CN106507865B - Add O2 in-situ leaching uranium techniques in heavy carbonic root type subsoil water - Google Patents
Add O2 in-situ leaching uranium techniques in heavy carbonic root type subsoil waterInfo
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- CN106507865B CN106507865B CN200910125409.5A CN200910125409A CN106507865B CN 106507865 B CN106507865 B CN 106507865B CN 200910125409 A CN200910125409 A CN 200910125409A CN 106507865 B CN106507865 B CN 106507865B
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Abstract
The present invention provides a kind of heavy carbonic root type subsoil water and adds O2Uranium extracting process is leached, which adopts the uranium ore layer in Situ Leaching method exploitation heavy carbonic root type water-bearing layer.The technique is by O2Underground is injected after directly mixing with leaching solution, containing HCO3 -In subsoil water after oxygen, uranium in Oxidation Leaching Ore is formed and contains [UO2(CO3)3]4-Or [UO2(CO3)2]2-The leachate of complex anion, then pulls out earth's surface, delivers to hydrometallurgy operation and is processed.The present invention adds O2As oxidant, using the HCO in heavy carbonic root type subsoil water3 -Ion makees the leaching agent of uranium, be capable of effective control electroless Ni-P-C-O plating generation, improve in-situ leaching uranium leaching rate.Relatively conventional acid system is leached and alkaline Leaching technique, is reduced process costs, is preferably protected mining environment.From in terms of result of the test, using in heavy carbonic root type subsoil water plus O2The uranium concentration of leaching can reach 30mg/L, meet industrial requirement.
Description
Technical field
The present invention relates to a kind of process of in-situ leaching uranium, particularly a kind of using weight carbon
Acid group type subsoil water adds O2In-situ leaching uranium process.
Background technology
In-situ leaching uranium (abbreviation ground-dipping uranium extraction) is by the note from earth drilling to ledge
The leaching solution for preparing by a certain percentage is injected into ore bed by liquid well, in the leaching solution of injection and Ore
Useful component contact there is chemical reaction, the soluble compound of generation is made in diffusion and convection current
Chemical reaction zone is left with enters formation leachate along the solution liquid stream of ore bed infiltration migration；
Leachate is promoted to earth's surface through ore bed from drawing liquid well, and the leachate of extraction is delivered to recovery workshop
The PROCESS FOR TREATMENT such as ion exchange are carried out, qualified products are finally obtained.In-situ leaching uranium is a kind of
Centralized procurement, smelting are in the new uranium mining method of one.In-situ leaching uranium method is widely used in
Permeable sandrock-type uranium deposit.
In-situ leaching uranium is leached by underground and leachate processes two large divisions and constitutes.Soak in ore body
Go out part and be divided to two classes according to the difference of the leaching solution for selecting：Acid in-situ leaching and alkaline in situ leach.Acid system
Ground leaching is exactly the dipped journey in ground for using acid solution as leachant.Can be used as the molten leaching of acid in-situ leaching
The reagent of agent has：Sulphuric acid, nitric acid, hydrochloric acid etc..Alkaline in situ leach is as molten using alkaline solution
The dipped journey in the ground of preserved material.Can mainly have as the leachant of alkaline in situ leach：Sodium carbonate, ammonium carbonate,
Sodium bicarbonate, ammonium hydrogen carbonate etc..Acid system easily causes underground ore bed blocking, and acid-base method is not
The pollution for causing subsoil water with degree.In view of the deficiency that acid system and alkaline Leaching are present, crow
Hereby the country such as other Bolkestein, Kazakhstan carries out for the higher uranium deposit of carbonate content
Weak-acid leaching technical study, mainly uses the sulfuric acid solution of low concentration while making using air
HCO is generated for oxidant with the carbonate reaction in Ore3 -, HCO3 -Again with Ore in uranium
Mineral react, and generate uranyl carbonate, reach the purpose of leaching.Uranium technology is adopted with alkaline in situ leach is
The main U.S. has carried out the research that alkalescence (neutrality) is leached, using CO2It is suitably added simultaneously
A certain amount of sodium bicarbonate makees leaching agent.These researchs and application are directed to some ground of their this country
The exploitation in leaching mine serves good impetus.
Uranium-bearing ore bed is found that in China somewhere in bicarbonate root type water-bearing layer.These stratum because
Carbonate content is high, and the bicarbonate radical in water-bearing layer has reached 2.6g/L or so, using traditionally
Dipping uranium extraction method occurs in that various problems.Carbonatite content in Ore is higher, leaches acid consumption greatly,
The acidifying cycle is long, and Ore is more with acid consumpting substance in subsoil water, is not suitable for using conventional acidleach skill
Art.During using conventional alkaline Leaching, need to consume substantial amounts of chemical reagent, meeting behind injection underground
Change the chemical composition of subsoil water, formation blockage also easily occurs in leaching process.Even with
The alkalescence leaching of the Weak-acid leaching or addition sodium bicarbonate of above-mentioned country's research also has same
Problem.
Content of the invention
It is an object of the invention to provide adding O in a kind of heavy carbonic root type subsoil water2Situ Leaching
Uranium extracting process.Uranous in uranium ore only initial oxidation is just easily moved into after hexavalent uranium
Move, the oxidation reaction of uranium is as follows：
2UO2+O2→2UO3
Carbonate or bicarbonate radical complex reaction in hexavalent uranium and leaching solution, generates uranyl carbonate
Ion in the solution stable existence, form leachate.The complex reaction of uranium is as follows：
UO3+2HCO3 -→UO2(CO3)2 2-+H2O
UO3+3CO3 2-+H2O→UO2(CO3)3 4-+2OH-
UO2(CO3)2 2-+HCO3 -→UO2(CO3)3 4-+H+
Some stratum are high because of carbonate content, and the heavy carbonic root of higher concentration is contained in water-bearing layer containing ore deposit
Type subsoil water, plus O2First the uranium of underground uranium ore layer is aoxidized, is recycled in natural groundwater
Heavy carbonic root (HCO3 -) complexing by Uranium extraction formed uranium-bearing leachate, its leaching process
It is similar to the inverse process of Uranium Deposits process.
Present invention process only adds O in water-bearing layer containing ore deposit2Gas, does not add and can change ground
Other chemical reagent compositions of lower water, can reduce the generation of electroless Ni-P-C-O plating to greatest extent, subtract
Light pollution of the in-situ leaching uranium to groundwater environment, the uranium concentration of its leachate can also reach
The requirement of industrialness production.
Realize the technical scheme of the object of the invention：A kind of heavy carbonic root type subsoil water adds O2Leaching
Go out uranium extracting process, which adopts the uranium ore in Situ Leaching method exploitation heavy carbonic root type water-bearing layer
Layer.The technique injects underground after oxygen is directly mixed with leaching solution, containing HCO3 -Underground
In water after oxygen, uranium in Oxidation Leaching Ore is formed and contains [UO2(CO3)3]4-Or
[UO2(CO3)2]2-The leachate of complex anion, then pulls out earth's surface, and delivering to hydrometallurgy operation is carried out
Process.
A kind of heavy carbonic root type subsoil water adds O as mentioned above2Uranium extracting process is leached, when mineral deposit ground
HCO in lower water3 -Content is in the range of 1.0～3.0g/L, pH value at 6.2～8.9, injection
Oxygen concentration is 200～400mg/L；With the carrying out of molten leaching reaction, if subsoil water Solution H CO3 -
Content supplements CO less than 1.0g/L2And adjust liquid filling pressure in the range of 0.5～0.7MPa,
Maintain the HCO of its subsoil water3 -Content is in the range of 1.0～3.0g/L.
A kind of heavy carbonic root type subsoil water adds O as mentioned above2Uranium extracting process is leached, the initial stage soaks
Go out, note oxygen concentration is 400mg/L；When the concentration of residual oxygen in leachate is in 10mg/L or so
When, note oxygen concentration is reduced to 200mg/L；When leaching rate reaches 60～70%, oxygen concentration is noted
50～150mg/L is down to, until leach terminating.
A kind of heavy carbonic root type subsoil water adds O as mentioned above2Leach uranium extracting process, its technique
The leaching solution for adopting is for the subsoil water containing bicarbonate radical extracted out from underground, or other contain carbonic acid
The aqueous solution of hydrogen radical.
Effect of the invention is that：
Leached using heavy carbonate subsoil water oxygenation, be a kind of cost-effective ground dipping uranium extracting process
Method, better than the alkaline Leaching system such as ammonium carbonate/ammonium hydrogen carbonate, because ammonium carbonate/ammonium hydrogen carbonate
In NH4 +Calcium, sodium ion exchange with being contained in stratum in clay, makes clay swell, makes
Into jamming of ore bed, it is unfavorable for the leaching process of metal；Free NH4 +Ion also pollutes underground
Water.
The in-situ leaching uranium process of utilization heavy carbonic root type subsoil water of the present invention,
Add O2As oxidant, using the HCO in heavy carbonic root type subsoil water3 -Ion makees uranium
Leaching agent or chelating agent, are capable of the generation of effective control electroless Ni-P-C-O plating, raising Situ Leaching and adopt
The leaching rate of uranium.Relatively conventional acid system is leached and alkaline Leaching technique, reduces process costs,
Easy to operate, preferably protect mining environment.From the point of view of result of the test, using heavy carbonic root
Add O in type subsoil water2The uranium concentration average energy of leaching reaches 30mg/L or so, meets industry
The requirement of production.
Specific embodiment
With reference to specific embodiment to adding O in heavy carbonic root type subsoil water of the present invention2
In-situ leaching uranium technique is further described.
Embodiment 1
Heavy carbonic root type subsoil water in-situ leaching uranium of the present invention is adopted in certain uranium mining area
Technique.The mining area water-bearing layer containing ore deposit water yield 27m3/ d, specific capacity 0.01L/s m, water
Position buried depth 5.3m, artesian head height 230m, infiltration coefficient 0.02m/d.Uranium-bearing layer top bottom
Plate is mainly mud stone, and thickness is more stable, and water isolating is preferable.The subsoil water chemical conversion of uranium-bearing water-bearing layer
Classifying type is with HCO3- Na and HCO3Based on Cl-Na types, salinity 3.5g/L, 15 DEG C of water temperature,
PH value 6.8, Eh：150mV, HCO3 -：2.0g/L, Cl-：280mg/L, SO4 2-：
170mg/L, Fe2+/Fe3+：0.5, O2＜ 2mg/L, H2S seldom has found that the hydrology is geochemical
Learn environment and be in weak oxide-reduction transition carrier state.Comprise the following steps that：
(1) oxygen pre-oxidation ore bed is noted
Oxygen can be made to be sufficiently mixed with leaching solution by pipe-line mixer, then be injected into ground
Under.The leaching solution that adopts for the subsoil water containing bicarbonate radical extracted out from underground, or other contain
The aqueous solution of bicarbonate radical.
HCO in the subsoil water of mineral deposit3 -Content is 2.0g/L, pH value is 6.8；The leaching initial stage,
Note oxygen concentration is 400mg/L；Concentration of residual oxygen in leachate is noted in 10mg/L or so
Oxygen concentration is reduced to 200mg/L or so；When leaching rate reaches 60%, note oxygen concentration is down to
150mg/L, until leach terminating, stops oxygenation.
With the carrying out of molten leaching reaction, if subsoil water Solution H CO3 -Ion concentration is less than 1.0g
/ L, in addition to adding appropriate oxygen according to different times, in addition it is also necessary to the appropriate CO of supplement2
Gas simultaneously adjusts liquid filling pressure to 0.7MPa so as to the HCO of underground aqueous solution3 -Ion concentration
Stablize in the range of 1.0～3.0g/L.
(2) the water-soluble leaching uranium in heavy carbonic root type underground is utilized
In natural heavy carbonic root type subsoil water after oxygen, the uranium in Ore is aoxidized and leaches,
Formed and contain [UO2(CO3)3]4-[UO2(CO3)2]2-The leachate of ion, is drawn to earth's surface, leaching
Go out addition carbon dioxide in liquid, deliver to hydrometallurgy operation and processed.
Using effect：
(1) drill average drawing liquid amount about 7.0m3/h；There is no electroless Ni-P-C-O plating.
(2) the average uranium concentration of leachate about 28mg/L；Reach the requirement of industrialness production.
(3) ton metal consumption CO2For 22t；Ton metal consumption O2For 20t；Cost compared with
Low, other chemical reagent are not added in technique, preferably protect groundwater environment.
Embodiment 2
Heavy carbonic root type subsoil water in-situ leaching uranium of the present invention is adopted in certain uranium mining area
Technique.The mining area water-bearing layer containing ore deposit water yield 108m3/ d, specific capacity 0.03L/s m, water
Position buried depth 7m, artesian head height 260m, infiltration coefficient 0.23m/d.Uranium-bearing layer roof and floor
Predominantly mud stone, thickness are more stable, and water isolating is preferable.The subsoil water chemical conversion point of uranium-bearing water-bearing layer
Type is with HCO3- Na and HCO3Based on Cl-Na types, salinity 5.7g/L, 16 DEG C of water temperature,
PH value 8.4, Eh：400mV, HCO3 -：3.0g/L, Cl-：640mg/L, 8O4 2-：
680mg/L, Fe2+/Fe3+：1.5, O2＜ 1mg/L, hydro-geochemical environment is in weak
Redox zone state.Comprise the following steps that：
(1) oxygen pre-oxidation ore bed is noted
Oxygen can be made to be sufficiently mixed with leaching solution containing bicarbonate radical by pipe-line mixer, then will
Which injects underground.
HCO in the subsoil water of mineral deposit3 -Content is 3.0g/L, pH value is 8.4；The leaching initial stage,
Note oxygen concentration is 300mg/L；Concentration of residual oxygen in leachate is noted in 10mg/L or so
Oxygen concentration is reduced to 200mg/L or so；When leaching rate reaches 70%, note oxygen concentration is down to
50mg/L, until leach terminating, stops oxygenation.
With the carrying out of molten leaching reaction, subsoil water Solution H CO3 -Content is needed less than 1.0g/L
The appropriate CO of supplement2, regulation liquid filling pressure is 0.6MPa, controls subsoil water Solution H CO3 -
Stable content is in the range of 1.0～3.0g/L.
(2) the water-soluble leaching uranium metal in bicarbonate radical underground is utilized
In natural heavy carbonic root type subsoil water after oxygen, the uranium in Ore is aoxidized and leaches,
Formed and contain [UO2(CO3)3]4-[UO2(CO3)2]2-The leachate of ion, is drawn to earth's surface, leaching
Go out addition carbon dioxide in liquid, deliver to hydrometallurgy operation and processed.
The using effect of leaching：
(1) the average drawing liquid amount about 6.2m in group hole3/h；There is no electroless Ni-P-C-O plating.
(2) the average uranium concentration of leachate about 30mg/L；Reach the requirement of industrialness production.
(3) ton metal consumption CO2For 18t；Ton metal consumption O2For 17t；Cost compared with
Low, other chemical reagent are not added in technique, preferably protect groundwater environment.
Embodiment 3
Heavy carbonic root type subsoil water in-situ leaching uranium of the present invention is adopted in certain uranium mining area
Technique.The mining area water-bearing layer containing ore deposit water yield 90m3/ d, specific capacity 0.02L/s m, water
Position buried depth 6m, artesian head height 254m, infiltration coefficient 0.12m/d.Uranium-bearing layer roof and floor
Predominantly mud stone, thickness are more stable, and water isolating is preferable.The subsoil water chemical conversion point of uranium-bearing water-bearing layer
Type is with HCO3- Na and HCO3Based on Cl-Na types, salinity 5g/L, 16 DEG C of water temperature,
PH value 7.0, Eh：300mV, HCO3 -：1.2g/L, Cl-：500mg/L, SO4 2-：500
Mg/L, Fe2+/Fe3+：1, O2＜ 1mg/L, H2S seldom have found, hydrogeochemistry ring
Border is in weak oxide-reduction transition carrier state.Comprise the following steps that：
(1) oxygen pre-oxidation ore bed is noted
Oxygen can be made to be sufficiently mixed with leaching solution by pipe-line mixer, then be injected into ground
Under.The leaching solution that adopts for the subsoil water containing bicarbonate radical extracted out from underground, or other contain
The aqueous solution of bicarbonate radical.
HCO in the subsoil water of mineral deposit3 -Content is 1.2g/L, pH value is 7.0；The leaching initial stage,
Note oxygen concentration is 250mg/L；Concentration of residual oxygen in leachate is noted in 10mg/L or so
Oxygen concentration is reduced to 200mg/L or so；When leaching rate reaches 70%, note oxygen concentration is down to
100mg/L, until leach terminating, stops oxygenation.
With the carrying out of molten leaching reaction, subsoil water Solution H CO3 -Content is needed less than 1.2g/L
The appropriate CO of supplement2, regulation liquid filling pressure is 0.5MPa, controls subsoil water Solution H CO3 -
Stable content is in the range of 1.0～3.0g/L.
(2) the water-soluble leaching uranium in heavy carbonic root type underground is utilized
In natural heavy carbonic root type subsoil water after oxygen, the uranium in Ore is aoxidized and leaches,
Formed and contain [UO2(CO3)3]4-[UO2(CO3)2]2-The leachate of ion, is drawn to earth's surface, leaching
Go out addition carbon dioxide in liquid, deliver to hydrometallurgy operation and processed.
The using effect of leaching：
(1) drill average drawing liquid amount about 6m3/h；There is no electroless Ni-P-C-O plating.
(2) the average uranium concentration of leachate about 25mg/L；Reach the requirement of industrialness production.
(3) ton metal consumption CO2For 14t；Ton metal consumption O2For 15t；Cost compared with
Low, other chemical reagent are not added in technique, preferably protect groundwater environment.
Described above is only the section Example of the present invention.It should be pointed out that for this area
For those of ordinary skill, under the premise without departing from the principles of the invention, can also make some
Deformation and improvement, also should be regarded as the protection category for belonging to the present invention.
Claims (2)
1. a kind of heavy carbonic root type subsoil water adds O2Uranium extracting process is leached, which adopts Situ Leaching
Uranium ore layer in method exploitation heavy carbonic root type water-bearing layer, it is characterised in that：The technique is straight by oxygen
Injection underground after mixing is connect with leaching solution, and the uranium in Oxidation Leaching Ore, formation contain
[UO2(CO3)3]4-Or [UO2(CO3)2]2-The leachate of complex anion, then pulls out earth's surface, send
Processed to hydrometallurgy operation；
As HCO in the subsoil water of mineral deposit3 -Content is in the range of 1.0～3.0g/L, pH value exists
When 6.2～8.9, oxygen is injected；Leaching initial stage, note oxygen concentration are 400mg/L, when in leachate
Concentration of residual oxygen in 10mg/L, note oxygen concentration be reduced to 200mg/L；When leaching rate reaches
During to 60～70%, note oxygen concentration is down to 50～150mg/L, until leach to terminate to stop oxygenation；
With the carrying out of molten leaching reaction, if subsoil water Solution H CO3 -Content is adjusted less than 1.0g/L
Section liquid filling pressure supplements CO in the range of 0.5～0.7MPa2Maintain its underground aqueous solution
HCO3 -Content is in the range of 1.0～3.0g/L.
2. a kind of heavy carbonic root type subsoil water adds O as claimed in claim 12Leach uranium extracting process,
It is characterized in that：The leaching solution that the technique is adopted is for the underground containing bicarbonate radical extracted out from underground
Water, or contain the aqueous solution of bicarbonate radical for other.
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| CN200910125409.5A CN106507865B (en) | 2009-12-30 | 2009-12-30 | Add O2 in-situ leaching uranium techniques in heavy carbonic root type subsoil water |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106930738A (en) * | 2015-12-30 | 2017-07-07 | 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 |
| CN110438353A (en) * | 2019-08-29 | 2019-11-12 | 中广核铀业新疆发展有限公司 | A kind of severely-weathered Strong oxdiative molding sand conglomerate uranium ore hydrometallurgy method |
| CN110684907A (en) * | 2019-10-23 | 2020-01-14 | 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 |
| CN110777272A (en) * | 2019-11-12 | 2020-02-11 | 核工业北京化工冶金研究院 | Use method of organic chlorine oxidant in neutral in-situ leaching uranium mining |
| CN113025816A (en) * | 2021-03-09 | 2021-06-25 | 中南大学 | Method for promoting uranium ore leaching by applying magnetic field |
| CN115506768A (en) * | 2022-09-27 | 2022-12-23 | 重庆大学 | Supercritical CO of sandstone-type uranium ore 2 Frac-dip recovery and CO 2 Sealing and storing integrated method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106930738A (en) * | 2015-12-30 | 2017-07-07 | 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 |
| 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 |
| CN110438353A (en) * | 2019-08-29 | 2019-11-12 | 中广核铀业新疆发展有限公司 | A kind of severely-weathered Strong oxdiative molding sand conglomerate uranium ore hydrometallurgy method |
| CN110684907A (en) * | 2019-10-23 | 2020-01-14 | 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 |
| 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 |
| CN110777272A (en) * | 2019-11-12 | 2020-02-11 | 核工业北京化工冶金研究院 | Use method of organic chlorine oxidant in neutral in-situ leaching uranium mining |
| CN113025816A (en) * | 2021-03-09 | 2021-06-25 | 中南大学 | Method for promoting uranium ore leaching by applying magnetic field |
| CN115506768A (en) * | 2022-09-27 | 2022-12-23 | 重庆大学 | Supercritical CO of sandstone-type uranium ore 2 Frac-dip recovery and CO 2 Sealing and storing integrated method |
| CN115506768B (en) * | 2022-09-27 | 2024-05-10 | 重庆大学 | Sandstone type uranium ore supercritical CO2Fracturing-in-situ leaching mining and CO2Sealing and storing integrated method |
| CN115725837A (en) * | 2022-11-17 | 2023-03-03 | 核工业北京化工冶金研究院 | Neutral in-situ leaching uranium mining method and system |
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