CN106148737B - A method of recycling association rhenium resource from sandstone-type uranium mineralization with respect ground dipping uranium extracting process adsorption tail liquid - Google Patents
A method of recycling association rhenium resource from sandstone-type uranium mineralization with respect ground dipping uranium extracting process adsorption tail liquid Download PDFInfo
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- CN106148737B CN106148737B CN201610523002.8A CN201610523002A CN106148737B CN 106148737 B CN106148737 B CN 106148737B CN 201610523002 A CN201610523002 A CN 201610523002A CN 106148737 B CN106148737 B CN 106148737B
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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
- C22B60/0221—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching
- C22B60/0226—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors
- C22B60/0234—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors sulfurated ion as active agent
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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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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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
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
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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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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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
- 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
- C22B60/0278—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries by chemical methods
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The method that the invention discloses a kind of to recycle association rhenium resource from the poor resin of sandstone-type uranium mineralization with respect ground dipping uranium extracting process, sandstone-type uranium mineralization with respect is added in the sulfuric acid solution containing oxidant, at a certain temperature, concussion is impregnated after a certain period of time, the uranium rhenium in leachate is adsorbed with anion exchange resin, Uranium In Ion-exchange Resin is desorbed using ammonium nitrate solution after resin saturation, absorbing process is returned to after poor ion exchange resin conversion, the uranium enrichment liquid of desorption uses sodium hydroxide pellets, rhenium in resin is desorbed, obtain the Ammonium rhenate solution of concentration, rehenic acid ammonium product is obtained after recrystallizing.Present invention process process is simple, is easy to be mass produced；Product purity is high, and rhenium overall recovery is up to 80% or more in leachate, and agents useful for same is environmental-friendly, has apparent Social benefit and economic benefit.
Description
Technical field
It is specifically a kind of to be returned from sandstone-type uranium mineralization with respect ground dipping uranium extracting process adsorption tail liquid the present invention relates to field of hydrometallurgy
The method for receiving association rhenium resource
Technical background
Rhenium is a kind of valuable uncommon dispersed metallic, has high-melting-point, high-intensitive good plasticity and excellent mechanical stability
The features such as, it is widely used in the key areas such as national defence, Aeronautics and Astronautics, petrochemical industry and electronics industry, especially petroleum reforming is urged
Agent and superalloy account for the main part of rhenium consumption.Rhenium is silvery white non-ferrous metal, but the rhenium color of powdery is between grey and coffee
Between coffee color.Rhenium metal is in the hexagonal crystallographic texture of solid matter, and rhenium is very hard, corrosion-resistant, wear-resisting, has good ductility, and
High rigidity and ductility can be kept at low temperature, and high-intensitive and good creep resisting property is kept in temperature shock and high temperature
Energy[3-7].Rhenium is insoluble metal, and fusing point is up to 3180 DEG C (3453K), is only second to tungsten in a metal.The density of rhenium is 21102g/
mm3, boiling point 6173K.In refractory metal, rhenium is not react with carbon uniquely, generates the element of carbide.Seven oxides of rhenium
(Re2O7) volatility it is high, and be easily soluble in water and oxo solvent, both properties are utilized extensively in the recycling of rhenium.
In weak acid or weak caustic solution, rhenium is with septivalency anion Re04 -In the presence of such as ammonium perrhenate, potassium perrhenate, generally in wet process smelting
Jin Zhongjun is extracted with anionic form.The method of rhenium is extracted from aqueous solution mainly by method of cementation, reduction method, solvent extraction
Method and ion-exchange.
Ion-exchange is to achieve the purpose that separation using its selective absorption to different ions, active group in resin
Containing rhenium ion ion exchange occurs for group with solution, makes rhenium and other ion isolations, ion-exchange have simply, it is efficient,
Labor intensity is low, it is quick, pollute small, high income and it is renewable the advantages that.But selectivity is good, adsorption capacity is high, raw due to lacking
Ion exchange resin at low cost is produced, is not popularized for industrial production.Using ion exchange resin recycling rhenium have strong basicity yin from
Subtree rouge, weak anion resin, the related of chelating type resin anion (R.A.) are reported.Strong-base anion-exchange resin to rhenium,
Molybdenum ion adsorptive selectivity is strong, but need to use HClO4、HNO3Or NH4SCN solution elutes rhenium from resin, due to introducing
ClO4 -、NO3 -Equal foreign ions, it is more difficult to prepare high-purity ammonium perrhenate[33]；Weak-base anion-exchange resin is to rhenium, molybdenum ion
Adsorptive selectivity it is low, but can will contain rhenium ion with ammonia spirit and be eluted from resin, without introduce other impurity from
High-purity ammonium perrhenate can be made in son；Chelating resin overcomes that general ion exchange resins selective is poor, mass transfer velocity is slower
The shortcomings that, but its synthesis technology is complicated and preparation cost is higher.
Summary of the invention
In order to overcome the shortcomings of that existing extractive technique, the present invention provide a kind of from the absorption of sandstone-type uranium mineralization with respect ground dipping uranium extracting process
The method of association rhenium resource is recycled in tail washings.
To achieve the above object, the present invention takes following technical scheme (process flow is as shown in annex):
(1) acidleach: the dilute sulfuric acid that the sandstone-type uranium mineralization with respect containing association rhenium resource is added to the oxidant containing a certain concentration is molten
(guarantee leachate PH<2, Eh>500mV) in liquid, after room temperature oscillation is impregnated 12-24 hours, uranium, rhenium acidic mixed are obtained after filtering
Solution.
(2) it adsorbs: using D263 anion exchange resin as adsorbent, with absorbing process again is saturated, by uranium in leachate
Absorption, using 6% ammonium nitrate (NH4NO3) desorption uranium after, resin returns to adsorption process after making the transition.
(3) precipitate uranium: the uranium solution that will be got off in step (2) with elution with ammonium nitrate, with sodium hydroxide pellets, through precipitating,
Sodium diuranate product (yellow cake) is obtained after drying.
(4) Adsorption of Rhenium: the adsorption tail liquid after uranium will adsorb in step (2), with the mixed amine of the sequestered of designed, designed synthesis
Macroreticular resin is adsorbent, under conditions of guaranteeing certain time of contact, adsorbs to the rhenium in adsorption tail liquid, reaches absorption
After balance, using certain density ammonium hydroxide as strippant, under certain conditions, rhenium is got off from resin desorption, obtains rehenic acid ammonium
Solution.
(5) evaporative crystallization rhenium product: step (4) rehenic acid ammonium concentrate obtained is concentrated by evaporation at a certain temperature,
It stands still for crystals at a certain temperature, mother liquor of precipitation of ammonium returns to strip liquor preparing process.Purification is recrystallized after crystal is filtered, and obtains rhenium
Sour potassium product.
In above-mentioned process flow, it is characterised in that press uranium ore: leachate (volume ratio)=1:1~1 in leaching process:
The excellent molten slag of monazite is added to sulfuric acid+(0-2g/L) hydrogen peroxide that concentration is (5-15g/L) and (guarantees PH < 2, Eh by 10 ratio
> 500mV) in solution, stirring at normal temperature 12~24 hours, clarifies 1~3 hour, the solution of uranium-bearing, rhenium is obtained after filtering.
In above-mentioned process flow, it is characterised in that in the technical process of Adsorption of Rhenium, the mixed amine macroporous ion-exchange resin that dissociates is primary
The free amine type series plastics of amine, tertiary amine macropore, the resin are 1.6 × 10 to the rate of adsorption of rhenium-3 s-1, i.e. time of contact is
15-20min, for acidity in pH 2.0~5.0 conducive to rhenium absorption, adsorption equilibrium obeys Freundish adsorption isotherm, can be in room temperature
Lower progress；Small-sized dynamic adsorption test shows resin to underwater trace rhenium adsorption rate up to 95% or more, 25 times of resin bed volume
3mol/L NH4OH can elute completely rhenium.Immersion liquid coexisting ion in ground does not influence the absorption and desorption of rhenium, H2SO4Solution can make
Resin regeneration.Resin is to adsorbable 0.03mg/L rhenium solution, and the rate of recovery is up to 96%~102%.
In above-mentioned process flow, it is characterised in that in evaporative crystallization rhenium Product Process, in rehenic acid potassium recrystallization process, rhenium
Sour potassium thickening temperature is no more than 80 DEG C, and recrystallization temperature is lower than 4 DEG C.
Process flow of the invention is simple, is easy to be mass produced；Chemical materials is common and consumption is low；It can be effectively not
On the Process ba- sis for changing ground-dipping uranium extraction, the mode for taking interruption to recycle recycles the valuable rhenium resource adsorbed in poor resin, product
Purity is high, overall recovery is up to 95% or more in poor resin, and agents useful for same is environmental-friendly, has apparent social benefit and economy
Benefit.
Detailed description of the invention
Fig. 1 is the infrared spectrogram that special efficacy adsorbs resin,
Fig. 2 is that the special efficacy after Adsorption of Rhenium adsorbs resin infrared spectrum,
Fig. 3 adsorpting rate curve,
Fig. 4 acidity and adsorbance relation curve,
Fig. 5 adsorption isothermal curve,
Fig. 6 isothermal adsorption (lgQ-lgCe) relation curve,
Fig. 7 acidity and adsorption rate relation curve,
Adsorption curve Fig. 8 different in flow rate, in figure
1—0.5mL·min-1, 2-1mLmin-1, 3-2mLmin-1, 4-3mLmin-1, 5-4mLmin-1
Fig. 9 adsorption curve,
The elution curve of Figure 10 difference stripping liquid concentration,
(1+1) NH 1-in figure4OH, 2-3mol/L NH4OH, 3-1.5mol/L NH4OH；
Figure 11 DU, DRe, β Re/U~pH relation curve.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Embodiment 1:
By the sandstone-type uranium mineralization with respect containing association rhenium resource, according in uranium ore: leachate (volume ratio)=1:10 ratio,
It is added in 15g/L dilution heat of sulfuric acid, 1g/L is added and obtains uranium, rhenium acidic mixed after filtering after room temperature oscillation is impregnated 18 hours
Solution.Slag is washed slag three times with a small amount of leaching solution, wash water is incorporated in leachate, obtains uranium, rehenic acid mixed solution
With filter residue (leaching rate of slag meter uranium is 90%, and the leaching rate of rhenium is 80%, PH=1.77.Eh=533mv).With D263 anion
Exchanger resin is adsorbent, with absorbing process again is saturated, uranium, rhenium in leachate is adsorbed, using 6% ammonium nitrate (NH4NO3)
After desorbing uranium, resin returns to adsorption process after making the transition.After certain cycle period, resin basically reaches absorption to low concentration rhenium
Balance, rhenium content maintains about 1mg/g in resin at this time.The uranium solution eluted (14g/L) is dried with sodium hydroxide pellets
Sodium diuranate product (yellow cake) is obtained after dry.The adsorption tail liquid after uranium will be adsorbed, amine is mixed with the sequestered of designed, designed synthesis
Macroreticular resin is adsorbent, under conditions of guaranteeing 15min, is adsorbed to the rhenium in adsorption tail liquid, after reaching adsorption equilibrium,
Rhenium content reaches 24mg/g in resin at this time, using certain density ammonium hydroxide as strippant, under certain conditions, by rhenium from resin
Desorption is got off, and is obtained Ammonium rhenate solution (6g/L).Evaporative crystallization rhenium product: by step (4) rehenic acid ammonium concentrate obtained,
It is concentrated by evaporation under certain temperature, stands still for crystals at a certain temperature, mother liquor of precipitation of ammonium returns to strip liquor preparing process.Crystal is filtered
Recrystallization purification afterwards obtains rehenic acid potassium product, and the comprehensive recovery of rhenium is up to 85% at this time.
The chemical composition (%) of sodium diuranate in 1 embodiment 1 of table
Note: the rate of recovery of uranium is 89.2%.
2 resin physical and chemical index of table
It is seen in fig. 1, that the big ionic porogen constituted in special efficacy absorption resin with numerous groups such as primary amine, secondary amine, hydroxyl
Exchanger resin, the presence of these groups, which has, to be conducive to form complex with rehenic acid root or forms hydrogen bond.From the special efficacy of rhenium after Fig. 2 absorption
It is found on the infared spectrum of resin, in 943cm-1The peak that place occurs is that the oxide of rhenium is attracted to the characteristic peak on resin.
Adsorption reaction rate constants k=1.6 × 10 are found out by Fig. 3 straight slope-3 s-1.Enable F=0.5 ,-ln (1-F)=
0.693, then it can obtain exchange half-time t1/2=433s, i.e. 7.22min, also show ZGT75Resin has the faster rate of adsorption to rhenium.
From fig. 4, it can be seen that the adsorbance of rhenium increases with the increase of solution ph, as pH 2.0-5.0, adsorbance tends to
Steadily.Experimental selection pH 2.0 is as absorption acidity.
As shown in Figure 5, as water phase rhenium equilibrium concentration increases, the adsorbance of rhenium is gradually increased.When rhenium equilibrium concentration continues
460mg/L is increased to, adsorbance tends to definite value, static saturated adsorption capacity 166mg/g.
lnQe&lnCeIt is in a linear relationship, with lg Q to lg CeIt maps to obtain a straight line, sees Fig. 6, this shows ZGT75Anion is handed over
It changes resin and Freundlich isothermal adsorption formula is met to the absorption of rhenium, acquire absorption constant n=3.84 from straight slope.N value
Show that the reaction of resin adsorption rhenium is easier to carry out between 2-10.
As can be seen from Figure 7, rhenium adsorption rate is maximum in pH 1.0-6.0, when pH value is less than 1.0 or greater than 6.0 under adsorption rate
Drop, it is seen that best upper prop acidity should select pH 2.0-5.0 to be advisable.
Fig. 8 is adsorption curve different in flow rate, 1-0.5mLmin in figure-1, 2-1mLmin-1, 3-2mLmin-1, 4-3mLmin-1, 5-4mLmin-1
Fig. 8 shows that flow velocity is faster, and solution is shorter with resin contact time, and resin bed breakthrough point is more forward, and adsorption rate is got over
It is low.For guarantee rhenium adsorption rate, answer 1~2mL/min of coutroi velocity be it is suitable, if flow velocity is too small, although can guarantee that rhenium can
Absorption completely, but disengaging time is extended, influence working efficiency.It is right in 1~2mL/min of flow velocity and under conditions of do not penetrate
The adsorption rate of low concentration rhenium is up to 95% or more.
As seen from Figure 9, each 2mL of 1mg/mL rhenium solution flows through exchange column, and breakthrough point occurs at 80mL, and penetration is
0.02mg, saturated adsorption capacity with the difference of rhenium content and stoste in every part of efflux add up method calculate saturated adsorption capacity is
162mg/g。
The elution curve of Figure 10 difference stripping liquid concentration, 1-(1+1) NH4OH in figure, 2-3mol/L NH4OH, 3-
1.5mol/L NH4OH.As seen from Figure 10,1.5mol/L, 3mol/L and (1+1) NH4OH elution volume are respectively 8,6,4mL, are washed
De- rate is respectively 99.6%, 100.6%, 100.1%.Eluant strength is higher, and elution curve peak value is higher, more precipitous, elution
Volume is also fewer, but excessively high concentration easily causes experiment to waste, and comprehensively considers, and experiment is eluted using 3mol/L NH4OH.
As shown in Figure 11: for absorption acidity in pH value 1.0, rhenium distribution coefficient is minimum, and system is distributed within the scope of pH value 2.0-5.0
Number is relatively stable.The distribution coefficient of uranium is increased slightly with pH increase, and the distribution coefficient of rhenium is relatively large with the increased amplitude of pH.Rhenium
Uranium separation has maximum value β Re/U=79.65 in pH value 2.0, is much larger than 1, indicates that the two is easily isolated.Therefore, pH is selected
Value 2.0 is the optimum acidity of ZGT75 resin SEPARATION OF URANIUM rhenium.PH value is about 2 in In Pregnant Solution From In-situ Leaching, this is to realize the separation of uranium rhenium
Factor advantageously.
Embodiment 2:
By the sandstone-type uranium mineralization with respect containing association rhenium resource, according in uranium ore: leachate (volume ratio)=1:12 ratio,
It is added in 20g/L dilution heat of sulfuric acid, 1.5g/L is added, it is mixed that uranium, rehenic acid are obtained after room temperature oscillation is impregnated 20 hours, after filtering
Close solution.Slag is washed slag three times with a small amount of leaching solution, wash water is incorporated in leachate, and it is molten to obtain uranium, rhenium acidic mixed
Liquid and filter residue (leaching rate of slag meter uranium is 92%, and the leaching rate of rhenium is 84%, PH=1.68.Eh=541mv).With D263 yin from
Sub-exchange resin is adsorbent, with absorbing process again is saturated, uranium, rhenium in leachate is adsorbed, using 6% ammonium nitrate
(NH4NO3) desorption uranium after, resin returns to adsorption process after making the transition.After certain cycle period, resin is basic to low concentration rhenium
Reach adsorption equilibrium, rhenium content maintains about 1mg/g in resin at this time.By the uranium solution eluted (16g/L), sodium hydroxide is used
Precipitating obtains sodium diuranate product (yellow cake) after drying.The adsorption tail liquid after uranium will be adsorbed, with the free of designed, designed synthesis
It is that adsorbent adsorbs the rhenium in adsorption tail liquid under conditions of guaranteeing 17min that type, which mixes amine macroreticular resin, reaches absorption
After balance, rhenium content reaches 31mg/g in resin at this time, under certain conditions, will using certain density ammonium hydroxide as strippant
Rhenium gets off from resin desorption, obtains Ammonium rhenate solution (7.4g/L).Evaporative crystallization rhenium product: by step (4) rehenic acid obtained
Ammonium concentrate, is concentrated by evaporation at a certain temperature, stands still for crystals at a certain temperature, and mother liquor of precipitation of ammonium returns to strip liquor and prepares work
Skill.Purification is recrystallized after crystal is filtered, is obtained rehenic acid potassium product (purity 98%), and the comprehensive recovery of rhenium is up to 87% at this time.
Embodiment 3:
By the sandstone-type uranium mineralization with respect containing association rhenium resource, according in uranium ore: leachate (volume ratio)=1:8 ratio,
It is added in 20g/L dilution heat of sulfuric acid, 2g/L is added and obtains uranium, rhenium acidic mixed after filtering after room temperature oscillation is impregnated 16 hours
Solution.Slag is washed slag three times with a small amount of leaching solution, wash water is incorporated in leachate, obtains uranium, rehenic acid mixed solution
With filter residue (leaching rate of slag meter uranium is 91%, and the leaching rate of rhenium is 83%, PH=1.69.Eh=535mv).With D263 anion
Exchanger resin is adsorbent, with absorbing process again is saturated, uranium, rhenium in leachate is adsorbed, using 6% ammonium nitrate (NH4NO3)
After desorbing uranium, resin returns to adsorption process after making the transition.After certain cycle period, resin basically reaches absorption to low concentration rhenium
Balance, rhenium content maintains about 1mg/g in resin at this time.The uranium solution eluted (17g/L) is dried with sodium hydroxide pellets
Sodium diuranate product (yellow cake) is obtained after dry.The adsorption tail liquid after uranium will be adsorbed, amine is mixed with the sequestered of designed, designed synthesis
Macroreticular resin is adsorbent, under conditions of guaranteeing 15min, is adsorbed to the rhenium in adsorption tail liquid, after reaching adsorption equilibrium,
Rhenium content reaches 23mg/g in resin at this time, using certain density ammonium hydroxide as strippant, under certain conditions, by rhenium from resin
Desorption is got off, and is obtained Ammonium rhenate solution (5.8g/L).Evaporative crystallization rhenium product: by step (4) rehenic acid ammonium concentrate obtained,
It is concentrated by evaporation, stands still for crystals at a certain temperature at a certain temperature, mother liquor of precipitation of ammonium returns to strip liquor preparing process.By crystal mistake
Purification is recrystallized after filter, is obtained rehenic acid potassium product (purity reaches 96.2%), and the comprehensive recovery of rhenium is up to 82% at this time.
Claims (4)
1. a kind of method for recycling association rhenium resource from sandstone-type uranium mineralization with respect ground dipping uranium extracting process adsorption tail liquid, it is characterised in that should
Technique includes the following steps:
(1) acidleach: the sandstone-type uranium mineralization with respect containing association rhenium resource is added in the dilution heat of sulfuric acid of the oxidant containing a certain concentration,
Guarantee that leachate PH<2, Eh>500mV obtain uranium, rehenic acid mixed solution after room temperature oscillation is impregnated 12-24 hours after filtering；
(2) it adsorbs: using D263 anion exchange resin as adsorbent, with saturation absorbing process again, by uranium absorption in leachate,
After desorbing uranium using 6% ammonium nitrate, resin returns to adsorption process after making the transition；
(3) precipitate uranium: the uranium solution that will be got off in step (2) with elution with ammonium nitrate is precipitated, is dried with sodium hydroxide pellets
Sodium diuranate product is obtained afterwards；
(4) Adsorption of Rhenium: the adsorption tail liquid after uranium will adsorb in step (2), with the mixed amine macropore of the sequestered of designed, designed synthesis
Resin is adsorbent, the sequestered mix amine macroreticular resin be the macropore that is constituted with the numerous groups such as primary amine, secondary amine, hydroxyl from
Sub-exchange resin, the presence of these groups, which has, to be conducive to form complex with rehenic acid root or forms hydrogen bond, when guaranteeing certain contact
Between under conditions of, the rhenium in adsorption tail liquid is adsorbed, after reaching adsorption equilibrium, using certain density ammonium hydroxide as strippant,
Under certain conditions, rhenium is got off from resin desorption, obtains Ammonium rhenate solution；
(5) evaporative crystallization rhenium product: step (4) rehenic acid ammonium concentrate obtained is concentrated by evaporation, at a certain temperature one
Determine to stand still for crystals at temperature, mother liquor of precipitation of ammonium returns to strip liquor preparing process；Purification is recrystallized after crystal is filtered, and obtains rehenic acid potassium
Product.
2. the method for recycling association rhenium resource from sandstone-type uranium mineralization with respect ground dipping uranium extracting process adsorption tail liquid as described in claim 1,
It is characterized in that in uranium ore in leaching process: uranium ore is entered to concentration and is by ratio of the leachate volume than=1:1~1:10
The sulfuric acid of 5-15 g/L, 0-2g/L hydrogen peroxide guarantee PH<2, in Eh>500mV solution, stirring at normal temperature 12~24 hours, and clarification 1
~3 hours, the solution of uranium-bearing, rhenium is obtained after filtering.
3. the method for recycling association rhenium resource from sandstone-type uranium mineralization with respect ground dipping uranium extracting process adsorption tail liquid as described in claim 1,
It is characterized in that the mixed amine macroporous ion-exchange resin that dissociates is primary amine, the free amine type series tree of tertiary amine macropore in the technical process of Adsorption of Rhenium
Rouge, the resin are 1.6 × 10-3 s-1 to the rate of adsorption of rhenium, i.e. time of contact is 15-20min, acidity pH 2.0~
5.0, which are conducive to rhenium, adsorbs, and adsorption equilibrium obeys Freundish adsorption isotherm, can carry out at normal temperature；Small-sized Dynamic Adsorption examination
Test show resin to underwater trace rhenium adsorption rate up to 95 % or more, 3 mol/L NH4OH of 25 times of resin bed volumes can be by rhenium
Elution, ground immersion liquid coexisting ion do not influence the absorption and desorption of rhenium completely, and H2SO4 solution can make resin regeneration；Resin is to can inhale
Attached 0.03 mg/L rhenium solution, the rate of recovery is up to the % of 96 %~102.
4. the method for recycling association rhenium resource from sandstone-type uranium mineralization with respect ground dipping uranium extracting process adsorption tail liquid as described in claim 1,
It is characterized in that in rehenic acid potassium recrystallization process, rehenic acid potassium thickening temperature is no more than 80 DEG C, weight in evaporative crystallization rhenium Product Process
Crystallization temperature is lower than 4 DEG C, and the mixed amine macroporous ion-exchange resin that dissociates is primary amine, the free amine type series plastics of tertiary amine macropore, is guaranteeing one
Under conditions of determining time of contact, the rhenium in adsorption tail liquid is adsorbed, after reaching adsorption equilibrium, is with certain density ammonium hydroxide
Strippant under certain conditions gets off rhenium from resin desorption, obtains Ammonium rhenate solution.
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| CN107460316B (en) * | 2017-07-10 | 2019-02-01 | 核工业北京化工冶金研究院 | A method of from uranium ore recycling low concentration rhenium in immersion liquid |
| CN107686900B (en) * | 2017-07-10 | 2019-09-17 | 核工业北京化工冶金研究院 | A kind of method of uranium rhenium in spent ion exchange resin synthetical recovery leachate |
| CN107519948B (en) * | 2017-08-09 | 2020-06-05 | 中国地质科学院郑州矿产综合利用研究所 | Composite amino weakly-alkaline anion exchange resin and method for recovering rhenium from arsenic sulfide slag leachate |
| CN108677010A (en) * | 2018-06-14 | 2018-10-19 | 中核通辽铀业有限责任公司 | A kind of ground-dipping uranium extraction comprehensive recycling process |
| CN110923480B (en) * | 2019-12-20 | 2020-10-02 | 华中科技大学 | Application of aminoimidazole type ionic liquid loaded resin in adsorption separation of rhenium or technetium |
| CN111437891A (en) * | 2020-03-03 | 2020-07-24 | 东华理工大学 | Anion exchange resin and preparation method and application thereof |
| CN111621653B (en) * | 2020-05-09 | 2022-08-05 | 中国石油天然气集团有限公司 | Method for recovering trace rhenium from uranium ore leaching liquid |
| CN115072789A (en) * | 2022-08-08 | 2022-09-20 | 中国地质科学院郑州矿产综合利用研究所 | Preparation method of high-purity ammonium rhenate |
| 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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