CN107686900B - A kind of method of uranium rhenium in spent ion exchange resin synthetical recovery leachate - Google Patents
A kind of method of uranium rhenium in spent ion exchange resin synthetical recovery leachate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/0265—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries extraction by solid resins
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
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Abstract
The present invention relates to a kind of methods of spent ion exchange resin synthetical recovery uranium, rhenium from rhenium-containing uranium ore leachate.For the problem that uranium, rhenium mass concentration ratio are big in rhenium-containing uranium ore leachate, the stronger strong-base anion-exchange resin of difficult separation and recycling, preferably adsorption capacity first adsorbs uranium, the rhenium in leachate simultaneously；Then for loading uranium, rhenium resin, being better than the binding ability to uranium using binding ability of the resin to rhenium the characteristics of, the difference Desorption separation of uranium, rhenium is successively realized using the different strippant of desorption ability, the final synthetical recovery for realizing uranium, rhenium in leachate.Using the method, 98% or more uranium and 95% rhenium in rhenium-containing uranium ore leachate can be recycled, ρ (U) reaches 10g/L or more, ρ (Re) < 1.0mg/L in gained uranium qualifying liquid；ρ (Re) reaches 0.5g/L, ρ (U) < 5mg/L in rhenium qualifying liquid.This method uranium, rhenium good separating effect, the rate of recovery are high, and technical process is simple, is the effective way of uranium, rhenium in synthetical recovery leachate.
Description
Technical field
The invention belongs to uranium rhenium development of resources technical fields in hydrometallurgy, and in particular to a kind of spent ion exchange resin is comprehensive
The method for closing uranium rhenium in recycling leachate.
Background technique
Rhenium is due to high-melting-point, high intensity and good plasticity, and without brittleness critical transition temperature and in height
Under the conditions of mild rapid heat cycle the advantages that good creep-resistant property, it is used widely, becomes national defence, aerospace, nuclear energy
Etc. the extremely important new material of modern high-tech fields, be a kind of important military strategy goods and materials.And reserves are very on earth for rhenium
Few, global proven reserve about 2500t, major consumers country is the developed countries such as the U.S., West Europe, Japan and Russia, military power sieve
This, the total annual consumption in the world had reached 40t in recent years, and with the fast development of aerospace field, the demand of rhenium is in quick-fried
Hair property growing trend.China is considered as poor rhenium country traditionally, and the reserves of rhenium is 237t at present, and integrated distribution is in Shan
In the mineral deposits such as the western city Jin Dui molybdenum ore, Luanchuan In Henan molybdenum ore, the big Black Hills molybdenum ore in Jilin, Heilungkiang more Baoshan Coppers (molybdenum) mine.Market side
Face, China's rhenium yield are much unable to satisfy demand, especially the fast development of China's aeronautical and space technology in recent years, so that this
One imbalance between supply and demand further increases.
Rhenium is usually present in the form of association in other mineral deposits as a kind of extremely rare and dispersion element.Wherein
Rhenium resource is usually associated in sandrock-type, Volcanic-type and carbonaceous siliceous-pelitic rock type U-ore.Uranium rhenium is carried out for this kind of resource to integrate back
Technical research is received, the development of natural uranium extractive technique can be not only promoted, the supply of China's natural uranium is further ensured, can also increase
Add the supply of China's rhenium product, provides rare rhenium resource in short supply for China's national defense modernization construction and development, alleviate its supply and demand
Contradiction.When generalling use sulfuric acid or carbonate and leaching to this kind of association uranium resource, rhenium can all be leached and enter solution.But
Since rhenium grade is usually lower in above-mentioned ore, rhenium concentration is not also high in gained leachate, leads to uranium, rhenium mass concentration ratio
Greatly, difficult separation and recycling.
Currently, both at home and abroad to the research of the separation and recovery technology of rhenium be concentrated mainly on the relatively high rhenium-containing molybdenum ore of rhenium content,
In rhenium-containing copper mine etc., and to the few of the Comprehensive Recovery Technology of uranium in rhenium-containing uranium ore, rhenium report.The former Soviet Union once uses ion exchange
Method for certain rhenium-containing uranium ore immersion liquid carried out research, but the rate of recovery of rhenium only has 30%, inefficient.The country is also to a small amount of
The relatively high association uranium ore of rhenium content carried out correlative study, as China once carried out the synthesis time of uranium, molybdenum, rhenium to certain uranium factory
It receives, and proposes P204 and first extract uranium, amine extractant extracts the process of molybdenum, rhenium, but solvent extraction method used in the method again
Lower to the extraction efficiency of rhenium, rhenium concentration is 5~8mg/L in stoste, and rhenium is still up to 1.0mg/L or more in gained raffinate water, far
Not up to the high efficiente callback of rhenium.
In short, there are no simple processes, the separation of extraction efficiency height, strong operability at present for rhenium-containing association uranium ore
Recovery method, this will lead to the loss of rhenium in the rhenium-containing uranium ore of China part, causes the waste of rhenium resource.Therefore, it researches and develops, design
A kind of method of uranium rhenium in spent ion exchange resin synthetical recovery leachate.
Summary of the invention
The technical problem to be solved in the present invention is to provide uranium rheniums in a kind of spent ion exchange resin synthetical recovery leachate
Method, to solve the problem of uranium, rhenium mass concentration ratio are big, and rhenium concentration is lower, difficult separation and recycling in rhenium-containing uranium ore leachate.
In order to realize the purpose, the technical solution adopted by the present invention is that:
A kind of method of uranium rhenium in spent ion exchange resin synthetical recovery leachate, comprising the following steps:
(1) for acid leaching solution:
1) uranium rhenium adsorbs simultaneously
Absorption stoste is rhenium-containing uranium ore acid leaching solution, wherein ρ (U)=50~1000mg/L, ρ (Re)=1.0~
10.0mg/L；Resin is strong-base anion-exchange resin；
Uranium, rhenium adsorb time of contact simultaneously as 3~12min, and uranium absorption saturation stops absorption, obtain uranium saturated resin；
2) desorption of uranium
Uranium saturated resin obtained by step 1) is taken, the desorption of uranium is carried out, obtains carrying rhenium resin；
Strippant is one of following two:
1. sodium chloride+sulfuric acid solution, ρ (NaCl)=40~80g/L, ρ (H2SO4)=3~10g/L；
②ρ(H2SO4The sulfuric acid solution of)=50~150g/L；
Desorption time of contact is 20~60min, and desorption volume is 4~8BV, must carry rhenium resin after uranium desorption；
3) desorption of rhenium
The resulting load rhenium resin of step 2) is desorbed, resin after desorption rhenium is obtained；
Strippant be 0.5~3mol/L perchloric acid solution, time of contact be 30~80min, desorption volume be 4~
10BV；
4) ion exchange resin conversion
Resin after desorption rhenium obtained by step 3) is first used into ρ (H2SO4)=1~5g/L acid water washs 1~3BV, then uses concentration
It makes the transition for the sulfuric acid solution of 50~100g/L, chloranion concentration is down to 2g/L or less up to poor tree after transition in the liquid that makes the transition
Rouge, the poor resin after being made the transition, the poor resin return step 1) it continues to use；
(2) for alkaline leaching liquid:
1) uranium rhenium adsorbs simultaneously
Absorption stoste is rhenium-containing uranium ore alkaline leaching liquid, wherein ρ (U)=50~500mg/L, ρ (Re)=1.0~
10.0mg/L；Resin is strong-base anion-exchange resin；
Uranium, rhenium adsorb 3~12min of time of contact simultaneously, and uranium absorption saturation stops absorption, obtains uranium saturated resin；
2) desorption of uranium
Uranium saturated resin obtained by step 1) is taken, the desorption of uranium is carried out；
Strippant is one: sodium chloride+sodium bicarbonate solution, two: one of sodium chloride+sodium carbonate liquor, wherein NaCl
Concentration is 40~80g/L, and the concentration of sodium bicarbonate or sodium carbonate is 2~8g/L；
Desorption time of contact is 20~60min, and desorption volume is 4~8BV, must carry rhenium resin after uranium desorption；
3) desorption of rhenium
3~5BV is first washed with water by rhenium resin is carried obtained by step 2), then is desorbed, resin after desorption rhenium is obtained；
Strippant be 0.5~3mol/L perchloric acid solution, time of contact be 30~80min, desorption volume be 4~
10BV；
4) ion exchange resin conversion after desorption rhenium
1~3BV, then the carbonic acid for being 50~100g/L with concentration is first washed with water in resin after desorption rhenium obtained by step 3)
Sodium solution makes the transition, and chloranion concentration is down to 2g/L or less up to poor resin after transition in the liquid that makes the transition, which, which returns, walks
It is rapid 1) to continue to use.
Further, in a kind of spent ion exchange resin synthetical recovery leachate as described above uranium rhenium method, step
(1) 1) and step (2) 1) in, one of model ZGA352, D380, D201 of resin.
Further, in a kind of spent ion exchange resin synthetical recovery leachate as described above uranium rhenium method, step
(1) 1) in, the internal diameter of resin column is 6mm, and resin bed height is 750mm.
Further, in a kind of spent ion exchange resin synthetical recovery leachate as described above uranium rhenium method, step
(1) 1) in, the breakthrough point for controlling uranium is 2.0mg/L, is penetrated when adsorbing 150BV, and saturation is reached when adsorbing 300BV, and uranium saturation is held
Measure 33mg/mL, uranium absorption rate 99%；Entire adsorption process tail washings rhenium concentration < 0.1mg/L, 97% or more rhenium adsorption rate, load
Resin rhenium capacity 0.9mg/mL.
Further, in a kind of spent ion exchange resin synthetical recovery leachate as described above uranium rhenium method, step
(1) 1) in, one of model ZGA352, D380, D201 of resin；The internal diameter of resin column is 6mm, and resin bed height is
750mm；The breakthrough point for controlling uranium is 2.0mg/L, penetrates when adsorbing 150BV, reaches saturation, uranium saturated capacity when adsorbing 300BV
33mg/mL, uranium absorption rate 99%；Entire adsorption process tail washings rhenium concentration < 0.1mg/L, 97% or more rhenium adsorption rate, load tree
Rouge rhenium capacity 0.9mg/mL.
Further, in a kind of spent ion exchange resin synthetical recovery leachate as described above uranium rhenium method, step
(2) 1) in, resin column internal diameter is 6mm, and resin bed height is 750mm.
Further, in a kind of spent ion exchange resin synthetical recovery leachate as described above uranium rhenium method, step
(2) 1) in, the breakthrough point for controlling uranium is 2.0mg/L, reaches breakthrough point when adsorbing 200BV, reaches saturation when adsorbing 350BV；Entirely
Adsorption process tail washings rhenium concentration < 0.05mg/L, rhenium adsorption rate 98%, loaded resin rhenium capacity 1.0mg/mL.
Further, in a kind of spent ion exchange resin synthetical recovery leachate as described above uranium rhenium method, step
(2) 1) in, resin model 353E, resin column internal diameter is 6mm, and resin bed height is 750mm, and the breakthrough point for controlling uranium is
2.0mg/L reaches breakthrough point when adsorbing 200BV, reaches saturation when adsorbing 350BV；Entire adsorption process tail washings rhenium concentration <
0.05mg/L, rhenium adsorption rate 98%, loaded resin rhenium capacity 1.0.
The beneficial effect of technical solution of the present invention is: method provided by the invention is low in cost, easy to operate, Ke Yida
The purpose of the separation and recovery of uranium, rhenium in leachate, the synthetical recovery for uranium in China's rhenium-containing uranium ore leachate, rhenium provide one
Kind new way.This method is using the strong-base anion-exchange resin extraction that adsorption uranium, rhenium-desorb respectively simultaneously and separation work
Skill handles uranium, rhenium leachate, and adsorption tail liquid uranium concentration can be down to 5.0mg/L hereinafter, the uranium rate of recovery 98%；Tail washings rhenium concentration can
0.1mg/L is down to hereinafter, Rhenium recovery rate 95%；ρ (U) is up to 10g/L or more, ρ (Re) < 1mg/ in elution gained uranium qualifying liquid
L；ρ (Re) is up to 0.5g/L or more, ρ (U) < 5mg/L in rhenium qualifying liquid.Both the high efficiente callback of uranium in leachate, rhenium had been realized,
Again realize uranium, rhenium efficiently separates, and technical process is simple, and industrial application value is higher.
Detailed description of the invention
Fig. 1 is mode flow diagram of the present invention.
Specific embodiment
Technical solution of the present invention is described in detail in the following with reference to the drawings and specific embodiments.
As shown in Figure 1, in a kind of spent ion exchange resin synthetical recovery leachate of the present invention uranium rhenium method, including it is following
Step:
(1) for acid leaching solution:
1) uranium rhenium adsorbs simultaneously
Absorption stoste is rhenium-containing uranium ore acid leaching solution, wherein ρ (U)=50~1000mg/L, ρ (Re)=1.0~
10.0mg/L；Resin is strong-base anion-exchange resin；
Uranium, rhenium adsorb time of contact simultaneously as 3~12min, and uranium absorption saturation stops absorption, obtain uranium saturated resin；
In the present embodiment, one of model ZGA352, D380, D201 of resin；The internal diameter of resin column is 6mm, resin bed
Height is 750mm；The breakthrough point for controlling uranium is 2.0mg/L, is penetrated when adsorbing 150BV, and saturation is reached when adsorbing 300BV, and uranium is full
With capacity 33mg/mL, uranium absorption rate 99%；Entire adsorption process tail washings rhenium concentration < 0.1mg/L, 97% or more rhenium adsorption rate,
Loaded resin rhenium capacity 0.9mg/mL.
2) desorption of uranium
Uranium saturated resin obtained by step 1) is taken, the desorption of uranium is carried out, obtains carrying rhenium resin；
Strippant is one of following two:
1. sodium chloride+sulfuric acid solution, ρ (NaCl)=40~80g/L, ρ (H2SO4)=3~10g/L；
②ρ(H2SO4The sulfuric acid solution of)=50~150g/L；
Desorption time of contact is 20~60min, and desorption volume is 4~8BV, must carry rhenium resin after uranium desorption；
3) desorption of rhenium
The resulting load rhenium resin of step 2) is desorbed, resin after desorption rhenium is obtained；
Strippant be 0.5~3mol/L perchloric acid solution, time of contact be 30~80min, desorption volume be 4~
10BV；
4) ion exchange resin conversion
Resin after desorption rhenium obtained by step 3) is first used into ρ (H2SO4)=1~5g/L acid water washs 1~3BV, then uses concentration
It makes the transition for the sulfuric acid solution of 50~100g/L, chloranion concentration is down to 2g/L or less up to poor tree after transition in the liquid that makes the transition
Rouge, the poor resin after being made the transition, the poor resin return step 1) it continues to use；
(2) for alkaline leaching liquid:
1) uranium rhenium adsorbs simultaneously
Absorption stoste is rhenium-containing uranium ore alkaline leaching liquid, wherein ρ (U)=50~500mg/L, ρ (Re)=1.0~
10.0mg/L；Resin is strong-base anion-exchange resin；
Uranium, rhenium adsorb 3~12min of time of contact simultaneously, and uranium absorption saturation stops absorption, obtains uranium saturated resin；
In the present embodiment, resin model 353E, resin column internal diameter is 6mm, and resin bed height is 750mm, controls uranium
Breakthrough point is 2.0mg/L, reaches breakthrough point when adsorbing 200BV, reaches saturation when adsorbing 350BV；Entire adsorption process tail washings rhenium is dense
Spend < 0.05mg/L, rhenium adsorption rate 98%, 1.0 mg/mL of loaded resin rhenium capacity.
2) desorption of uranium
Uranium saturated resin obtained by step 1) is taken, the desorption of uranium is carried out；
Strippant is one: sodium chloride+sodium bicarbonate solution, two: one of sodium chloride+sodium carbonate liquor, wherein NaCl
Concentration is 40~80g/L, and the concentration of sodium bicarbonate or sodium carbonate is 2~8g/L；
Desorption time of contact is 20~60min, and desorption volume is 4~8BV, must carry rhenium resin after uranium desorption；
3) desorption of rhenium
3~5BV is first washed with water by rhenium resin is carried obtained by step 2), then is desorbed, resin after desorption rhenium is obtained；
Strippant be 0.5~3mol/L perchloric acid solution, time of contact be 30~80min, desorption volume be 4~
10BV；
4) ion exchange resin conversion after desorption rhenium
1~3BV, then the carbonic acid for being 50~100g/L with concentration is first washed with water in resin after desorption rhenium obtained by step 3)
Sodium solution makes the transition, and chloranion concentration is down to 2g/L or less up to poor resin after transition in the liquid that makes the transition, which, which returns, walks
It is rapid 1) to continue to use.
It is the specific embodiment being described in further detail below:
In terms of acid leaching solution uranium rhenium synthetical recovery, specific embodiment includes following two:
Embodiment 1
Leachate composition is shown in Table 1.
1 Acidic Uranium of table, rhenium leachate component test result 1
| Ingredient | U | Re | ΣFe | Fe3+ | SO4 2- | Spent acid |
| ρB/(g·L-1) | 0.172 | 0.003 | 2.54 | 0.87 | 15.3 | 8.7 |
1) uranium, rhenium adsorb simultaneously.Resin is ZGA352 resin, resin column internal diameter 6mm, resin bed height 750mm.Absorption
Time of contact 5min, the breakthrough point for controlling uranium is 2.0mg/L, is penetrated when adsorbing 150BV, and saturation is reached when adsorbing 300BV, and uranium is full
With capacity 33mg/mL (wet resin), uranium absorption rate 99%；Entire adsorption process tail washings rhenium concentration < 0.1mg/L, rhenium adsorption rate
97% or more, loaded resin rhenium capacity 0.9mg/mL (wet resin).
2) desorption of uranium.Strippant is 5g/L sulfuric acid+50g/L sodium chloride solution, desorbs time of contact 30min, desorbs body
Product 8BV, uranium desorption efficiency is up to 99%；Take the stripping liquid of 3~5BV as qualifying liquid, then uranium concentration 10g/L, rhenium are dense in qualifying liquid
Spend < 1mg/L.
3) desorption of rhenium.It desorbs uranium rear bearing rhenium resin rhenium to be desorbed with 1.5mol/L perchloric acid solution, time of contact 1h, warp
6BV is crossed, rhenium desorption efficiency takes the stripping liquid of 2.5~4BV as qualifying liquid up to 98%, then ρ (Re) reaches 0.51g/L in qualifying liquid,
ρ (U) is 2.6mg/L.
4) ion exchange resin conversion.Resin first uses ρ (H after desorption rhenium2SO4)=3g/L acid water washs 3BV, then uses 50g/L sulphur
Acid solution makes the transition 8BV, and chloranion concentration is 1.3g/L in the liquid that makes the transition, and the poor resin of gained returns to adsorption uranium, rhenium again, still reaches
Former absorption property.
Embodiment 2
Leachate composition is shown in Table 2.
2 Acidic Uranium of table, rhenium leachate component test result 2
| Ingredient | U | Re | ΣFe | Fe3+ | SO4 2- | Spent acid |
| ρB/(g·L-1) | 0.332 | 0.007 | 6.31 | 1.42 | 30.2 | 17.6 |
1) uranium, rhenium adsorb simultaneously.Resin is D380 resin, resin column internal diameter 6mm, resin bed height 750mm.Absorption contact
Time 5min, the breakthrough point for controlling uranium is 5.0mg/L, is penetrated when adsorbing 100BV, and saturation, uranium saturation are reached when adsorbing 200BV
Capacity 43mg/mL (wet resin), uranium absorption rate 99%；Entire adsorption process tail washings rhenium concentration < 0.1mg/L, rhenium adsorption rate
98%, loaded resin rhenium capacity 1.3mg/mL (wet resin).
2) desorption of uranium.Strippant is 5g/L sulfuric acid+50g/L sodium chloride solution, desorbs time of contact 30min, desorbs body
Product 8BV, uranium desorption efficiency is up to 99%；Take the stripping liquid of 3~5BV as qualifying liquid, then uranium concentration reaches 15g/L, rhenium in qualifying liquid
Concentration < 1mg/L.
3) desorption of rhenium.It desorbs uranium rear bearing rhenium resin to be desorbed with 2mol/L perchloric acid solution, time of contact 1h passes through
6BV, rhenium desorption efficiency take the stripping liquid of 2~4BV as qualifying liquid up to 98%, then ρ (Re) reaches 0.63g/L, ρ (U) in qualifying liquid
For 3.5mg/L.
4) ion exchange resin conversion.Resin after desorption rhenium first uses ρ (H2SO4)=3g/L acid water washs 3BV, then uses 50g/L sulphur
Acid solution makes the transition 7BV, and chloranion concentration is 1.8g/L in the liquid that makes the transition, and the poor resin of gained returns to adsorption uranium rhenium again, still reaches
Former absorption property.
In terms of alkaline leaching liquid uranium rhenium synthetical recovery, specific embodiment includes following two:
Embodiment 1
Leachate composition is shown in Table 3.
Table 3 alkaline uranium, rhenium leachate component test result 1
| Ingredient | U | Re | HCO3 - | CO3 2- | SO4 2- | Cl- |
| ρB/(g·L-1) | 0.121 | 0.003 | 2.03 | 0.178 | 1.46 | 0.313 |
1) uranium, rhenium adsorb simultaneously.Resin is D750 resin, resin column internal diameter 6mm, resin height 750mm.When absorption contact
Between 5min, the breakthrough point for controlling uranium is 2.0mg/L, reaches breakthrough point when adsorbing 200BV, the adsorption rate of uranium is up to 98.5% at this time；It inhales
Reach saturation, uranium saturated capacity 36mg/mL (wet resin) when attached 350BV；Entire adsorption process tail washings rhenium concentration < 0.05mg/L,
Rhenium adsorption rate 98%, loaded resin rhenium capacity 1.0mg/mL (wet resin).
2) desorption of uranium.Strippant is 5g/L sodium bicarbonate+50g/L sodium chloride solution, desorbs time of contact 30min, solution
Inhale volume 6BV, uranium desorption efficiency 99%；Take the stripping liquid of 2~4BV as qualifying liquid, then uranium concentration reaches 15g/L in qualifying liquid,
Rhenium concentration < 0.5mg/L.
3) desorption of rhenium.3BV is first washed with water in desorption uranium rear bearing rhenium resin, then is desorbed with 1.5mol/L perchloric acid solution,
Time of contact is 1h, and by 6BV, rhenium desorption efficiency takes the stripping liquid of 2~4BV as qualifying liquid, then qualifying liquid ρ up to 98.5%
(Re) 0.52g/L is reached, ρ (U) is 1.5mg/L or less.
4) rhenium ion exchange resin conversion is desorbed.3BV is first washed with water in resin after desorption rhenium, then is made the transition with 50g/L sodium carbonate liquor
6BV, chloranion concentration is 1.4g/L in the liquid that makes the transition, and the poor resin of gained returns to adsorption uranium rhenium again, still reaches former absorption property.
Embodiment 2
Leachate composition is shown in Table 4.
Table 4 alkaline uranium, rhenium leachate component test result 2
| Ingredient | U | Re | HCO3 - | CO3 2- | SO4 2- | Cl- |
| ρB/(g·L-1) | 0.412 | 0.008 | 7.13 | 10.3 | 6.4 | 0.51 |
1) uranium rhenium adsorbs simultaneously.Resin is D231YT resin, resin column internal diameter 6mm, resin height 750mm.Absorption contact
Time 5min, the breakthrough point for controlling uranium is 5.0mg/L, reaches breakthrough point when adsorbing 130BV, and saturation is reached when adsorbing 180BV, and uranium is full
With capacity 46mg/mL (wet resin), uranium absorption rate 99%；Entire adsorption process tail washings rhenium concentration < 0.1mg/L, rhenium adsorption rate
99%, loaded resin rhenium capacity 1.4mg/mL (wet resin).
2) desorption of uranium.Strippant is 5g/L sodium bicarbonate+50g/L sodium chloride solution, desorbs time of contact 30min, solution
Inhale volume 6BV, uranium desorption efficiency 99%；Take the stripping liquid of 2~4BV as qualifying liquid, then uranium concentration reaches 18g/L in qualifying liquid,
Rhenium concentration < 0.5mg/L.
3) desorption of rhenium.
Desorption uranium rear bearing rhenium resin is first washed with water 3BV, then with the desorption of 2.0mol/L perchloric acid solution, and time of contact is
1h, by 6BV, rhenium desorption efficiency takes the stripping liquid of 2~4BV as qualifying liquid, then qualifying liquid ρ (Re) reaches 0.65g/ up to 98%
L, ρ (U) are 2.0mg/L.
4) rhenium ion exchange resin conversion is desorbed.3BV is first washed with water in resin after desorption rhenium, then is made the transition with 50g/L sodium carbonate liquor
6BV, chloranion concentration is 1.6g/L in the liquid that makes the transition, and the poor resin of gained returns to adsorption uranium rhenium again, still reaches former absorption property.
Claims (6)
1. a kind of method of uranium rhenium in spent ion exchange resin synthetical recovery leachate, which comprises the following steps:
(1) for acid leaching solution:
1) uranium rhenium adsorbs simultaneously
Absorption stoste is rhenium-containing uranium ore acid leaching solution, wherein ρ (U)=50~1000mg/L, ρ (Re)=1.0~10.0mg/L；
Resin is strong-base anion-exchange resin；
Uranium, rhenium adsorb time of contact simultaneously as 3~12min, and uranium absorption saturation stops absorption, obtain uranium saturated resin；
2) desorption of uranium
Uranium saturated resin obtained by step 1) is taken, the desorption of uranium is carried out, obtains carrying rhenium resin；
Strippant is one of following two:
1. sodium chloride+sulfuric acid solution, ρ (NaCl)=40~80g/L, ρ (H2SO4)=3~10g/L；
②ρ(H2SO4The sulfuric acid solution of)=50~150g/L；
Desorption time of contact is 20~60min, and desorption volume is 4~8BV, must carry rhenium resin after uranium desorption；
3) desorption of rhenium
The resulting load rhenium resin of step 2) is desorbed, resin after desorption rhenium is obtained；
Strippant is the perchloric acid solution of 0.5~3mol/L, and time of contact is 30~80min, and desorption volume is 4~10BV；
4) ion exchange resin conversion
Resin after desorption rhenium obtained by step 3) is first used into ρ (H2SO4)=1~5g/L acid water wash 1~3BV, then with concentration be 50
The sulfuric acid solution of~100g/L makes the transition, and chloranion concentration is down to 2g/L or less up to poor resin after transition in the liquid that makes the transition, and obtains
Poor resin after to transition, the poor resin return step 1) it continues to use；
(2) for alkaline leaching liquid:
1) uranium rhenium adsorbs simultaneously
Absorption stoste is rhenium-containing uranium ore alkaline leaching liquid, wherein ρ (U)=50~500mg/L, ρ (Re)=1.0~10.0mg/L；
Resin is strong-base anion-exchange resin；
Uranium, rhenium adsorb 3~12min of time of contact simultaneously, and uranium absorption saturation stops absorption, obtains uranium saturated resin；
2) desorption of uranium
Uranium saturated resin obtained by step 1) is taken, the desorption of uranium is carried out；
Strippant is one: sodium chloride+sodium bicarbonate solution, two: one of sodium chloride+sodium carbonate liquor, wherein NaCl concentration
For 40~80g/L, the concentration of sodium bicarbonate or sodium carbonate is 2~8g/L；
Desorption time of contact is 20~60min, and desorption volume is 4~8BV, must carry rhenium resin after uranium desorption；
3) desorption of rhenium
3~5BV is first washed with water by rhenium resin is carried obtained by step 2), then is desorbed, resin after desorption rhenium is obtained；
Strippant is the perchloric acid solution of 0.5~3mol/L, and time of contact is 30~80min, and desorption volume is 4~10BV；
4) ion exchange resin conversion after desorption rhenium
1~3BV, then the sodium carbonate liquor for being 50~100g/L with concentration is first washed with water in resin after desorption rhenium obtained by step 3)
Make the transition, chloranion concentration is down to 2g/L or less up to poor resin after transition, the poor resin return step 1 in the liquid that makes the transition) after
It is continuous to use；
Step (1) 1) and step (2) 1) in, one of model ZGA352, D380, D201 of resin.
2. the method for uranium rhenium, feature exist in a kind of spent ion exchange resin synthetical recovery leachate as described in claim 1
In: step (1) 1) in, the internal diameter of resin column is 6mm, and resin bed height is 750mm.
3. the method for uranium rhenium, feature exist in a kind of spent ion exchange resin synthetical recovery leachate as described in claim 1
In: step (1) 1) in, the breakthrough point for controlling uranium is 2.0mg/L, penetrates when adsorbing 150BV, reaches saturation, uranium when adsorbing 300BV
Saturated capacity 33mg/mL, uranium absorption rate 99%；Entire adsorption process tail washings rhenium concentration < 0.1mg/L, rhenium adsorption rate 97% with
On, loaded resin rhenium capacity 0.9mg/mL.
4. the method for uranium rhenium, feature exist in a kind of spent ion exchange resin synthetical recovery leachate as described in claim 1
In: step (1) 1) in, one of model ZGA352, D380, D201 of resin；The internal diameter of resin column is 6mm, resin bed height
For 750mm；The breakthrough point for controlling uranium is 2.0mg/L, is penetrated when adsorbing 150BV, and saturation is reached when adsorbing 300BV, and uranium saturation is held
Measure 33mg/mL, uranium absorption rate 99%；Entire adsorption process tail washings rhenium concentration < 0.1mg/L, 97% or more rhenium adsorption rate, load
Resin rhenium capacity 0.9mg/mL.
5. the method for uranium rhenium, feature exist in a kind of spent ion exchange resin synthetical recovery leachate as described in claim 1
In: step (2) 1) in, resin column internal diameter is 6mm, and resin bed height is 750mm.
6. the method for uranium rhenium, feature exist in a kind of spent ion exchange resin synthetical recovery leachate as described in claim 1
In: step (2) 1) in, the breakthrough point for controlling uranium is 2.0mg/L, reaches breakthrough point when adsorbing 200BV, reaches full when adsorbing 350BV
With；Entire adsorption process tail washings rhenium concentration < 0.05mg/L, rhenium adsorption rate 98%, loaded resin rhenium capacity 1.0mg/mL.
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| CN108364704B (en) * | 2018-02-26 | 2019-11-01 | 核工业二三0研究所 | The environment-friendly treatment method and device of triuranium octoxide detection waste liquid |
| CN110184458A (en) * | 2019-05-17 | 2019-08-30 | 核工业北京化工冶金研究院 | It is a kind of to handle the technique containing uranium solution using Chemical adsorptive fiber |
| CN112708759A (en) * | 2020-11-27 | 2021-04-27 | 核工业北京化工冶金研究院 | Method for enriching uranium from sulfuric acid leaching solution |
| CN113584330A (en) * | 2020-11-30 | 2021-11-02 | 核工业北京化工冶金研究院 | From CO2+O2Method for comprehensively recovering rhenium from in-situ leaching uranium mining leachate |
| CN112680608B (en) * | 2020-12-16 | 2022-08-19 | 核工业北京化工冶金研究院 | Method for extracting uranium from chlorinated carbonate system |
| CN112853122B (en) * | 2021-01-04 | 2022-08-02 | 北京地科绿色资源科技有限公司 | Clean production process for recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore |
| CN115572848B (en) * | 2022-09-26 | 2023-12-15 | 核工业北京化工冶金研究院 | Technological method capable of realizing efficient leaching of uranium-bearing resin and regeneration of leaching agent |
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