CN104726725B - Low-concentration sulfuric acid oxygen in-situ leaching uranium method - Google Patents
Low-concentration sulfuric acid oxygen in-situ leaching uranium method Download PDFInfo
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Abstract
The present invention relates to a kind of in-situ leaching uranium method of low-concentration sulfuric acid oxygen.From ore bed, original place Leaching of Gold belongs to uranium, the technique relating to reclaiming uranium from carbonate content skewness uranium deposit.The method include chemical composition of groundwater analysis, note oxygen oxidation ore bed, preparation leaching solution, leaching solution Leaching Uranium metal, maintain leaching to carry out, the step such as resin absorption.Can apply to carbonate content uranium deposit pockety, effectively control the generation of electroless Ni-P-C-O plating, improve original place and adopt the leaching efficiency of uranium, relative to conventional acid ground-dipping uranium extraction, alleviate the pollution to exploiting field groundwater environment.The effect using low-concentration sulfuric acid oxygen extract technology shows, this is a kind of effective ground dipping uranium extracting process.
Description
Technical field
The invention belongs to in-situ leaching uranium technical field, be specifically related to the former of a kind of low-concentration sulfuric acid oxygen
Ground leaches uranium extraction method.
Background technology
In-situ leaching uranium (abbreviation ground-dipping uranium extraction) is by will be by from the fluid injection well of earth drilling to ledge
The leaching solution that certain proportion prepares is injected into ore bed, and the leaching solution of injection contacts with the useful component in Ore to be sent out
Biochemical reaction, the soluble compound of generation leaves entrance edge, chemical reaction zone under diffusion and convection action
The solution liquid stream of ore bed infiltration migration is formed leachate；Leachate is promoted to earth's surface through ore bed from drawing liquid well,
The leachate extracted out is delivered to recovery workshop and carries out the PROCESS FOR TREATMENT such as ion exchange, finally obtains qualified products.
In-situ leaching uranium is that a kind of centralized procurement, smelting are in the novel oil field recovery method of one.In-situ leaching uranium method
It is widely used in permeable sandrock-type uranium deposit.
In-situ leaching uranium is leached by underground and leachate processes two large divisions and forms.Depend at ore body leaching section
Two classes are divided: acid in-situ leaching and alkaline in situ leach according to the difference of leaching solution selected.Acid in-situ leaching uses acidity exactly
Solution is as the dipped journey in ground of leachant.Can have as the reagent of acid in-situ leaching leachant: sulphuric acid, nitric acid,
Hydrochloric acid etc..Alkaline in situ leach is to use alkaline solution as the dipped journey in ground of leachant.Can be as alkaline in situ leach
Leachant mainly has: sodium carbonate, ammonium carbonate, sodium bicarbonate, ammonium hydrogen carbonate etc..
Owing to the intensity of sulfuric acid leaching uranium is big, the exploiting field production time is short, leaching rate advantages of higher, on ground, the world
Leaching is adopted uranium mine and is used widely.Kazakhstan of natural uranium yield the first big country, nearly all product at present
Product are all from acid in-situ leaching mine.It addition, the leaching mine, ground of Uzbekistan, Australia and China
Most use sulphuric acid are as leaching agent.
At certain uranium deposit that Xinjiang of China Yili Basin finds, in ore bed sand body, carbonate content change is the most multiple
Miscellaneous, content range is 0.52%～5.19%.The acid system using routine in such uranium deposit leaches,
Owing to part ore body carbonate content is high, the acidifying cycle is long, and pH value declines slowly, and leaching process unit acid consumes
Greatly, leachate uranium concentration is low.Meanwhile, leaching process the most easily occurs electroless Ni-P-C-O plating, and causes subsoil water
Pollute.
Summary of the invention
It is an object of the invention to: provide a kind of low-concentration sulfuric acid oxygen to carry out the work of in-situ leaching uranium
Skill, can apply to carbonate content uranium deposit pockety, effectively controls the generation of electroless Ni-P-C-O plating, carries
The leaching efficiency of uranium is adopted in plateau, relative to conventional acid ground-dipping uranium extraction, alleviates exploiting field groundwater environment
Pollute.
Technical scheme is as follows: a kind of low-concentration sulfuric acid oxygen in-situ leaching uranium method, including
Following steps:
Step one: note oxygen oxidation ore bed, this mineral deposit subsoil water HCO3 -Content in the range of 100～400mg/L,
PH value, in the range of 6.0～8.0, leaches the initial stage, and note oxygen concentration is 400～500mg/L；When in leachate
Concentration of residual oxygen when reaching 15mg/L, note oxygen concentration is reduced to 300mg/L；Leach mid-term, keep note oxygen
Concentration is 300mg/L；When leaching rate reaches 65%, stop injecting oxygen；
Step 2: preparation leaching solution, adds H in subsoil water2SO4, it is configured to leaching solution, according in subsoil water
HCO3-content and pH, add H2SO4Concentration be 0.3～0.5g/L, keep leaching solution pH value be 3.0～
4.0；
Step 3: leaching solution Leaching Uranium metal, leaching solution carries out complex reaction, shape with the hexavalent uranium in Ore
Become [UO2(CO3)3]4-With [UO2(CO3)3]2-, when uranium concentration is more than 10mg/L in leachate, use immersible pump
Leachate is extracted out；
Step 4: resin absorption, uses D231YT strong-base anion-exchange resin；
Also included before described step one, extract subsoil water out and carry out the step of chemical composition analysis: definitely
Lower water salinity is less than 5g/L, Cl-Concentration is less than 2g/L.
The mass exchange capacity 3.7mmol/g of the D231YT strong-base anion-exchange resin in described step 4,
Granularity 0.63～1.40mm, the wet R of wet apparent density 0.70g/ml, oozes mill rate of small round spheres >=90%.
Also include with before step 4 after described step 3: maintain and leach the step carried out, along with leaching
Constantly carry out, leachate HCO3 -Concentration constantly raises；As leachate HCO3Concentration is more than 450mg/L, will
H2SO4The concentration added is reduced to 0.1～0.2g/L, and keeping pH of leaching solution is 7.0～8.0, until leaching
Terminate.
The remarkable result of the present invention is: out well average drawing liquid amount is 5.0～6.0m3/ h, injects well average
Reservoir quantity is 2.0～2.2m3/ h, there is not obvious electroless Ni-P-C-O plating in leaching process, the average uranium concentration of leachate
It is 35～40mg/L, reaches industrial design objective.
Reagent consumption is low, and ton metallic uranium consumes H2SO4Being 9.6～11.2t, ton metallic uranium consumes O2Be 13.1～
15.0t, relative to in-situ acid uranium leaching, ton metallic uranium consumes H2SO4It is 45～60t, can reduce and produce into
This.
Relative to in-situ acid uranium leaching, the H added in subsoil water2SO4Concentration and total amount significantly reduce, permissible
Alleviate the pollution to exploiting field groundwater environment.
The effect using low-concentration sulfuric acid oxygen extract technology shows, this is a kind of effective ground-dipping uranium extraction work
Skill.
Detailed description of the invention
Embodiment 1.
The in-situ leaching uranium technique of low-concentration sulfuric acid oxygen, comprises the following steps that:
1, extract subsoil water out and carry out chemical composition analysis
Extraction ore bed subsoil water, carries out subsoil water component analysis, mainly determines the degree of mineralization of ground water and underground
Cl in water-Concentration.
Analysis result shows: subsoil water chemical conversion classifying type is SO4·HCO3-Ca Mg type, salinity is 0.76
g/L。ρ(Ca2+) it is 130.5mg/L, ρ (Mg2+) it is 57.5mg/L, ρ (SO42-) it is 230mg/L, ρ (Cl-)
For 124.2mg/L, ρ (HCO3 -) it is 130.5mg/L, pH value is 7.34, and Eh value is 314mV.
This mineral deposit degree of mineralization of ground water is less than 5g/L, subsoil water Cl-Concentration is less than 2g/L, meets utilization low concentration
The condition of sulphuric acid oxygen in-situ leaching uranium technique.
2, note oxygen oxidation ore bed
This mineral deposit subsoil water HCO3 -Content is in the range of 100～400mg/L, and pH value is in the range of 6.0～8.0.
At the leaching initial stage, note oxygen concentration is 400～500mg/L；When the concentration of residual oxygen in leachate reaches 15mg/L,
Note oxygen concentration is reduced to 300mg/L；Leaching mid-term, keeping note oxygen concentration is 300mg/L；When leaching rate reaches
When 65%, stop injecting oxygen.
3, preparation leaching solution
H is added in subsoil water2SO4, it is configured to leaching solution.According to HCO in subsoil water3 -Content and the feelings of pH
Condition, adds H2SO4Concentration be 0.4～0.5g/L, keep leaching solution pH value be 3.0～4.0.
4, leaching solution Leaching Uranium metal
Leaching solution carries out complex reaction with the hexavalent uranium in Ore, forms [UO2(CO3)3]4-With [UO2(CO3)3]2-,
When uranium concentration is more than 10mg/L in leachate, immersible pump is used to be extracted out by leachate.
5, leaching is maintained to carry out
Along with that leaches is constantly carried out, leachate HCO3 -Concentration constantly raises.As leachate HCO3Concentration is more than
450mg/L, in addition to adding appropriate oxygen according to different times, by H2SO4Add concentration be reduced to 0.1～
0.2g/L, keeping pH of leaching solution is 7.0～8.0, terminates until leaching.
6, resin absorption
Use D231YT strong-base anion-exchange resin, mass exchange capacity 3.7mmol/g, granularity
0.63-1.40mm, the wet R of the wet R of wet apparent density 0.70g/ml, wet true density 1.05g/ml, ooze mill rate of small round spheres
≥90%.When resin is saturated, adsorption capacity reaches the wet R of 122mgU/ml.
Embodiment 2.
The in-situ leaching uranium technique of low-concentration sulfuric acid oxygen, comprises the following steps that:
1, extract subsoil water out and carry out chemical composition analysis
Extraction ore bed subsoil water, carries out component analysis, mainly determines Cl in the degree of mineralization of ground water and subsoil water-
Concentration.
Analysis result shows: subsoil water chemical conversion classifying type is SO4Cl-Na type, salinity be 1.48～
1.73g/L。ρ(Ca2+) it is 7.13mg/L, ρ (Mg2+) it is 0.73mg/L, ρ (SO4 2-) it is 464.93mg/L,
ρ(Cl-) it is 324.37mg/L, ρ (HCO3 -) it is 245.95mg/L, pH value is 7.25, and Eh value is 282mV.
This mineral deposit degree of mineralization of ground water is less than 5g/L, subsoil water Cl-Concentration is less than 2g/L, meets utilization low concentration
The condition of sulphuric acid oxygen in-situ leaching uranium technique.
2, note oxygen oxidation ore bed
This mineral deposit subsoil water HCO3 -Content is in the range of 100～400mg/L, and pH value is in the range of 6.0～8.0.
At the leaching initial stage, note oxygen concentration is 400～500mg/L；Concentration of residual oxygen in leachate reaches about 15mg/L
Time, note oxygen concentration is reduced to about 300mg/L；Leaching mid-term, keeping note oxygen concentration is 300mg/L；；When
When leaching rate reaches 65%, stop injecting oxygen.
3, preparation leaching solution
H is added in subsoil water2SO4, it is configured to leaching solution.According to HCO in subsoil water3 -Content and the feelings of pH
Condition, adds H2SO4Concentration be 0.3～0.4g/L, keep leaching solution pH be 3.0～4.0.
4, leaching solution Leaching Uranium metal
Leaching solution carries out complex reaction with the hexavalent uranium in Ore, forms [UO2(CO3)3]4-With [UO2(CO3)3]2-,
When uranium concentration is more than 10mg/L in leachate, immersible pump is used to be extracted out by leachate.
5, leaching is maintained to carry out
Along with that leaches is constantly carried out, HCO in leachate3 -Concentration constantly raises.As HCO in leachate3Concentration
More than 450mg/L, in addition to adding oxygen according to different times, by H2SO4Add concentration be reduced to 0.1～
0.2g/L, keeping pH of leaching solution is 7.0～8.0, terminates until leaching.
6, resin absorption
Use D231YT strong-base anion-exchange resin, mass exchange capacity 3.7mmol/g, granularity 0.63～
1.40mm, the wet R of the wet R of wet apparent density 0.70g/ml, wet true density 1.05g/ml, ooze mill rate of small round spheres >=90%.
When resin is saturated, adsorption capacity reaches the wet R of 110mgU/ml.
Claims (4)
1. a low-concentration sulfuric acid oxygen in-situ leaching uranium method, it is characterised in that: comprise the following steps:
Step one: note oxygen oxidation ore bed, this mineral deposit subsoil water HCO3 -Content is in the range of 100～400mg/L, and pH value, in the range of 6.0～8.0, leaches the initial stage, and note oxygen concentration is 400～500mg/L；When the concentration of residual oxygen in leachate reaches 15mg/L, note oxygen concentration is reduced to 300mg/L；Leaching mid-term, keeping note oxygen concentration is 300mg/L；When leaching rate reaches 65%, stop injecting oxygen；
Step 2: preparation leaching solution, adds H in subsoil water2SO4, it is configured to leaching solution, according to HCO in subsoil water3 -Content and pH, add H2SO4Concentration be 0.3～0.5g/L, keep leaching solution pH value be 3.0～4.0；
Step 3: leaching solution Leaching Uranium metal, leaching solution carries out complex reaction with the hexavalent uranium in Ore, forms [UO2(CO3)3]4-With [UO2(CO3)3]2-, when uranium concentration is more than 10mg/L in leachate, use immersible pump to be extracted out by leachate；
Step 4: resin absorption, uses D231YT strong-base anion-exchange resin.
A kind of low-concentration sulfuric acid oxygen in-situ leaching uranium method the most according to claim 1, it is characterised in that: also included before described step one, extract subsoil water out and carry out the step of chemical composition analysis: determine that the degree of mineralization of ground water is less than 5g/L, Cl-Concentration is less than 2g/L.
A kind of low-concentration sulfuric acid oxygen in-situ leaching uranium method the most according to claim 1, it is characterized in that: the mass exchange capacity 3.7mmol/g of the D231YT strong-base anion-exchange resin in described step 4, granularity 0.63～1.40mm, the wet R of wet apparent density 0.70g/ml, oozes mill rate of small round spheres >=90%.
A kind of low-concentration sulfuric acid oxygen in-situ leaching uranium method the most according to claim 1, it is characterised in that: also include with before step 4 after described step 3: maintain and leach the step carried out, along with that leaches is constantly carried out, leachate HCO3 -Concentration constantly raises；As leachate HCO3 -Concentration is more than 450mg/L, by H2SO4The concentration added is reduced to 0.1～0.2g/L, and keeping pH of leaching solution is 7.0～8.0, terminates until leaching.
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| CN105370285B (en) * | 2015-12-15 | 2017-09-29 | 中核第四研究设计工程有限公司 | It is a kind of soak the method that level of ground water declines in mode uranium mining with preventing |
| CN106930738B (en) * | 2015-12-30 | 2019-02-26 | 新疆中核天山铀业有限公司 | Hydrochloric acid improves layer of sand permeability ground-dipping uranium extraction leaching technology |
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| CN107130122B (en) * | 2017-05-27 | 2018-11-02 | 中核通辽铀业有限责任公司 | A kind of In-situ Leaching Uranium Mine enhanced leaching method |
| CN110669950B (en) * | 2019-10-23 | 2021-06-29 | 核工业北京化工冶金研究院 | Enhanced leaching method for in-situ leaching uranium mining |
| CN110684907B (en) * | 2019-10-23 | 2021-08-17 | 核工业北京化工冶金研究院 | In-situ leaching uranium extraction leaching method for high-mineralization-degree underground water uranium ore |
| CN111020243A (en) * | 2019-11-29 | 2020-04-17 | 南华大学 | In-situ leaching uranium mining method by low-concentration sulfuric acid synergistic organisms |
| CN111101005A (en) * | 2019-11-29 | 2020-05-05 | 南华大学 | Supercritical CO2In-situ leaching uranium mining method by fluid synergistic organisms |
| CN111074068B (en) * | 2019-11-29 | 2021-06-15 | 南华大学 | Uranium mining method for sandstone uranium ore through surfactant combined acid method in-situ leaching |
| CN111455173A (en) * | 2020-04-24 | 2020-07-28 | 核工业北京化工冶金研究院 | In-situ leaching uranium mining method for sandstone-type uranium deposit |
| CN114686681B (en) * | 2020-12-30 | 2023-10-20 | 中核通辽铀业有限责任公司 | Remote uranium deposit resource recovery system and method |
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