CN101429860B - Desalination little-reagent ground-dipping uranium extraction method - Google Patents
Desalination little-reagent ground-dipping uranium extraction method Download PDFInfo
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Abstract
The invention relates to a method for extracting uranium by desalting and on-site leaching with less agent, in particular to a technique for extracting uranium from uranium ores with high degree of mineralization of underground water in an ore bed. The technique adopts a desalting plus less agent step, and the concrete steps of the technique include: 1. desalting underground water and reducing the degree of mineralization of the underground water; and 2 extracting uranium by a leaching agent containing a latent solvent HCO3<->, oxygen and a pH adjustment agent. The invention solves problems of blockage caused by calcium sulphate and calcium carbonate in area with underground water of high degree of mineralization during on-site leaching, ensures smooth uranium extraction by on-site leaching and improves the uranium leaching efficiency.
Description
Technical field
The present invention relates to a kind of method of ground-dipping uranium extraction, particularly (extract the method for uranium ore＞5g/L) uranium ore from the ore bed degree of mineralization of ground water is higher.
Background technology
Sandrock-type uranium deposit mainly adopts the Situ Leaching exploitation, generally referred to as ground-dipping uranium extraction.Dipping uranium extracting process mainly is divided into acid system (sulfuric acid) and two kinds of methods of alkaline process (carbonic hydroammonium) routinely.But when the salinity of ledge underground water was higher, the ground-dipping uranium extraction technology was restricted (SANDSTONE URANIUM DEPOSITS that the ledge degree of mineralization of ground water is surpassed 5g/L abroad be decided to be can not ground soak the mineral deposit)
[1-2]Under the groundwater condition of high salinity, the exploitation of sandrock-type uranium deposit is a global ground-dipping uranium extraction difficult problem.The ten red beach Shihongtan deposit bed degrees of mineralization of ground water are up to 8～11g/L, because the ledge degree of mineralization of ground water is high, forefathers' acid system on probation and alkaline process ground soak and all produce chemical precipitation and cause ground-dipping uranium extraction to carry out, namely utilize acid system to produce calcium sulfate precipitation, make the ledge hole and take out/the liquid injection hole obstruction, finally causing to carry out ground-dipping uranium extraction; Utilize alkaline process to produce a large amount of precipitations of calcium carbonate, cause equally stopping up
[3]Therefore, the degree of mineralization of ground water too high (carbonate in water, gypsum approach the precipitation critical condition) is to cause that acid system and alkaline process ground soak obstruction and the main cause that makes ground-dipping uranium extraction work be difficult to proceed.
Forefathers have carried out the ground-dipping uranium extraction test of the little reagent of large flow (hydrogen peroxide+carbon dioxide) to this mining area.This achievement in research remains the deficiency aspect two: the one, and the leachate uranium concentration is lower, can extend leaching cycle, and cost of production is higher, affects economic benefit; The 2nd, even use concentrated water in soaking the uranium process without reagent, in leachate, calcium, heavy carbonic root and sulfate radical are also higher, and soak CO in the uranium process
2Can cause CaCO
3Dissolving, increase Ca
2+Concentration, therefore still have the danger of calcium precipitation.
[1] fault is the people. Situ Leaching adopt the several problems of uranium discussion. Uranium .2006,25 (2): 57-60.
[2] Shu Milin MB. etc., ground soaks uranium exploration, Inst. No.203, Xibei Bureau of Geologic Exploration, Ministry of Nuclear Industry, 1992.
[3]Su?Xuebin，Wang?Haifeng，Yao?Yixuan，2002，Field?test?of?ISL?uranium?at?Shihongtan?deposit?inXinjiang，China，IAEA-TECDOC-1396，pp：204-212
An above-mentioned difficult problem based on high salinity groundwater province ground-dipping uranium extraction existence, be badly in need of a kind of new ground soaking technology technical method of research, can solve under the salinity higher strip part of ore bed underground water chemical precipitation blockage problem in the ground-dipping uranium extraction process, can reach again the purpose that improves the leachate uranium concentration, further improve the uranium resource rate of recovery, thereby the solution route of an essence is provided for the economic exploitation of the SANDSTONE URANIUM DEPOSITS resource of this more difficult exploitation.
Summary of the invention
The present invention relates to a kind of method (or technique) of desalination little-reagent ground-dipping uranium extraction, the method is being avoided producing on the basis of precipitation obstruction, can improve Efficiency of bioleaching uranium, shorten and soak the uranium cycle, solve the ground dipping uranium extracting process technology of the regional SANDSTONE URANIUM DEPOSITS of high salinity underground water.
The present invention protects a kind of ground-dipping uranium extraction method (or technique) of high salinity uranium ore, and the method comprises desalination underground water step, and this step can reduce salinity, reduces leaching solution pH and remove calcium, can avoid the precipitation of calcium sulfate and calcium carbonate.Desalinating process creates conditions for the enforcement that few reagent soaks the technology such as uranium.The desalination step comprises injects ledge with desalination water, contains ore deposit underground water with mixed diluting, reduces the salinity that contains mineral water.Wherein desalination water is the water that can reduce salinity after any concentrated water with containing mineral water layer underground water mixes and not produce mineral precipitation.Desalination water is selected from low mineralization tap water, low mineralization underground water, artificial demineralized water, distilled water, and the tail water of low mineralization after uranium ore is extracted in the hydrometallurgy that also can be recycled workshop, perhaps recycles the hydrometallurgy workshop low mineralization tail water of processing through past calcium.
The present invention protects a kind of desalination little-reagent ground-dipping method (or technique), comprises two large steps: desalination and few molten lixiviate of reagent are got, and they are basic technical schemes of two indispensable one of the ground-dipping uranium extraction of the regional SANDSTONE URANIUM DEPOSITS of high salinity underground water.Under the desalination prerequisite, suitably add the cosolvent of uranium, help to improve the leaching rate of uranium ore.
Increase in theory molten amount of soaking reagent, can improve leaching efficiency, but many restrictions are arranged in practice.Except the factor restriction of economic benefit, in the ground dipping uranium extracting process of the regional SANDSTONE URANIUM DEPOSITS of high salinity underground water, add the too much molten reagent that soaks to cause precipitation to be stopped up in production practices, finally affect carrying out smoothly of ground-dipping uranium extraction.Therefore very few and too much molten to soak reagent dosage all unreasonable, determines the suitable molten key that reagent dosage is few reagent technical scheme of soaking.Compare " little reagent " and " without reagent " technique, " few reagent " technique has obvious superiority, because its Efficiency of bioleaching uranium is higher and be unlikely to occur precipitation and stop up.
Cosolvent HCO in step is got in molten lixiviate
3 -Concentration be controlled at the HCO of precipitation of calcium carbonate
3 -Boundary value.Contain HCO
3 -Cosolvent be any HCO of containing
3 -And do not cause that salinity improves and the chemical agent of mineral precipitation, preferred HCO
3 -Alkali metal salt, ammonium salt, particularly preferably carbonic hydroammonium.
Precipitation of calcium carbonate is subjected to HCO
3 -Concentration, calcium ion concentration, pH three factor controllings are mutually the inverse correlation relation between three factors of control precipitation of calcium carbonate.When the free energy of reaction of setting hydrogeochemical process is zero, and when setting other reaction condition relevant with this effect and being definite value, the ideal value according to another studied reaction condition of thermodynamic principles calculating gained is referred to as reaction condition boundary value.Reaction condition boundary value calculates according to the saturation index principle, this Computing Principle belongs to known technology, such as " application hydrogeochemistry " (Shi Weijun, Sun Zhanxue, Atomic Energy Press, in December, 2005) chapter 4 (p.139) content introduction the computational methods of boundary value.Control the fringe conditions value of each factor of precipitation, can calculate by following formula and try to achieve.Reactional equation is:
Wherein D and E are reactant, and A is product.Other reaction condition in following formula ([D], [E], T (temperature)) is given regularly, activity (or concentration) boundary value---[A] of another reaction condition A that studies
bFor
For example, with regard to the precipitating HCO of calcium carbonate of the present invention
3 -The boundary value of concentration, calcium ion concentration, pH three factors calculates in accordance with the following methods.
HCO
3 -+Ca
2++OH
-＝CaCO
3+H
2O
log[HCO
3 -]
b＝14-pH-logK-log[Ca
2+]
According to this design formulas, calcium ion content and pH (utilizing the analysis of data of on-the-spot leachate to obtain) under fixed condition, can calculate when in leachate, precipitation of calcium carbonate occuring the boundary value [HCO of heavy carbonic radical content in water
3 -]
b: same reason also can calculate respectively pH value and Ca
2 +Boundary value (consider CaSO
4And/or CaCO
3Precipitation).
According to this Computing Principle, at Shihongtan deposit bed, HCO
3 -Border concentration be 1200mg/L, so HCO
3 -Interpolation concentration should control Steep cencentration below 1200mg/L, preferably control HCO in leachate
3 -Concentration at 300-900mg/L, further the concentration of preferred leachate is 500-850mg/L, particularly preferably 600-800mg/L.
Few molten lixiviate of reagent is got step and is also comprised oxidation step, and described oxidation is that oxidising agent is injected ledge, and oxidising agent can add in desalination underground water step, or gets step in molten lixiviate and add, or adds two steps simultaneously.Described oxidising agent comprises and anyly can and not cause that with the oxidation of mineral uranium salinity improves and the oxidisability reagent of mineral precipitation, preferably oxygen, air, hydrogen peroxide, hypochlorous acid alkali metal salt, hypochlorous acid ammonium, hypochlorous acid or perchloric acid, particularly preferably oxygen.When wherein using oxygen, adding concentration is 150-450mg/L, preferred 250-350mg/L, particularly preferably 300mg/L.
Few molten lixiviate of reagent is got step and can also be comprised calcium or pH value regulating step, the described calcium that goes refers to before the tail water that uranium ore extracts recycles, when the calcium ion content of tail water during higher than the border content value of precipitation of calcium carbonate, high salinity tail water is reduced the salinity step, this step can be gone calcon, ion-exchange by interpolation, and the modes such as absorption deliming are carried out.The boundary value of calcium ion is calculated by at that time field data according to aforementioned Computing Principle.In addition, use cosolvent (HCO
3 -) after will cause the pH value of leaching solution to raise, can use pH value regulating step that pH is adjusted to acidity on the weak side (pH≤7), the adjusting of pH value is to realize by interpolation pH value conditioning agent or the mode by acid-exchange resin.PH value conditioning agent comprises acid and CO
2, can use separately acid or CO
2Or use simultaneously acid and CO
2, wherein acid does not improve and causes any acid of mineral precipitation for not causing the salinity that contains ore deposit underground water.Example hydrochloric acid (HCl), acid-exchange resin etc.The preferred CO that uses
2Or HCl+CO
2Regulate the pH value.The boundary value of the pH value that should control leachate during lower than precipitation of calcium carbonate, the Computing Principle according to aforesaid boundary value calculates in conjunction with on-the-spot at that time data equally, controls pH≤6.9 at the Shihongtan deposit bed.
Few molten lixiviate of reagent is got and is not used the pH regulating step can reach the effect that greatly improves the uranium ore leaching rate equally in step, only by adding oxygen and HCO
3 -Get final product, at this moment HCO
3 -Interpolation concentration equally must be at the HCO of precipitation of calcium carbonate
3 -Boundary value below.At Shihongtan deposit bed, HCO
3 -Interpolation concentration be controlled to be that in leachate, concentration is 300-500mg/L, preferred 400-500mg/L.
The method of a kind of desalination little-reagent ground-dipping uranium extraction of special protection of the present invention comprises:
A1. oxidant is added desalination water,
A2. by liquid injection hole, desalination water is injected underground ledge,
A3. pass through the underground ledge underground water of drawing liquid hole extracting,
A4. send hydrometallurgy workshop extraction uranium, tail water is recycling, enters B1 as the molten base fluid that soaks, and the fresh water that the underground water step is desalinated in all right conduct of the softening tail water of processing of the tail water of low mineralization or process inject underground ledge.
B1. recycle the tail water in hydrometallurgy workshop,, need to increase and go the calcium step during higher than the calcium ion boundary value of precipitation of calcium carbonate when the calcium ion content of tail water,
B2. add cosolvent HCO
3 -,
B3. use HCl and CO
2PH value to leaching solution is regulated,
B4. by liquid injection hole, leaching solution is injected underground ledge,
B5 extracts leaching solution by the drawing liquid hole, forwards the A4 step to.
Under the groundwater condition of high salinity, the exploitation of sandrock-type uranium deposit is a global ground-dipping uranium extraction difficult problem.Forefathers' acid system on probation and alkaline process ground soak and all produce chemical precipitation and cause ground-dipping uranium extraction to carry out, desalination little-reagent ground-dipping technique efficiently solves sandrock-type uranium deposit ground under the groundwater condition of high salinity and soaks calcium sulfate, precipitation of calcium carbonate blockage problem in process, has solved area and the similar concentrated water SANDSTONE URANIUM DEPOSITS Area Uranium resources development and utilization problem of breathing out of telling.Ground soaks and needs in process to improve Efficiency of bioleaching uranium by soaking uranol, the present invention has overcome prior art in the technique of the ground-dipping uranium extraction of the regional SANDSTONE URANIUM DEPOSITS of high salinity underground water, dare not add soak uranol or only the trace add the shortcoming of soaking uranol content, greatly improved Efficiency of bioleaching uranium.The uranium method of soaking desalination little-reagent of the present invention can reduce the salinity (being reduced to 3.4g/L by 10.5g/L) of mining layer underground water greatly, the calcium sulfate of leachate, calcium carbonate saturation index are all less than zero, and the leachate uranium concentration improves 3 times (being increased to 36.5mg/L by 12mg/L) than soak the uranium method without reagent.
The present invention obtains the calculating of the suitable amounts of these additives, particularly boundary value by series of experiments.These test procedures comprise:
One, desalination underground water.
Two, desalination water+O
2The pre-oxidation ledge
Three, desalination water removes calcium
Four, remove desalination water+HCO after calcium
3 -+ CO
2+ O
2The preparation leachant leaches.After the groundwater of highly mineralized desalination, add appropriate carbonic hydroammonium in leaching solution, and by adding carbon dioxide to carry out to leaching solution the pH value that leaching solution is regulated in acidifying, to guarantee not produce precipitation of calcium carbonate.At last by adding oxidant to carry out ground-dipping uranium extraction.
Five, HCl acidifying+optimum content HCO
3 -+ CO
2+ O
2The preparation leachant leaches.Leaching solution is carried out acidifying, reduce the pH value, progressively improve the heavy carbonic radical content, make the heavy carbonic radical content reach optimum value, reach best leaching effect.
Description of drawings
Fig. 1 tail water and local mixing of fresh water water salinity and saturation index relation curve
Fig. 2 is molten soaks salinity change curve in process, and M=5.55g/L is the critical condition that precipitation occurs
Fig. 3 HCO
3 - bCa curve (VIIIBg2-5., SI
Calcite=0, pH value=6.9)
Fig. 4 in mixed liquor goes calcium sodium carbonate demand at 4: 1
Fig. 5 HCO
3 -Content equilibrium valve (boundary value)
The pH value result of calculation (PHREEQC) of Fig. 6 carbon dioxide acidifying test IX leaching solution
The technological process of Fig. 7 desalination little-reagent ground-dipping uranium extraction
Fig. 8 soaks test reagent on-the-spotly and adds situation and soak the uranium result map
Salinity, conductivity variations in Fig. 9 underground water desalination process
The variation of calcium carbonate, calcium sulfate saturation index in Figure 10 desalination stage underground water
Figure 11 desalination+O
2Leach uranium concentration variation in the leaching stage leachate
Figure 12 desalination little-reagent (border content HCO
3 -+ O
2) result of the test Figure 13 acidifying, desalination, best HCO
3 -Content soaks the uranium effect
Figure 14 desalination little-reagent leaching effect
The specific embodiment
1. desalination little-reagent ground-dipping uranium extraction technique
Test procedure of the present invention comprises the following steps:
Desalination little-reagent ground-dipping uranium extraction technique is desalinated, is gone calcium, adds and soak uranium cosolvent (carbonic hydroammonium), add HCl and CO in right amount by utilization
2Five guardian techniques such as leaching solution pH, oxygenation are controlled in acidifying, easily produce the difficult problem of chemistry obstruction when having solved preferably in the high salinity area with the conventional method ground-dipping uranium extraction, have created condition for the leaching rate that improves leachate uranium concentration and uranium simultaneously.
A. use desalination technology (desalination operation), avoided calcium sulfate precipitation obstruction (seeing Fig. 1), create conditions for implementing few reagent technique again simultaneously, having fresh water to have the area, the desalination operation is cost-effective technology.
Desalination technology is to contain aquifer, ore deposit underground water by injection fresh water with high salinity to mix, extract out simultaneously and contain aquifer, ore deposit underground water, the technology of high salinity underground water in the dilution ledge, containing aquifer, the ore deposit degree of mineralization of ground water in the operation block section drops to below 5g/L, namely can avoid the precipitation (seeing Fig. 1,2) of calcium sulfate, soak the uranium cosolvent for adding simultaneously, improve and to soak the uranium chemical potential usefull space is provided.
B. add sodium carbonate and go the calcium technology.The calcium ion of high-load is the hidden danger that calcium salt (calcium sulfate, calcium carbonate) produces precipitation, although the desalination operation can be eliminated the danger of calcium sulfate precipitation, to a certain degree reduces calcium ion content, not necessarily can avoid the precipitation of calcium carbonate; Under certain pH condition, in leaching solution, calcium ion content is lower in addition, and what can add soaks uranium cosolvent (HCO
3 -) just more (seeing Fig. 3), reduce calcium ion content and create conditions for implementing few reagent Uranium leaching.Sodium carbonate is the good precipitating reagent of calcium ion, and a small amount of sodium carbonate can be reduced to calcium ion concentration in water the limit and require (seeing Fig. 4).
C. add the cosolvent technology and (add HCO
3 -Operation), leachate uranium concentration and uranium leaching rate have been improved
Soak HCO in uranium solution by adding the method for amount of ammonium bicarbonate, having improved
3 -Concentration, and then improved the uranium concentration in the leachate, accelerated the leaching velocity of uranium.But HCO in leaching solution
3 -Content is not The more the better, and it is to have certain limiting the quantity of to require, the concept that Here it is so-called " few reagent ".This project achievement in research provides the HCO with precipitation of calcium carbonate
3 -Boundary value deducts the molten HCO in process that soaks
3 -Increment limit HCO in direction for solvent solutions
3 -The method of content, the HCO in the direction for solvent solutions of calculating gained
3 -Content is the best HCO of desalination little-reagent ground-dipping uranium extraction technique
3 -Content.The HCO of precipitation of calcium carbonate
3 -Boundary value can be by calculating obtains according to the curve (seeing Fig. 5) of experimental data making or according to the hydrochemical analyse data.
D. use Acidizing Technology (to add CO
2With add the HCl operation) control leaching solution pH, prevented that effectively ground from soaking the precipitation of calcium carbonate in process
Precipitation of calcium carbonate is jointly controlled by heavy carbonic radical content, pH and calcium ion content three factors.PH and calcium ion content are lower, in direction for solvent solutions, the border content of heavy carbonic root just can be higher, in the water of certain content heavy carbonic root and calcium ion, have the pH boundary value of corresponding precipitation of calcium carbonate on the other hand, the pH value of the leaching solution of configuration can not surpass this boundary value.Because of after the carbonic hydroammonium that adds alkalescence, the pH of leaching solution goes back up to again greater than 8 simultaneously, therefore must carry out acidifying to leaching solution, namely requires pH is reduced to a safer value (the pH boundary value of＜precipitation of calcium carbonate).Desalination little-reagent ground-dipping uranium extraction technique is taked first with hydrochloric acid the pre-acidifying of fresh water after adding carbonic hydroammonium, then is used CO
2The pH value of leaching solution is transferred to less than its boundary value, has been reached the purpose of avoiding precipitation of calcium carbonate.Use again CO
2The result of calculation that the pH value of leaching solution reduces is seen Fig. 6
E. the oxygenation technology (adds O
2Operation) promote uranous oxidation, improved the leaching concentration of uranium
In ore, uranium exists with tetravalence and sexavalence form usually.Cosolvent can only leach hexavalent uranium, and at first uranous leaching must be oxidized to hexavalent uranium.Add oxidant when adding cosolvent, optimum oxygen concentration is 250～350mg/L.
2 desalination little-reagent ground-dipping uranium extraction technique field trial example and achievements thereof
The ground dipping uranium extracting process field trial on October 24th, 2006 formally, to end of day February 25 in 2007, last 125 days.As previously mentioned, whole test is divided into four-stage, and each step-by-step test situation summary is as follows:
A. underground water desalination.Reach by injecting tap water the purpose that reduces the ledge degree of mineralization of ground water.This stage is lasted 36 days,, approximately can be with the ledge degree of mineralization of ground water from being down to below 5g/L more than 10.5g/L about 20 days.Do not add any reagent in process of the test, leachate uranium concentration＜1;
B. desalinate without reagent and soak the uranium test.Add O in leaching solution
2And CO
2, this stage purpose be research application desalination non-reagent ground dipping uranium extracting method this test block section soak the uranium effect, and compare with follow-up desalination little-reagent test.Last 29 days, leachate uranium concentration 2～11mg/L, uranium leaching amount 10.06kg.
C. desalination little-reagent (border content HCO
3 -+ O
2) leaching test.Add O in leaching solution
2And CO
2And HN
4HCO
3, this stage main purpose is in conjunction with HCO under laboratory test achievement research field condition
3 -With O
2Soak the uranium fringe conditions.Last 34 days, the leachate uranium concentration rises to 32mg/L gradually by 12mg/L, uranium leaching amount 57.88kg.
D.HCl acidifying+optimum content HCO
3 -+ CO
2+ O
2Leaching test.Add HCl, O in leaching solution
2And CO
2And HN
4HCO
3, this stage is utilized above several stage achievements, works out optimum content HCO
3 -+ CO
2+ O
2Leaching condition, and soak with this understanding uranium.Last 26 days, leachate uranium content 32～38mg/L, to off-test, uranium concentration still has the trend of rising, uranium leaching amount 58kg.
Soak the uranium test by desalination little-reagent, progressively worked out on-the-spot the best and soaked the uranium condition, do not having under the prerequisite of stopping up, Leaching Uranium metal 125.94Kg, uranium concentration is elevated to 36.5mg/L, has obtained expected result, specifically sees Fig. 8 and table 1.
The table 1 different tests stage is soaked uranium situation statistical form
2.1 desalination test
Test block section ledge underground water is desalinated, and is to guarantee under the condition of not stopping up, and adds few reagent to carry out the basis of ground-dipping uranium extraction test.The salinity of underground water and conductivity variations such as Fig. 9 in the desalination process.
Desalination through 36 days, contain aquifer, ore deposit salinity and be down to 3.4g/L by 10.5g/L, salinity after desalination is about original 1/3rd, electrical conductivity is reduced to 6.5 μ s/cm by 18.4 μ s/cm, be approximately original 1/3rd, to reduce ratio consistent with salinity.Fig. 3 shows, 10 days desalination initial stages, desalinates successful, and electrical conductivity and salinity are reduced to approximately 10.5 μ s/cm, 6g/L by 18.4 μ s/cm, 10.5g/L respectively, and the range of decrease is respectively 8 μ s/cm, 4.5g/L; Desalinate after 12 days, electrical conductivity and salinity underspeed and obviously reduce, and desalinate after 38 days, and electrical conductivity and the salinity range of decrease are very little, substantially tend towards stability, and salinity is 3.9g/L approximately, and electrical conductivity is 6.2 μ s/cm approximately.
Saturation index is the index of judging in underground water, whether chemical substance precipitates.In test block section desalination process in underground water calcium carbonate and calcium sulfate saturation index change as shown in figure 10, when making salinity less than 5g/L with fresh water desalination tail water, the calcium sulfate saturation index is reduced to-0.4～-0.6 by original+0.2～0.55, has eliminated the possibility that calcium sulfate precipitation stops up; Calcium carbonate saturation index is reduced between 0～-0.6 by+0.2, as long as suitably control pH value condition, can increase HCO
3 -Concentration, and can not cause CaCO
3Precipitation, thus the space provided for improving the uranium leaching concentration.
2.2 desalination is without reagent (+O
2) leaching test
Desalinate to the basis of 3.4g/L in the degree of mineralization of ground water, carry out while desalinating leaching test.Employing is without the reagent leaching method, and leaching solution is fresh water, does not add any other reagent, and oxidant is high pressure oxygen.According to different test conditionss, adopt different oxygen concentrations, to soak the optimum oxygen concentration parameter with inquiring into.Leach result as shown in figure 11
Dissolved oxygen concentration is stabilized under the 300mg/L condition, and the Leaching Uranium concentration stabilize is 12mg/L.
Due to adding of oxygen, ledge uranium mineral generation oxidation is increased the leachate uranium concentration, and under the excessive prerequisite of oxygen, maximum Leaching Uranium concentration is 12mg/L, illustrates in this test block section to adopt without reagent (+O
2) uranium concentration is restricted in leachate, soaks the uranium poor effect.
2.3 desalination little-reagent (border content HCO
3 -+ O
2) leaching test
Can not reach desirable leaching effect owing to leaching without reagent, not add any reagent only to add under the condition of oxygen, the uranium concentration in leachate only reaches 12mg/L, further improve uranium concentration in leachate, must add appropriate reagent.For this reason, at desalination+O
2Soak on the basis in uranium stage, carry out few reagent Leaching Test.
Desalination little-reagent (border content HCO
3 -Concentration) the leaching test stage since on December 28th, 2007, to end of day January 30 in 2007, amounts to 34 days, and result of the test as shown in figure 12.Dissolved oxygen in leachate is under 250～400mg/L prerequisite, and result of the test has following feature: tested HCO 16 days
3 -Concentration increases to approximately 400mg/L by nearly 300mg/L, and uranium concentration rises to 30mg/L by 12mg/L, uranium concentration and HCO
3 -Concentration has the relation of growing simultaneously preferably; Then, work as HCO
3 -Concentration increases to approximately 500mg/L by nearly 400mg/L, after uranium concentration is stabilized in about 33mg/L, when increasing HCO again
3 -During concentration, uranium concentration increases and is not obvious.
2.4HCl acidifying+optimum content HCO
3 -+ O
2+ CO
2Leaching test
Adopt hydrochloric acid to carry out acidification.Namely with hydrochloric acid, the pH value of fresh water is acidified to 3～5, then mixes with the solution that has dissolved high-load carbonic hydroammonium, then use the little adjust pH of carbon dioxide, the pH value of leaching solution is down to below 6.8.This step-by-step test began on February 25th, 2007 from January 31st, 2007.Its result of the test is plotted in Fig. 6 .8, shows that in leaching solution, dissolved oxygen concentration remains on 300～400mg/L, HCO in leachate
3 -Concentration increases to 600mg/L gradually by nearly 500mg/L, and in leachate, uranium concentration is risen at 35mg/L by 32.5mg/L; HCO in leachate
3 -When-concentration increased to 800mg/L gradually by nearly 600mg/L, in leachate, uranium concentration was basicly stable at 35～37mg/L, is up to 38.2mg/L.Until off-test, average uranium concentration is stabilized in 36mg/L, even higher (Figure 13) from February 6th, 2007 beginning.
Adopt the hcl acidifying leaching solution, add the carbonic hydroammonium of optimum condition, can increase substantially the concentration of heavy carbonic root, thereby water-rock reaction is accelerated, improve the uranium leaching effect.
3 desalination little-reagent ground-dipping uranium extraction test result analysis
Desalination little-reagent leaches field trial and is divided into desalination stage and leaching stage.After desalination, few reagent leaches general effect such as Figure 14 shows.
As seen from the figure, in front 20 days of test second stage and the phase III, the HCO of leachate
3 -Concentration is 250～280mg/L, and in leaching solution, dissolved oxygen keeps increasing to 300～450mg/L, and the uranium concentration of leachate is basicly stable at 12mg/L, 6 days stabilization time.Under without the reagent leaching condition, test block section leachate uranium concentration is that low concentration leaches characteristics.
In 15 days later stages of test phase III, in leaching solution, dissolved oxygen is controlled between 250～350mg/L, by controlling the pH value of leaching solution, is guaranteeing to increase in right amount HCO under the minus prerequisite of calcium carbonate saturation index
3 -Concentration makes that in leaching solution, heavy carbonic root concentration increases to 400mg/L by nearly 250mg/L, and in leachate, uranium concentration correspondingly is upgraded to 32mg/L by 12mg/L;
Test the quadravalence section, in leaching solution, dissolved oxygen keeps 300～400mg/L, continues to increase HCO
3 -Concentration is to 550mg/L, and in leachate, uranium concentration stabilizes to 32mg/L; Continue to increase the HCO of leaching solution
3 -Concentration is to 850mg/L, and in leachate, uranium concentration stabilizes to the 36mg/L left and right.
Claims (11)
1. the ground-dipping uranium extraction method of a high salinity uranium ore, comprise
A, desalination underground water, desalination water are selected from the tail water in low mineralization tap water, low mineralization underground water, artificial demineralized water, distilled water and hydrometallurgy workshop;
B, few molten lixiviate of reagent are got, and desalination underground water is that desalination water is injected ore bed, and the desalination high salinity contains the step of aquifer, ore deposit underground water, and desalination underground water step should be reduced to 5g/L with the salinity of underground water; It is that uranium cosolvent HCO is soaked in interpolation that few molten lixiviate of reagent is got
3 -Leaching solution inject undergroundly, improve the step of the leaching rate of uranium ore, this leaching solution can be that general low salinity water can be also the circulation tail water after uranium extracts, cosolvent HCO in step is got in molten lixiviate
3 -Concentration be controlled at the HCO of precipitation of calcium carbonate
3 -Below the concentration of border, contain HCO
3 -Cosolvent comprise any HCO of containing
3 -And do not cause that salinity improves and the chemical agent of mineral precipitation.
2. method as claimed in claim 1, wherein, contain HCO
3 -Cosolvent be HCO
3-
-Alkali metal salt, ammonium salt.
3. method as claimed in claim 1, in the method, also comprise oxidation step, described oxidation is that oxidising agent is injected ledge, oxidising agent can add in desalination underground water step, or get step in molten lixiviate and add, or adding two steps simultaneously, described oxidising agent comprises and anyly can and not cause that with the uranium oxidation salinity improves and the oxidisability reagent of mineral precipitation.
4. method as claimed in claim 3, wherein preferably oxygen, air, hydrogen peroxide, hypochlorous acid alkali metal salt, hypochlorous acid ammonium, hypochlorous acid or perchloric acid of oxidisability reagent.
5. method as claimed in claim 3, wherein, oxidisability reagent is oxygen.
6. method as claimed in claim 5, wherein to add concentration be 150-450mg/L to oxygen.
7. method as claimed in claim 5, wherein oxygen adds concentration to be preferably 250-350 mg/L.
8. as method as described in one of claim 1-7, the B step increases calcium and pH value regulating step individually or simultaneously, described go calcium to refer to that the circulation tail washings uses after uranium ore extracts before, when calcium ion content surpasses its border content value, reduce the step of calcium content; It is to be undertaken by the pH control method that this area is commonly used that the pH value is regulated, by adding CO
2, acid or use one or more modes that combine of acid-exchange resin to carry out, the boundary value of the pH value of controlling leachate during lower than precipitation of calcium carbonate.
9. method as claimed in claim 8, the wherein said calcium step of going is used to add and is gone calcium agent, ion-exchange and absorption deliming to carry out; During the pH value is regulated, the pH of control leachate≤6.9.
10. method as claimed in claim 8, wherein going the calcium step is the method for calcon of going by interpolation, and the described calcon that goes is solvable carbonate, and described soluble carbonate salt is the alkali metal salt of carbonic acid or the ammonium salt of carbonic acid; PH regulates by adding separately or jointly acid and CO
2Carry out, wherein acid does not improve and can not cause any acid of mineral precipitation for not causing the salinity that contains ore deposit underground water.
11. the method for a desalination little-reagent ground-dipping uranium extraction comprises:
A1. oxidising agent is added desalination water, desalination water is the water that can reduce salinity after any concentrated water with containing mineral water layer underground water mixes and not produce mineral precipitation; Desalination water is selected from low mineralization tap water, low mineralization underground water, artificial demineralized water, distilled water, recycle the hydrometallurgy workshop extracts the tail water of low mineralization after uranium ore or recycles the hydrometallurgy workshop low mineralization tail water of processing through past calcium;
A2. by liquid injection hole, desalination water is injected underground ledge;
A3. by the underground ledge underground water of drawing liquid hole extraction;
A4. send hydrometallurgy workshop extraction uranium, tail water is recycling, as the molten base fluid that soaks of B1 step;
B1. tail water removes calcium, and condition is that calcium ion content surpasses boundary value;
B2. add cosolvent HCO
3 -, addition is for controlling the HCO of leachate
3 -Concentration less than the HCO of precipitation of calcium carbonate
3 -Border concentration contains HCO
3 -Cosolvent comprise any HCO of containing
3 -And do not cause that salinity improves and the chemical agent of mineral precipitation;
B3. regulate leaching solution pH value;
B4. by liquid injection hole, leaching solution is injected underground ledge;
B5. by the drawing liquid hole, leaching solution is extracted, forward the A4 step to.
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| CN101619401B (en) * | 2009-07-17 | 2011-05-04 | 云南佰盾环保技术有限公司 | Method for recycling uranium from uranium extraction tailings |
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| CN114687714B (en) * | 2022-04-12 | 2023-06-16 | 中国矿业大学 | Nanoparticle composite low-mineralization water for improving CO 2 Method for injection capability |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3792903A (en) * | 1971-08-30 | 1974-02-19 | Dalco Oil Co | Uranium solution mining process |
| US4024216A (en) * | 1975-07-02 | 1977-05-17 | Nalco Chemical Company | Carbonate leach uranium ore processing with sodium polyacrylate flocculant |
| US4360500A (en) * | 1977-09-12 | 1982-11-23 | Fly Anderson B | Mineral leaching |
| US4561696A (en) * | 1982-09-21 | 1985-12-31 | Phillips Petroleum Company | In situ recovery of mineral values |
| US7111246B2 (en) * | 2004-02-17 | 2006-09-19 | Microsoft Corporation | User interface accorded to tiered object-related trust decisions |
-
2008
- 2008-12-12 CN CN 200810183287 patent/CN101429860B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3792903A (en) * | 1971-08-30 | 1974-02-19 | Dalco Oil Co | Uranium solution mining process |
| US4024216A (en) * | 1975-07-02 | 1977-05-17 | Nalco Chemical Company | Carbonate leach uranium ore processing with sodium polyacrylate flocculant |
| US4360500A (en) * | 1977-09-12 | 1982-11-23 | Fly Anderson B | Mineral leaching |
| US4561696A (en) * | 1982-09-21 | 1985-12-31 | Phillips Petroleum Company | In situ recovery of mineral values |
| US7111246B2 (en) * | 2004-02-17 | 2006-09-19 | Microsoft Corporation | User interface accorded to tiered object-related trust decisions |
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