong, lethality is big, harmfulness is big and pollution sources are difficult to destroy,
Radiological hazard is brought to workplace and ambient enviroment.
In rare-earth smelting technique, the acid extract waste water that rare earth ore concentrate is formed through sour molten, extraction contains a certain amount of uranium
With thorium element.It is a kind of strongly acid wastewater to extract bothersome, in existing rare earth extraction wastewater treatment, directly using the side neutralized
Formula adjusts waste water to neutrality, and the heavy metal element and radioactive element in waste water are formed with alkali to be precipitated, and is largely neutralized
Slag.Since extraction wastewater is directly by neutralizing, containing a large amount of radioactive element in neutralization slag, belongs to low and put solid waste,
Its ionising radiation contained has carcinogenesis and hereditary effect to human body and causes physiochemical indice abnormal, it is therefore desirable to logical
Crossing special processing could safe storage.
At present for containing in radioactive RE waste water and slag, the mode for library storage of opening a position generally is taken to dispose, needs to accord with
It closes《Radwaste safety management regulations》, great amount of cost is increased to enterprise, also brings danger to the health of staff
Evil.At present, the existing treatment technology of neutralization slag that rare-earth smelting factory generates is to build library to keep in, since the ability of repository is limited,
Has there is the phenomenon that " swell-warehouse " in most of enterprise, it is powerless bear more and more to have it is radioactive in and slag.
Invention content
The content of present invention is higher for existing rare earth extraction waste water radioactive element content, and what waste water treatment process generated contains
In radioactivity and slag yield is big, and the problem of cannot function as general fixed-end forces, and disclosing a kind of completely new makes neutralization slag can
To reach the rare earth extraction waste water treatment process that radioactivity exempts standard.Mainly include following steps：
（1）The pH to 1-3 that alkali adjusts waste water is added in rare earth extraction waste water, radioactive element is made to form solid and is precipitated；
（2）To step（1）Flocculant is added in the water of middle generation, is stirred, precipitation makes the solid to be formed be detached with waste water；
（3）To step（2）The water of middle generation, adds in milk of lime and acid waste water, adjusting pH to 7-10 form neutralization slag,
Generated neutralization slag radioactivity is exempted.
Preferably, step（1）The middle pH for adjusting waste water is 2.3-2.8.
Preferably, step（2）In add flocculant as non-ionic PAM, dosage 4-8mg/L.
Preferably, step（3）Middle feeding lime breast to pH be 8-9.
The invention discloses a kind for the treatment of process of rare earth extraction waste water, and the present invention has the following advantages：
（1）Radioactive element is removed by enrichment.The neutralization of rare earth extraction waste water can be divided into two parts by the present invention, according to putting
The pH ranges that penetrating property element forms precipitation from other elements are different, and it is heavy that radioactive element can just be formed when pH is acid with alkali
It forms sediment.Therefore, the first step first adjusts wastewater pH to 1-3, is enriched with the radioactive elements such as thorium and uranium in waste water, passes through precipitation
The form removal of object, removal effect is good, and the step for the low waste residue yield of putting that is formed it is small, greatly reduce containing radioactivity
The yield of solid waste.
（2）Realize that the radioactivity for neutralizing slag is exempted.In the present invention, radioactive element in rare earth extraction waste water is acid in pH
It is removed during property.Therefore, remain in after radioactive element enrichment that radioactive element is extremely low in waste water, so as to make in neutralization slag
Radioactive element content is seldom, and radioactive level reaches Wave gear pair, can be used as general solidification disposal of waste, greatly reduce in radioactivity
With the processing cost of slag.
Specific embodiment
With reference to embodiment, the present invention is furture elucidated, it should be understood that following specific embodiments are only used for
It is bright the present invention rather than limit the scope of the invention.
Embodiment 1
Experiment carries out in the laboratory of Nanjing Ge Luote environmental projects limited company.Rare earth extraction gives up used in experiment
Water is derived from certain Rare Earth Enterprises.Sodium hydroxide being added in into waste water in experiment and adjusting pH to 1, adding in the PAM flocculants of 4mg/L makes analysis
Go out solid flocculation, filter and survey the quantity of slag, the content of thorium and uranium before and after detection process in waste water, stone is added in most backward waste water
Grey breast adjusts pH to 7 and forms the neutralization slag that radioactive level reaches Wave gear pair.
Embodiment 2
Experiment carries out in the laboratory of Nanjing Ge Luote environmental projects limited company.Rare earth extraction gives up used in experiment
Water is derived from certain Rare Earth Enterprises.Sodium hydroxide being added in into waste water in experiment and adjusting pH to 3, adding in the PAM flocculants of 8mg/L makes analysis
Go out solid flocculation, filter and survey the quantity of slag, the content of thorium and uranium before and after detection process in waste water, stone is added in most backward waste water
Grey breast adjusts pH to 10 and forms the neutralization slag that radioactive level reaches Wave gear pair.
Embodiment 3
Experiment carries out in the laboratory of Nanjing Ge Luote environmental projects limited company.Rare earth extraction gives up used in experiment
Water is derived from certain Rare Earth Enterprises.Sodium hydroxide being added in into waste water in experiment and adjusting pH to 2, adding in the PAM flocculants of 6mg/L makes analysis
Go out solid flocculation, filter and survey the quantity of slag, the content of thorium and uranium before and after detection process in waste water, stone is added in most backward waste water
Grey breast adjusts pH to 8 and forms the neutralization slag that radioactive level reaches Wave gear pair.
Embodiment 4
Experiment carries out in the laboratory of Nanjing Ge Luote environmental projects limited company.Rare earth extraction gives up used in experiment
Water is derived from certain Rare Earth Enterprises.Sodium hydroxide being added in into waste water in experiment and adjusting pH to 2.5, adding in the PAM flocculants of 5mg/L makes
Solid flocculation is precipitated, filters and surveys the quantity of slag, the content of thorium and uranium before and after detection process in waste water, added in most backward waste water
Milk of lime adjusts pH to 9 and forms the neutralization slag that radioactive level reaches Wave gear pair.
It measures and analyzes
Experiment equipment：PH analyzers, electronic balance, magnetic stirring apparatus, beaker, filter paper
Testing index：PH is measured using pH analyzers；Sediment weight：Baking oven drying, emperor's balance weigh；Thorium in waste water
And uranium content：ICP-MS is measured；
Experimental data is analyzed and counted using 2003 softwares of Word Office and Excel softwares.
The pH of waste water, thorium and uranium concentration, the good dry weight data of sediment are as shown in table 1 before and after experiment.
1 experimental result data of table
| Processing | pH | Th (μg/L) | U (μg/L) | The quantity of slag (mg/L) |
| Rare earth extraction waste water | 0.25 | 12.5 | 30.5 | |
| It adds in NaOH solution and pH is transferred to 2.5, add in PAM, dosage 6mg/L, filtering | 2.5 | 0 | 2.5 | 86.7 |
| It adds in NaOH solution and pH is transferred to 4.5, add in PAM, dosage 6mg/L, filtering | 4.5 | 0.25 | 1 | 343.3 |
When the pH of waste water being transferred to 2.5 with NaOH solution it can be seen from 1 data of table, the thorium and uranium element in waste water are exhausted
It is most of all to precipitate down, pH to be further turned up after this, the concentration variation of thorium and uranium is little, but due in waste water
Other metal ions contained can also be precipitated by the form of hydroxide, so sediment weight when pH is 4.5 is pH is
About 4 times of sediment weight when 2.5, this part of sediment belong to low and put solid waste, and processing cost of disposal is higher, so amount is smaller more
Good, therefore, the suitable pH in this technique is 2.5 or so.
Can be obtained from radioactive element removal experiment, added in into waste water NaOH solution adjust the pH value of waste water can be with
Success removes the thorium and uranium element in waste water, reduces the radioactivity of waste water, thus can be effective in follow-up neutralisation treatment step
Reduce the radioactivity for neutralizing slag.
The technical means disclosed in the embodiments of the present invention is not limited only to the technological means disclosed in the above embodiment, further includes
By more than technical characteristic arbitrarily the formed technical solution of combination.It should be pointed out that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (7)
1. the waste water treatment process exempted in a kind of rare earth extraction waste water with slag radioactivity, which is characterized in that mainly including following
Step：（1）The pH that alkali adjusts waste water is added in rare earth extraction waste water, radioactive element is made to form solid and is precipitated；
（2）To step（1）Flocculant is added in the water of middle generation, is stirred, precipitation makes the solid to be formed be detached with waste water；
（3）To step（2）It is added in the water of middle generation in milk of lime and acid waste water, adjusting pH formation neutralization slags is generated
Slag radioactivity is neutralized to exempt.
2. the waste water treatment process exempted in rare earth extraction waste water as described in claim 1 with slag radioactivity, which is characterized in that
The step（1）The middle pH for adjusting waste water is 1-3.
3. the waste water treatment process exempted in rare earth extraction waste water as claimed in claim 2 with slag radioactivity, which is characterized in that
The step（1）The middle pH for adjusting waste water is 2.3-2.8.
4. the waste water treatment process exempted in rare earth extraction waste water as described in claim 1 with slag radioactivity, which is characterized in that
The step（2）In add flocculant as non-ionic PAM.
5. exist in rare earth extraction waste water as described in claim 1 or 4 with the waste water treatment process of slag radioactivity exemption, feature
In the step（2）The dosage 4-8mg/L of middle flocculant.
6. the waste water treatment process exempted in rare earth extraction waste water as described in claim 1 with slag radioactivity, which is characterized in that
The step（3）Middle feeding lime breast to pH be 7-10.
7. the waste water treatment process exempted in rare earth extraction waste water as claimed in claim 6 with slag radioactivity, which is characterized in that
The step（3）Middle feeding lime breast to pH be 8-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610669577.0A CN106205760B (en) | 2016-08-16 | 2016-08-16 | A kind of waste water treatment process exempted in rare earth extraction waste water with slag radioactivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610669577.0A CN106205760B (en) | 2016-08-16 | 2016-08-16 | A kind of waste water treatment process exempted in rare earth extraction waste water with slag radioactivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106205760A CN106205760A (en) | 2016-12-07 |
| CN106205760B true CN106205760B (en) | 2018-06-19 |
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| CN201610669577.0A Active CN106205760B (en) | 2016-08-16 | 2016-08-16 | A kind of waste water treatment process exempted in rare earth extraction waste water with slag radioactivity |
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3677013B2 (en) * | 2002-06-20 | 2005-07-27 | 財団法人産業創造研究所 | Method for separating and recovering elements from radioactive liquid waste |
| JP4452837B2 (en) * | 2005-09-26 | 2010-04-21 | 国立大学法人静岡大学 | Extraction separation method |
| CN103288248B (en) * | 2013-07-01 | 2015-03-11 | 全南包钢晶环稀土有限公司 | Combined treatment method for rear earth smelting/separating wastewater |
| CN104835545B (en) * | 2015-03-19 | 2017-03-29 | 西南科技大学 | A kind of deep purifying and recovery method of the fluorine-containing uranium radioactive liquid waste of high salt |
| CN105448373B (en) * | 2015-11-06 | 2018-06-01 | 西南科技大学 | A kind of uranium-containing waste water with high salt or waste liquid quickly remove uranium salt reduction method |
| CN105967424A (en) * | 2016-06-28 | 2016-09-28 | 中铝广西国盛稀土开发有限公司 | Method for recycling rare earth extraction residual wastewater with high sodium salt content |
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| CN106205760A (en) | 2016-12-07 |
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