CN102900418A - In-situ uranium leaching and mining treatment method by adding O2 into CO2 - Google Patents

In-situ uranium leaching and mining treatment method by adding O2 into CO2 Download PDF

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CN102900418A
CN102900418A CN2012104091890A CN201210409189A CN102900418A CN 102900418 A CN102900418 A CN 102900418A CN 2012104091890 A CN2012104091890 A CN 2012104091890A CN 201210409189 A CN201210409189 A CN 201210409189A CN 102900418 A CN102900418 A CN 102900418A
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resin
leaching
uranium
add
eluent
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CN102900418B (en
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苏学斌
刘乃忠
杜志明
郭忠德
沈红伟
程宗芳
李建华
牛玉清
王晓东
廖文胜
谭亚辉
成弘
姚益轩
王云霞
马连春
杨少武
张万亮
原渊
张永明
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China Nuclear Uranium Industry Co ltd
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Beijing Research Institute of Chemical Engineering and Metallurgy of CNNC
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Abstract

The invention provides an in-situ uranium leaching and mining treatment method by adding O2 into CO2. The invention comprises the steps of (1) adding O2 into leaching solution, then injecting an underground mine-water contained layer into a liquid injection pipeline, and preparing the leaching solution by adopting different oxygenation concentrations according to different underground leaching periods; (2) adding 100-300mg/L of CO2 into the leaching solution containing uranium; (3) conducting ion exchange adsorption on the leaching solution containing uranium, adopting macroporous styrene strong-base anion exchange resin, adsorbing to obtain saturated resin adsorption tail solution; and (4) washing saturated resin by adopting an eluting agent, and then analyzing uranyl carbonate ion solution to obtain Na2U2O7 sediment slurry and sediment mother liquor. According to the method, a high-temperature heating device is eliminated, so that the energy consumption and equipment investment are lowered greatly, the alkali consumption is lowered, control parameters are refined, the consumption of alkali is saved, and the production cost is lowered.

Description

A kind of CO of uranium 2Add O 2Situ Leaching exploitation processing method
Technical field
The present invention relates to a kind of ground-dipping uranium extraction infusion solution treatment process, be specifically related to a kind of CO of uranium 2Add O 2Situ Leaching exploitation processing method.
Background technology
It is to be injected into ore bed by the leaching solution that the fluid injection well from earth drilling to ledge will prepare by a certain percentage that Situ Leaching is adopted uranium, the leaching solution that injects contacts with the useful component of ore chemical reaction occurs, and the soluble compound of generation leaves chemical reaction zone and enters along forming leachate in the solution liquid stream of ore bed infiltration migration under diffusion and convection action; Leachate is promoted to the earth's surface through ore bed from the drawing liquid well, and the leachate of extraction is delivered to PROCESS FOR TREATMENT such as carrying out ion-exchange between recovery vehicle, obtains at last qualified products.The Situ Leaching uranium extraction method is widely used in permeable sandrock-type uranium deposit, is that a kind of centralized procurement, smelting are in the novel uranium mining method of one.
Situ Leaching is adopted uranium and is comprised of underground leaching and leachate processing two large divisions.Can divide two classes according to the difference of the leaching solution of selecting at the ore body leaching section: acid system ground soaks with alkaline process ground and soaks.It is exactly to use acid solution to soak process as the ground of leachant that acid system ground soaks.Can be used as the reagent that soaks leachant in acid system ground has: sulfuric acid, nitric acid, hydrochloric acid etc.It is to adopt alkaline solution to soak process as the ground of leachant that alkaline process ground soaks.Can be used as the leachant that soaks on alkaline process ground mainly contains: sodium carbonate, ammonium carbonate, sodium acid carbonate, carbonic hydroammonium etc.Acid system causes underground ore bed obstruction easily, acid-base method all in various degree caused groundwater pollution.
At present, the deficiency that exists in view of acid system and alkaline Leaching, the member country of the Commonwealth of Independent States that is celebrated with the in-situ acid uranium leaching technology for carbonate content higher (with CO 2Greater than 2%) uranium deposit launch low Ore Leaching technical study, namely utilize the sulfuric acid solution of low concentration, adopt air as the generation of the carbonate reaction in oxidant and ore HCO simultaneously 3 -, HCO 3 -Again with ore in uranium mineral reaction, generate uranyl carbonate; The U.S. that is celebrated with alkaline process ground-dipping uranium extraction technology has carried out the research that alkalescent leaches, and uses CO 2Suitably add simultaneously a certain amount of sodium acid carbonate.But for carbonate content in the Uranium deposit ore greater than 2%, underground water high salinity (5~12g/L), (2.0~3.0g/L), above-mentioned weak acid method, weak base method leach the blockage problem that all can't avoid ore bed to high carbon acid hydrogen root, and ore body leaches operation and can't effectively implement.
There are a large amount of low-grade, low infiltration sandrock-type uranium deposit in China, and carbonate content bicarbonate radical high, that contain in the aquifer, ore deposit is high in its uranium bearing mineral, and using traditionally when this class ore body, variety of issue has appearred in dipping uranium extraction method.Use conventional acidleach technology, the carbonatite content in the ore is higher, and it is large to leach sour consumption, and the acidifying cycle is long, and acid consumpting substance is many in ore and the underground water, and the pH value descends slowly, and the condition that reaches the uranium leaching needs the long time, and has caused the pollution of groundwater environment.On the other hand, carbonate content is higher in this uranium-bearing ore bed, and a large amount of leachant that alkaline process need to be prepared injects the composition that has also changed underground water after underground, simultaneously, leaches and formation blockage also occurs easily.The U.S. that uses alkaline Leaching technique to be celebrated, its alkaline Leaching scheme all remains on the pH value 8.2~8.3.Yet basic carbonate leaches underground and has formed clay swelling, and with the clay component exchange cation, such as sodium, the calcium ion-exchanged from leachate causes the formation of calcium carbonate in the leachate.And in follow-up leachate processing procedure, form fouling, what impact was produced normally carries out.During its leachate post processing, resin adsorption concentration is low, traditional direct alkaline chemical precipitation method, and alkaline consumption is too high.Residual on the poor resin after the drip washing have a large amount of chlorions or other ions, and the tail washings circulation time can inject lithic drainage, affects the leaching effect of uranium in the subsurface mineral.In addition, also can affect the again absorption of resin, need to the poor resin after the drip washing be made the transition.
Summary of the invention
For having overcome above defective, the invention provides a kind of CO of uranium 2Add O 2Situ Leaching exploitation processing method, the underground aquifer, ore deposit that contains of having caused when having avoided using acid, alkaline process ground-dipping uranium extraction is stopped up and the groundwater pollution problem.
Realize the technical scheme of the object of the invention: a kind of CO of uranium 2Add O 2Situ Leaching exploitation processing method, it comprises the steps:
(1) leaching solution adds O 2Inject the underground aquifer, ore deposit that contains by liquid injecting pipeline afterwards, the liquid filling pressure of leaching solution is controlled at 1.5Mpa~1.6Mp, O 2Adding pressure be higher than the liquid filling pressure 0.1~0.2Mpa of leaching solution; According to the difference in Underground Leaching progress stage, adopt the different preparations that oxygen concentration carries out leaching solution that adds; Concrete steps are: the initial stage leaches, and annotating oxygen concentration in the leaching solution is 400~500mg/L, when the concentration of residual oxygen in the leachate during in the 10mg/L left and right sides, annotates oxygen concentration and is reduced to 200mg/L; When leaching rate reaches 60 ~ 70%, annotate oxygen concentration and be down to 50 ~ 150mg/L, finish until leach; Described leaching solution is for containing bicarbonate radical type underground water;
(2) in leaching the leachate of uranium-bearing of gained, step (1) adds CO 2, to regulate pH value to 7~8; CO 2Addition is 100~300mg/L, CO 2Add pressure and be higher than leachate pipeline pressure 0.1~0.2Mpa;
(3) ion-exchange absorption is carried out in the leachate of the uranium-bearing of step (2) gained, adopt macropore polystyrene strong-base anion-exchange resin, obtain saturated resin and adsorption tail liquid after the absorption;
(4) adopt eluent to carry out drip washing to the saturated resin of step (3) gained, described eluent is the NaHCO of 15~20g/L 3Mixed solution with the NaCl of 80~120g/L; Then the uranyl carbonate solion that obtains is resolved, namely in the uranyl carbonate solion, add hydrochloric acid, CO to be driven 2Be acidified to pH=4.0~5.0 o'clock, stop to add hydrochloric acid; Add again NaOH and regulate pH to 12.0~13.0, the normal temperature precipitation, sedimentation time 6~12h, lower floor obtains Na 2U 2O 7The precipitation slurry, upper solution is mother liquor of precipitation of ammonium.
The CO of aforesaid a kind of uranium 2Add O 2Situ Leaching exploitation processing method adopts the pressure-bearing adsorption tower of two series connection to carry out following current ion-exchange absorption with pressure uranium in its step (3), wherein first adsorption tower internal pressure is at 0.2MPa ~ 0.3MPa, and second adsorption tower internal pressure is less than 0.1Mpa.
The CO of aforesaid a kind of uranium 2Add O 2Situ Leaching exploitation processing method, after its step (4) drip washing finishes, utilize adsorption tail liquid regenerating resin transition, namely with compressed air solution in the adsorption tower is dried up, use adsorption tail liquid recoil resin bed, tail washings is 4~6BV/h by the flow velocity of resin, and the resin in the resin tower fully is evenly distributed, remove foreign material residual between most of resin particle and strippant composition, till observation recoil waste water is extremely limpid; Again with adsorption tail liquid with flow velocity 0.5~1BV/h by resin bed, carry out resin regeneration, the time is 1~2 hour, with about 1~2 hour of clear water following current flushing resin, treat that wash water clears after, again water backwash, colourless to eluate, without till the muddiness.
The CO of aforesaid a kind of uranium 2Add O 2Situ Leaching exploitation processing method, its step (4) gained contain Na 2CO 3, NaCl and NaOH mother liquor of precipitation of ammonium be formulated as the eluent that the drip washing resin is used, if the concentration that chlorion concentration requires less than eluent in the mother liquor, then the salt adding acid for adjusting pH is in the eluent scope, adding sodium chloride adjusting mother liquor chemical analysis is the desired scope of eluent, add simultaneously sodium acid carbonate to eluent requirement concentration value, return and do eluent, recycle.
Effect of the present invention is:
The present invention adds carbon dioxide to the leachate of uranium before carrying out ion-exchange absorption, can reduce leachate pH behind the adding carbon dioxide, increases UO in the leachate 2(CO 3) 2 2-Percentage, thereby can more effectively improve the saturated uranium capacity of resin, resin bed hardens when having alleviated absorption.Simultaneously, improve the bicarbonate concentration in the tail washings, directly formed effective leaching solution, can inject underground recycling.Relatively traditional other acid-base method ground soaking technology needs special leachant preparation process, and the preparation process of the present invention is integrated ion-exchange absorption echos leachant has been simplified operating procedure, has optimized production Technology.
The present invention is a kind of ground dipping uranium extracting process method of economical rationality.CO 2Water-soluble preserved material is better than the alkaline Leaching systems such as ammonium carbonate/carbonic hydroammonium, because ammonium carbonate/carbonic hydroammonium can and be contained in the calcium in the clay in the stratum, sodium ion exchange by ammonium ion, improved the salinity of underground water, caused groundwater pollution, also easily cause jamming of ore bed, be unfavorable for the leaching process of metal.
The present invention breaks the normal procedure, and has analyzed CO 2+ O 2After leachate adsorbs through macropore polystyrene strong-base anion-exchange resin, the HCO that wherein contains 3 -Ion concentration is higher, utilizes wherein abundant HCO 3 -The ion regeneration that can make the transition to the resin after the desorb, technique is reasonable, and is easy and simple to handle, and the effect of regeneration is splendid, can return to preferably absorption property through the macroreticular resin of regeneration, and keep stable, has long-lasting.Follow-up desorption efficiency also increases.
Compare with traditional coprecipitation mode, when the present invention processes the qualified solution of uranyl ion, saved high-temperature heating device, so that energy consumption, equipment investment reduce greatly, reduced alkaline consumption, refinement the control parameter, saved the consumption of alkali, reduced cost of production, simultaneously, mother liquor of precipitation of ammonium can transform to be done eluent and recycles, maximizedly reduced outer pollution discharging, technological operation of the present invention is simple, and cost of production is low, for enterprise has reduced cost of production, improved production efficiency.
The specific embodiment
Below in conjunction with the CO of specific embodiment to a kind of uranium of the present invention 2Add O 2Situ Leaching exploitation processing method is further described.
Embodiment 1
Certain uranium-bearing aquifer underground water changes into classifying type with HCO 3-Na and HCO 3The Cl-Na type is main, and uranium-bearing layer roof and floor is mainly mud stone, and thickness is more stable, and water isolating is better.Salinity 3.5g/L, 15 ℃ of water temperatures, pH value 6.8, Eh:150mv, HCO 3 -: 2000mg/L, O 2<2mg/L, hydro-geochemical environment are in weak oxide-reduction intermediate zone state.
Adopt the CO of a kind of uranium of the present invention 2Add O 2Situ Leaching exploitation processing method, it comprises the steps:
(1) leaching solution is natural bicarbonate radical type underground water (HCO in the underground water of mineral deposit 3 -Content is that 2000mg/L, pH value are 6.8), add O to this leaching solution 2Inject the underground aquifer, ore deposit that contains by liquid injecting pipeline afterwards, the liquid filling pressure of leaching solution is controlled at 1.6Mp, O 2Adding pressure be higher than the liquid filling pressure 0.2Mpa of leaching solution; According to the difference in Underground Leaching progress stage, adopt the different preparations that oxygen concentration carries out leaching solution that adds; Concrete steps are: the initial stage leaches, and annotating oxygen concentration in the leaching solution is 500mg/L, when the concentration of residual oxygen in the leachate during in the 10mg/L left and right sides, annotates oxygen concentration and is reduced to 200mg/L; When leaching rate reaches 60%, annotate oxygen concentration and be down to 150mg/L, finish until leach, stop oxygenation.The leachate that forms contains [UO 2(CO 3) 3] 4-[UO 2(CO 3) 2] 2-, extract leachate out to the earth's surface, deliver to the hydrometallurgy operation and process.
(2) uranium concentration is 45mg/L in the leachate of the uranium-bearing of step (1) gained, adds CO in this leachate 2, to regulate pH value to 8; CO 2Addition is 300mg/L, CO 2Add pressure and be higher than leachate pipeline pressure 0.2Mpa.
(3) ion-exchange absorption is carried out in the leachate of the uranium-bearing of step (2) gained, adopt macropore polystyrene strong-base anion-exchange resin, obtain saturated resin and adsorption tail liquid after the absorption; Ion-exchange absorption metal adopts the absorption of two adsorption towers series connection pressure-bearing, first tower pressure-bearing 0.3MPa wherein, inferior tower 0.1Mpa, cascade towers following current absorption with pressure.
(4) adopt eluent to carry out drip washing to the saturated resin of step (3) gained, described eluent is the NaHCO of 16g/L 3Mixed solution with the NaCl of 80g/L; Then the uranyl carbonate solion that obtains is resolved, namely in the uranyl carbonate solion, add hydrochloric acid, CO to be driven 2When being acidified to pH=4.4, stop to add hydrochloric acid; Add again NaOH and regulate pH to 12.5, the normal temperature precipitation, sedimentation time 6h, lower floor obtains Na 2U 2O 7The precipitation slurry, upper solution is mother liquor of precipitation of ammonium.
After step (4) drip washing finishes, utilize adsorption tail liquid regenerating resin transition, namely with compressed air solution in the adsorption tower is dried up, use adsorption tail liquid recoil resin bed, tail washings is 6BV/h by the flow velocity of resin, resin in the resin tower fully is evenly distributed, removes foreign material residual between most of resin particle and strippant composition, till observation recoil waste water is extremely limpid; Again with adsorption tail liquid with flow velocity 1BV/h by resin bed, carry out resin regeneration, the time is 2 hours, with about 2 hours of clear water following current flushing resin, treat that wash water clears after, again water backwash, colourless to eluate, without till the muddiness.
Step (4) gained contain Na 2CO 3, NaCl and NaOH mother liquor of precipitation of ammonium be formulated as the eluent that the drip washing resin is used, if the concentration that chlorion concentration requires less than eluent in the mother liquor, then the salt adding acid for adjusting pH is in the eluent scope, adding sodium chloride adjusting mother liquor chemical analysis is the desired scope of eluent, add simultaneously sodium acid carbonate to eluent requirement concentration value, return and do eluent, recycle.
In this technique, before carrying out ion-exchange absorption, the uranium leachate adds a certain amount of CO 2Gas can reduce the pH value in the leachate, and the capacity of resin adsorption metallic uranium can improve the 20mg/mL wet resin.Add behind the carbon dioxide that bicarbonate concentration has improved 65.92mg/L in the solution, improved the concentration of bicarbonate radical, the bicarbonate concentration in the adsorption tail liquid also increases than stoste.Circulation is injected underground, and uranium concentration progressively improves in the leachate, by 45mg.L originally -1Brought up to 50mg.L -1More than, improved the leaching rate of leaching solution.It is integrated that the present invention can make leachate processing and leaching solution prepare, and optimized ground and soaked production technology, can cut operating costs and enhance productivity.
Adopt eluent (to be formulated as NaHCO 316g.L -1With NaCl 80g.L -1Mixed solution) saturated resin of uranium is carried out the drip washing operation, get the qualifying liquid of 1L uranium, composition sees Table 1.Stir first adding hydrochloric acid (annotating: mention that herein hydrochloric acid is 32% technical hydrochloric acid) 40mL, drive CO 2When being acidified to pH=4.4, at this moment solution is the mixed complex of uranyl chloride and uranyl carbonate, presents yolk yellowly, stops acid adding.
Table 1 qualifying liquid composition
ρ(U) NaCl NaHCO 3 Na 2CO 3
/g·L -1 /g·L -1 /g·L -1 /g·L -1
30.9 49.27 73.12 0.78
Adding NaOH 20g(alkali consumption is 0.66/kg.kg again -1), slowly stir 50r/min and regulate pH=12.5, the normal temperature precipitation, sedimentation time 6h generates Na 2U 2O 7Precipitation, the mother liquor composition sees Table 2.
Table 2 mother liquor of precipitation of ammonium analysis of components
U/mg·L -1 NaCl/g·L -1 Na 2CO 3/g·L -1 NaOH/g·L -1 pH
5 72.2 17.6 5.8 12.5
Adding the salt acid for adjusting pH at last in above-mentioned mother liquor is the identical pH value of eluent, and this moment, the mother liquor composition saw Table 3, reached the eluent compound concentration of standard-required.As it is lower to process rear bicarbonate ion concentration, replenishes an amount of sodium acid carbonate and gets final product.
Mother liquor composition after table 3 acid adjustment
U/mg·L -1 NaCl/g·L -1 NaHCO 3/g·L -1 NaOH/g·L -1 pH
5 80.6 16 0 6.82
Mother liquor of the present invention has been realized circulating and has been done the purpose of eluent, without effluxing solution.Simultaneously, alkaline consumption and acid consumption have been reduced.Cost of production is low, compares with traditional coprecipitation mode, and this technique has been saved high-temperature heating device.Comparing conventional directly alkaline chemical precipitation unit's metal base consumption is 4.04/kgkg -1(seeing Table 4), this technique alkali consumption are 0.66/kgkg -1Comparing the traditional handicraft acid adding, to be adjusted to pH be that 1~3 process alkali consumption is 1.78/kgkg -1(seeing Table 5) compared, and it is nearly 63% to economize on alkali number, this technique invention refinement the control parameter, saved the consumption of alkali, reduced the heat request that adds to operating equipment.
The conventional directly alkaline chemical precipitation method of table 4
Figure BDA00002298813100081
Table 5 is regulated the rear alkali consumption of pH value to 1
Figure BDA00002298813100082
Embodiment 2
Contain aquifer, ore deposit water yield 108m at certain uranium ore 3/ d, transmission coefficient 0.23m/d.Uranium-bearing layer roof and floor is mainly mud stone, and thickness is more stable, and water isolating is better.Uranium-bearing aquifer underground water changes into classifying type with HCO 3-Na and HCO 3The Cl-Na type is main, salinity 5.7g/L, 16 ℃ of water temperatures, pH value 8.4, Eh:400mv, HCO 3 -: 2600mg/L, hydro-geochemical environment are in weak oxide-reduction intermediate zone state.
Adopt the CO of a kind of uranium of the present invention 2Add O 2Situ Leaching exploitation processing method, it comprises the steps:
(1) leaching solution is natural bicarbonate radical type underground water (HCO in the underground water of mineral deposit 3 -Content is that 2600mg/L, pH value are 6.8), add O to this leaching solution 2Inject the underground aquifer, ore deposit that contains by liquid injecting pipeline afterwards, the liquid filling pressure of leaching solution is controlled at 1.5Mp, O 2Adding pressure be higher than the liquid filling pressure 0.1Mpa of leaching solution; According to the difference in Underground Leaching progress stage, adopt the different preparations that oxygen concentration carries out leaching solution that adds; Concrete steps are: the initial stage leaches, and annotating oxygen concentration in the leaching solution is 400mg/L, when the concentration of residual oxygen in the leachate during in the 10mg/L left and right sides, annotates oxygen concentration and is reduced to 200mg/L; When leaching rate reaches 70%, annotate oxygen concentration and be down to 50mg/L, finish until leach, stop oxygenation.The leachate that forms contains [UO 2(CO 3) 3] 4-[UO 2(CO 3) 2] 2-, extract leachate out to the earth's surface, deliver to the hydrometallurgy operation and process.
(2) uranium concentration is 25mg/L in the leachate of the uranium-bearing of step (1) gained, adds CO in this leachate 2, to regulate pH value to 7.9; CO 2Addition is 100mg/L, CO 2Add pressure and be higher than leachate pipeline pressure 0.1Mpa.
(3) leachate of the uranium-bearing of step (2) gained carried out ion-exchange absorption, adopt macropore polystyrene strong-base anion-exchange resin, obtain saturated resin and adsorption tail liquid after the absorption.Ion-exchange absorption metal: two adsorption towers series connection pressure-bearing absorption.First tower pressure-bearing 0.2MPa wherein, inferior tower be less than 0.1Mpa, cascade towers following current absorption with pressure.
(4) adopt eluent to carry out drip washing to the saturated resin of step (3) gained, described eluent is the NaHCO of 20g/L 3Mixed solution with the NaCl of 120g/L; Then the uranyl carbonate solion that obtains is resolved, namely in the uranyl carbonate solion, add hydrochloric acid, when CO2 to be driven is acidified to pH=4.5, stop to add hydrochloric acid; Add again NaOH and regulate pH to 13, the normal temperature precipitation, sedimentation time 12h, lower floor obtains Na 2U 2O 7The precipitation slurry, upper solution is mother liquor of precipitation of ammonium.
Adopt eluent (to be formulated as NaHCO 320gL -1With NaCl 120gL -1Mixed solution) saturated resin of uranium is carried out the drip washing operation, get 9.15m 3The qualifying liquid of uranium, composition sees Table 5.
Table 5 qualifying liquid analysis of components
Figure BDA00002298813100091
Stir first and add hydrochloric acid 0.37m 3, drive CO 2When being acidified to pH=4.5, the cosmetic variation of liquid becomes yolk yellow slurry shape by yellow-green soln, specifically sees Table 6;
Table 6 hcl acidifying
Figure BDA00002298813100092
Figure BDA00002298813100101
Then adding NaOH 150.5kg(alkali consumption is 0.685/kgkg -1), stir 70r/min1h, regulate pH=13, the normal temperature precipitation, sedimentation time 12h generates Na 2U 2O 7Precipitation, deposition efficiency has reached 99.88%, specifically sees Table 7.
Table 7 alkali precipitation
Be the identical pH of eluent 8.8 to the mother liquid obtained middle adding salt acid for adjusting pH of above-mentioned precipitation.At this moment record NaCl 103.88g/L, NaHCO 36.68g/L.Add an amount of NaHCO 3, adjusting its concentration is about 20g/L, specifically sees Table 8 and table 9.
After the table 8 mother liquor reuse acid adjustment
Table 9 is added the eluent behind the reagent
Figure BDA00002298813100104
This technique has been saved the consumption of alkali, has reduced the heat request that adds to operating equipment, and deposition efficiency reaches 99.88%, has satisfied industrial requirement.
Absorption process adopts closely knit fixed bed, and (DN3000 * 7600mm), feed liquor cloth liquid mode is adsorbed on the cascade towers, single tower drip washing, the about 23m of every tower dress amount of resin 3, the about 3.3m of resin bed floor height.
After the drip washing operation finishes, use pressure-air to dry up wherein most of remaining strippant composition it first, envelope tower access adsorption tail liquid is rinsed foreign material and desorb composition in the resin well with the flow velocity of 4BV/h, and is colourless to eluate, without till the muddiness.Again adsorption tail liquid is passed through resin bed with the constant flow rate of 0.5BV/h, carry out resin regeneration, behind control 1h time of contact, again with clear water following current flushing about one hour of resin (the about 0.5BV of the water yield), after treating that wash water clears, again water backwash (the about 0.5BV of the water yield).
Regeneration effect: through circular regeneration repeatedly, the displacement volume of resin rises to more than the 100mg/mL from 86mg/mL.Resin returns to preferably absorption property, and can keep stable.
About 30V then RThe volume adsorption tail liquid is with 1V R/ h flow recoil resin tower utilizes the HCO in the adsorption tail liquid 3 -Ion is with Cl in the poor resin -Ion exchange is got off, with the HCO in the adsorption tail liquid 3 -Ion is with Cl -Type depleted uranium resin segment transition is HCO 3 -Type is avoided Cl -The accumulation of ion in the leachate circulating system; Tail washings waste water transition enters recoil waste water storage pond; Be 60m with disposal ability 3The reverse osmosis unit of/h is processed in the storage pond and is contained Cl -The recoil waste water that ion concentration is high, concentrated water drainage enters evaporation basin, and fresh water enters liquid injection system; Cl in recoil waste water and back-flushing (being adsorption tail liquid) -Ion concentration substantially near the time, stop recoil and counter-infiltration operation, wait for entering next time adsorption operations.
The average chloride content of resin is 55mg/mL before processing, and uses the tail washings rear average chloride content of resin transition to be 2.82mg/mL, and efficient 94.9% makes the transition.The system recoveries rate design load of reverse osmosis unit is 75%, minute double diffusion, and dense water volume tapers to about 20% of original wastewater volume.
Embodiment 3
Adopt heavy carbonic root type underground water Situ Leaching uranium extracting process of the present invention in certain uranium mining area.This mining area contains aquifer, ore deposit water yield 90m 3/ d, transmission coefficient 0.12m/d.Uranium-bearing layer roof and floor is mainly mud stone, and thickness is more stable, and water isolating is better.Uranium-bearing aquifer underground water changes into classifying type with HCO 3-Na and HCO 3The Cl-Na type is main, pH value 7, Eh:300mv, HCO 3 -: 2100mg/L, hydro-geochemical environment are in weak oxide-reduction intermediate zone state.
Adopt the CO of a kind of uranium of the present invention 2Add O 2Situ Leaching exploitation processing method, it comprises the steps:
(1) leaching solution is natural bicarbonate radical type underground water (HCO in the underground water of mineral deposit 3 -Content is that 2100mg/L, pH value are 7), add O to this leaching solution 2Inject the underground aquifer, ore deposit that contains by liquid injecting pipeline afterwards, the liquid filling pressure of leaching solution is controlled at 1.6Mp, O 2Adding pressure be higher than the liquid filling pressure 0.2Mpa of leaching solution; According to the difference in Underground Leaching progress stage, adopt the different preparations that oxygen concentration carries out leaching solution that adds; Concrete steps are: the initial stage leaches, and annotating oxygen concentration in the leaching solution is 450mg/L, when the concentration of residual oxygen in the leachate during in the 10mg/L left and right sides, annotates oxygen concentration and is reduced to 200mg/L; When leaching rate reaches 70%, annotate oxygen concentration and be down to 100mg/L, finish until leach, stop oxygenation.The leachate that forms contains [UO 2(CO 3) 3] 4-[UO 2(CO 3) 2] 2-, extract leachate out to the earth's surface, deliver to the hydrometallurgy operation and process.
(2) uranium concentration is 25mg/L in the leachate of the uranium-bearing of step (1) gained, adds CO in this leachate 2, to regulate pH value to 7; CO 2Addition is 100mg/L, CO 2Add pressure and be higher than leachate pipeline pressure 0.2Mpa.
(3) leachate of the uranium-bearing of step (2) gained carried out ion-exchange absorption, adopt macropore polystyrene strong-base anion-exchange resin, obtain saturated resin and adsorption tail liquid after the absorption.Ion-exchange absorption metal: two adsorption towers series connection pressure-bearing absorption.First tower pressure-bearing 0.2MPa wherein, inferior tower be less than 0.1Mpa, cascade towers following current absorption with pressure.Tail washings injects underground: carries out the attached leachate of ion-exchange absorption, at the bottom of resin tower, discharges, and underground via the liquid injection system injection, directly cook leachant, recycle.Need not special leachant preparing process.
(4) adopt eluent to carry out drip washing to the saturated resin of step (3) gained, described eluent is the NaHCO of 20g/L 3Mixed solution with the NaCl of 100g/L; Then the uranyl carbonate solion that obtains is resolved, namely in the uranyl carbonate solion, add hydrochloric acid, CO to be driven 2When being acidified to pH=4.5, stop to add hydrochloric acid; Add again NaOH and regulate pH to 13, the normal temperature precipitation, sedimentation time 12h, lower floor obtains Na 2U 2O 7The precipitation slurry, upper solution is mother liquor of precipitation of ammonium.
Adopt eluent (to be formulated as NaHCO 320gL -1+ NaCl 100gL -1) saturated resin of uranium is carried out the drip washing operation, get 9.15m 3The qualifying liquid of uranium, composition sees Table 10.
Table 10 qualifying liquid analysis of components
Figure BDA00002298813100131
Stir first and add hydrochloric acid 0.35m 3, drive CO 2When being acidified to pH=4.5, the cosmetic variation of liquid becomes yolk yellow slurry shape by yellow-green soln, specifically sees Table 11;
Table 11 hcl acidifying
Figure BDA00002298813100132
Then adding NaOH 150kg(alkali consumption is 0.685/kgkg -1), stir 70r/min1h, regulate pH=13, the normal temperature precipitation, sedimentation time 12h generates Na 2U 2O 7Precipitation, deposition efficiency has reached 99.8%, specifically sees Table 12.
Table 12 alkali precipitation
Figure BDA00002298813100133
Be the identical pH of eluent 8.9 to the mother liquid obtained middle adding salt acid for adjusting pH of above-mentioned precipitation.At this moment record NaCl 100.5g/L, NaHCO 36.68g/L.Add an amount of NaHCO 3, adjusting its concentration is about 20g/L, specifically sees Table 13 and table 14.
After the table 13 mother liquor reuse acid adjustment
Figure BDA00002298813100134
Table 14 is added the eluent behind the reagent
Figure BDA00002298813100141
This technique has been saved the consumption of alkali, has reduced the heat request that adds to operating equipment, and deposition efficiency reaches 99.87%, has satisfied industrial requirement.
After the resin tower drip washing operation of producing field monitoring finishes, use pressure-air to dry up wherein most of remaining strippant composition it first, envelope tower access adsorption tail liquid is rinsed foreign material and desorb composition in the resin well with the flow velocity of 5BV/h, and is colourless to eluate, without till the muddiness.Again adsorption tail liquid is passed through resin bed with the constant flow rate of 0.7BV/h, carry out resin regeneration, behind control 1h time of contact, again with clear water following current flushing about one hour of resin (the about 0.5BV of the water yield), after treating that wash water clears, again water backwash (the about 0.5BV of the water yield).Regeneration effect: through circular regeneration repeatedly, the displacement volume of resin rises to more than the 100mg/mL from 86mg/mL.Resin returns to preferably absorption property, and can keep stable.
About 30V then RThe volume adsorption tail liquid is with 1V R/ h flow recoil resin tower utilizes the HCO in the adsorption tail liquid 3 -Ion is with Cl in the poor resin -Ion exchange is got off, with the HCO in the adsorption tail liquid 3 -Ion is with Cl -Type depleted uranium resin segment transition is HCO 3 -Type is avoided Cl -The accumulation of ion in the leachate circulating system; Tail washings waste water transition enters recoil waste water storage pond; Be 60m with disposal ability 3The reverse osmosis unit of/h is processed in the storage pond and is contained Cl -The recoil waste water that ion concentration is high, concentrated water drainage enters evaporation basin, and fresh water enters liquid injection system; Cl in recoil waste water and back-flushing (being adsorption tail liquid) -Ion concentration substantially near the time, stop recoil and counter-infiltration operation, wait for entering next time adsorption operations.
The average chloride content of resin is 56mg/mL before processing, and uses the tail washings rear average chloride content of resin transition to be 2.7mg/mL, and efficient 95% makes the transition.The system recoveries rate design load of reverse osmosis unit is 74%, minute double diffusion, and dense water volume tapers to about 22% of original wastewater volume.

Claims (4)

1. the CO of a uranium 2Add O 2Situ Leaching exploitation processing method, it is characterized in that: the method comprises the steps:
(1) leaching solution adds O 2Inject the underground aquifer, ore deposit that contains by liquid injecting pipeline afterwards, the liquid filling pressure of leaching solution is controlled at 1.5Mpa~1.6Mp, O 2Adding pressure be higher than the liquid filling pressure 0.1~0.2Mpa of leaching solution; According to the difference in Underground Leaching progress stage, adopt the different preparations that oxygen concentration carries out leaching solution that adds; Concrete steps are: the initial stage leaches, and annotating oxygen concentration in the leaching solution is 400~500mg/L, when the concentration of residual oxygen in the leachate during in the 10mg/L left and right sides, annotates oxygen concentration and is reduced to 200mg/L; When leaching rate reaches 60 ~ 70%, annotate oxygen concentration and be down to 50 ~ 150mg/L, finish until leach; Described leaching solution is for containing bicarbonate radical type underground water;
(2) in leaching the leachate of uranium-bearing of gained, step (1) adds CO 2, to regulate pH value to 7~8; CO 2Addition is 100~300mg/L, CO 2Add pressure and be higher than leachate pipeline pressure 0.1~0.2Mpa;
(3) ion-exchange absorption is carried out in the leachate of the uranium-bearing of step (2) gained, adopt macropore polystyrene strong-base anion-exchange resin, obtain saturated resin and adsorption tail liquid after the absorption;
(4) adopt eluent to carry out drip washing to the saturated resin of step (3) gained, described eluent is the NaHCO of 15~20g/L 3Mixed solution with the NaCl of 80~120g/L; Then the uranyl carbonate solion that obtains is resolved, namely in the uranyl carbonate solion, add hydrochloric acid, CO to be driven 2Be acidified to pH=4.0~5.0 o'clock, stop to add hydrochloric acid; Add again NaOH and regulate pH to 12.0~13.0, the normal temperature precipitation, sedimentation time 6~12h, lower floor obtains Na 2U 2O 7The precipitation slurry, upper solution is mother liquor of precipitation of ammonium.
2. the CO of a kind of uranium according to claim 1 2Add O 2Situ Leaching exploitation processing method, it is characterized in that: adopt the pressure-bearing adsorption tower of two series connection to carry out following current ion-exchange absorption with pressure uranium in the step (3), wherein first adsorption tower internal pressure is at 0.2MPa~0.3MPa, and second adsorption tower internal pressure is less than 0.1Mpa.
3. the CO of a kind of uranium according to claim 1 2Add O 2Situ Leaching exploitation processing method, it is characterized in that: after step (4) drip washing finishes, utilize adsorption tail liquid regenerating resin transition, namely with compressed air solution in the adsorption tower is dried up, use adsorption tail liquid recoil resin bed, tail washings is 4~6BV/h by the flow velocity of resin, and the resin in the resin tower fully is evenly distributed, remove foreign material residual between most of resin particle and strippant composition, till observation recoil waste water is extremely limpid; Again with adsorption tail liquid with flow velocity 0.5~1BV/h by resin bed, carry out resin regeneration, the time is 1~2 hour, with about 1~2 hour of clear water following current flushing resin, treat that wash water clears after, again water backwash, colourless to eluate, without till the muddiness.
4. the CO of a kind of uranium according to claim 1 2Add O 2Situ Leaching exploitation processing method is characterized in that: step (4) gained contain Na 2CO 3, NaCl and NaOH mother liquor of precipitation of ammonium be formulated as the eluent that the drip washing resin is used, if the concentration that chlorion concentration requires less than eluent in the mother liquor, then the salt adding acid for adjusting pH is in the eluent scope, adding sodium chloride adjusting mother liquor chemical analysis is the desired scope of eluent, add simultaneously sodium acid carbonate to eluent requirement concentration value, return and do eluent, recycle.
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