CN101429860A - 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 from the ore bed degree of mineralization of ground water higher (〉 5g/L) uranium ore extract the method for uranium ore.
Background technology
Sandrock-type uranium deposit mainly adopts the original place to leach exploitation, generally abbreviates ground-dipping uranium extraction as.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 phreatic salinity of ledge was higher, the ground-dipping uranium extraction technology was restricted (SANDSTONE URANIUM DEPOSITS that abroad the ledge degree of mineralization of ground water is surpassed 5g/L be decided to be can not ground soak the mineral deposit)
[1-2]The exploitation of sandrock-type uranium deposit is a global ground-dipping uranium extraction difficult problem under the groundwater condition of high salinity.Ten red beaches, the ten red beach uranium deposit degrees of mineralization of ground water are up to 8～11g/L, because ledge degree of mineralization of ground water height, forefathers' acid system on probation and alkaline process ground soak and all produce chemical precipitation and cause ground-dipping uranium extraction to carry out, promptly utilize acid system to produce calcium sulfate precipitation, make the ledge hole and take out/the liquid injection hole obstruction, finally cause 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, gypsum are near the precipitation critical condition in the water) is to cause that acid system and alkaline process ground soak the main cause of stopping up and making ground-dipping uranium extraction work be difficult to proceed.
Forefathers have carried out the ground-dipping uranium extraction test of the little reagent of big 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 prolong leaching cycle, and cost of production is higher, influences economic benefit; Even two are to use concentrated water to soak in the uranium process at no reagent, calcium, heavy carbonic root and sulfate radical also are higher in the leachate, 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. the original place leach adopt the several problems of uranium discussion. uranium ore smelting .2006,25 (2): 57-60.
[2] Shu Milin M.B. 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
Above-mentioned difficult problem based on the existence of high salinity groundwater province ground-dipping uranium extraction, be badly in need of a kind of new ground soaking technology technical method of research, can solve under the higher condition of the phreatic salinity of ore bed chemical precipitation blockage problem in the ground-dipping uranium extraction process, can reach the purpose that improves the leachate uranium concentration again, further improve the uranium resource rate of recovery, thereby the solution route of YITIAOGEN person's character is provided for the economic exploitation of this difficult SANDSTONE URANIUM DEPOSITS resource of exploiting.
Summary of the invention
The present invention relates to a kind of method (or technology) of desalination little-reagent ground-dipping uranium extraction, this method is being avoided producing on the basis of precipitation obstruction, can improve and soak uranium efficient, shorten and to soak the uranium cycle, solve the ground dipping uranium extracting process technology of high salinity underground water area SANDSTONE URANIUM DEPOSITS.
The present invention protects a kind of ground-dipping uranium extraction method (or technology) of high salinity uranium ore, and this 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 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 be any with contain the water that can reduce salinity after the phreatic concentrated water of mineral water layer 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 perhaps recycles the hydrometallurgy workshop low mineralization tail water of handling through past calcium behind the hydrometallurgy that also the can be recycled workshop extraction uranium ore.
The present invention protects a kind of desalination little-reagent ground-dipping method (or technology), comprises two big 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 high salinity underground water area SANDSTONE URANIUM DEPOSITS.Under the desalination prerequisite, suitably add the cosolvent of uranium, help to improve the leaching rate of uranium ore.
Increase molten amount of soaking reagent in theory, can improve leaching efficiency, but many restrictions are arranged in practice.In production practices, except the factor restriction of economic benefit, in the ground dipping uranium extracting process of high salinity underground water area SANDSTONE URANIUM DEPOSITS, add the too much molten reagent that soaks and to cause precipitation to be stopped up, finally influence 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 " no reagent " technology, " few reagent " technology has obvious superiority, and is higher and be unlikely to take place precipitation and stop up because it soaks uranium efficient.
Cosolvent HCO in the 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, preferred especially carbonic hydroammonium.
Precipitation of calcium carbonate is subjected to HCO
3 -Concentration, calcium ion concentration, the control of pH three factors are the inverse correlation relation mutually 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 reaction condition that is studied of thermodynamic principles calculating gained is referred to as the reaction condition boundary value.The reaction condition boundary value calculates according to the saturation index principle, this calculating principle belongs to technique known, 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.The fringe conditions value of each factor of control precipitation can be calculated by following formula and try to achieve.Reactional equation is:
Wherein D and E are reactant, and A is a 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 is studied
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 the fixed condition can calculate when in the leachate precipitation of calcium carbonate taking place the boundary value [HCO of heavy carbonic radical content in water
3 -]
b: same reason also can calculate pH value and Ca respectively
2 +Boundary value (consider CaSO
4And/or CaCO
3Precipitation).
Calculate principle according to this, at ten red beach uranium deposits, HCO
3 -Border concentration be 1200mg/L, so HCO
3 -Interpolation concentration should control leachate concentration below 1200mg/L, preferably control HCO in the leachate
3 -Concentration at 300-900mg/L, further the concentration of preferred leachate is 500-850mg/L, preferred especially 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 the step adding in molten lixiviate, or adds two steps simultaneously.Described oxidising agent comprises and anyly can and not cause that salinity improves and the oxidisability reagent of mineral precipitation with the oxidation of mineral uranium, preferably oxygen, air, hydrogen peroxide, hypochlorous acid alkali metal salt, hypochlorous acid ammonium, hypochlorous acid or perchloric acid, preferred especially oxygen.When wherein using oxygen, adding concentration is 150-450mg/L, preferred 250-350mg/L, preferred especially 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 is meant before the tail water that uranium ore extracts recycles, when the calcium ion content of tail water is 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 modes such as absorption deliming are carried out.The boundary value of calcium ion calculates according to the former reason of aforementioned calculating field data at that time.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 acid or CO separately
2Or use acid and CO simultaneously
2, wherein acid does not contain any acid that the phreatic salinity in ore deposit improves and cause mineral precipitation for not causing.Example hydrochloric acid (HCl), acid-exchange resin etc.The preferred CO that uses
2Or HCl+CO
2Regulate the pH value.Boundary value when the pH value that should control leachate is lower than precipitation of calcium carbonate, the calculating principle according to aforesaid boundary value obtains in conjunction with on-the-spot at that time data computation equally, in uranium deposits control pH≤6.9, ten red beaches.
Few molten lixiviate of reagent is got and is not used the pH regulating step can reach the effect that improves the uranium ore leaching rate greatly equally in the 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 ten red beach uranium deposits, HCO
3 -Interpolation concentration be controlled to be that concentration is 300-500mg/L in the leachate, 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 the hydrometallurgy workshop to extract uranium, and tail water is recycling, enters B1 as the molten base fluid that soaks, and the softening tail water of handling of the tail water of low mineralization or process can also inject underground ledge as the fresh water of desalinating the underground water step.
B1. recycle the tail water in hydrometallurgy workshop, when the calcium ion content of tail water is higher than the calcium ion boundary value of precipitation of calcium carbonate, needs to increase and go the calcium step,
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.
The exploitation of sandrock-type uranium deposit is a global ground-dipping uranium extraction difficult problem under the groundwater condition of high salinity.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 technology 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 the process, has solved area and the similar concentrated water SANDSTONE URANIUM DEPOSITS area uranium resource development and use problem of breathing out of telling.Ground soaks to be needed in the process to improve and soak uranium efficient by soaking uranol, the present invention has overcome prior art in the technology of the ground-dipping uranium extraction of high salinity underground water area SANDSTONE URANIUM DEPOSITS, dare not add and soak uranol or the only micro-shortcoming of soaking uranol content that adds, improve greatly and soaked uranium efficient.The uranium method of soaking desalination little-reagent of the present invention can reduce mining layer phreatic salinity (being reduced to 3.4g/L by 10.5g/L) greatly, the calcium sulfate of leachate, calcium carbonate saturation index are all less than zero, and the leachate uranium concentration soaks the uranium method than no reagent and improves 3 times (being increased to 36.5mg/L by 12mg/L).
The present invention obtains the calculating of the suitable amounts, particularly boundary value of these additives by a series of tests.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 behind the calcium
3 -+ CO
2+ O
2The preparation leachant leaches.After the desalination of high mineralization underground water, in leaching solution, add an amount of carbonic hydroammonium, and leaching solution is carried out the pH value that leaching solution is regulated in acidifying, to guarantee not produce precipitation of calcium carbonate by adding carbon dioxide.Carry out ground-dipping uranium extraction by adding oxidant at last.
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 to soak salinity change curve in the process, and M=5.55g/L is the critical condition that precipitation takes place
Fig. 3 HCO
3 - bCa curve (VIIIBg2-5., SI
Calcite=0, pH value=6.9)
Go calcium sodium carbonate demand in Fig. 4 4:1 mixed liquor
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
Figure 10 desalinates the variation of calcium carbonate in the stage underground water, calcium sulfate saturation index
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 technology
Test procedure of the present invention may further comprise the steps:
Desalination little-reagent ground-dipping uranium extraction technology is by utilization desalination, remove calcium, add and soak uranium cosolvent (carbonic hydroammonium), add HCl and CO in right amount
2Five guardian techniques such as acidifying control leaching solution pH, oxygenation easily produce the difficult problem of chemistry obstruction when having solved in the high salinity area with the conventional method ground-dipping uranium extraction preferably, 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 to stop up (see figure 1), create conditions for implementing few reagent technology 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 phreatic technology of high salinity in the dilution ledge, containing aquifer, the ore deposit degree of mineralization of ground water in the operation block section drops to below the 5g/L, promptly can avoid the precipitation (seeing Fig. 1,2) of calcium sulfate, provide the usefull space for the uranium cosolvent is soaked in adding, the uranium chemical potential is soaked in raising simultaneously.
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, though 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, calcium ion content is low more in the leaching solution in addition, and what can add soaks uranium cosolvent (HCO
3 -) with regard to many more (see figure 3)s, reduce calcium ion content and create conditions for the few reagent of enforcement soaks uranium technology.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 the water limit and require (see figure 4).
C. add the cosolvent technology and (add HCO
3 -Operation), leachate uranium concentration and uranium leaching rate have been improved
By adding the method for amount of ammonium bicarbonate, improved and soaked HCO in the uranium solution
3 -Concentration, and then improved the uranium concentration in the leachate, accelerated the leaching velocity of uranium.But HCO in the leaching solution
3 -Content is not The more the better, and it is to have certain limiting the quantity of to require, the notion 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 the process that soaks
3 -Increment limit HCO in the leaching solution prescription
3 -The method of content, the HCO in the leaching solution prescription of calculating gained
3 -Content is the best HCO of desalination little-reagent ground-dipping uranium extraction technology
3 -Content.The HCO of precipitation of calcium carbonate
3 -Boundary value can be by obtaining according to the curve (see figure 5) of experimental data making or according to the hydrochemical analyse data computation.
D. use the acidifying 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 the 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 low more, the border content of heavy carbonic root just can be high more in the leaching solution prescription, in the water of certain on the other hand content heavy carbonic root and calcium ion, have the pH boundary value of corresponding precipitation of calcium carbonate, the pH value of the leaching solution of configuration can not surpass this boundary value.Because of behind 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, promptly requires pH is reduced to value (the pH boundary value of＜precipitation of calcium carbonate) of safety.Desalination little-reagent ground-dipping uranium extraction technology is taked earlier with hydrochloric acid the pre-acidifying of fresh water after adding carbonic hydroammonium, is used CO again
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 CO again
2The result of calculation that the pH value of leaching solution reduces is seen Fig. 6
E. the oxygenation technology (adds O
2Operation) promotes uranous oxidation, improved the leaching concentration of uranium
Uranium exists with tetravalence and sexavalence form usually in the ore.Cosolvent can only leach hexavalent uranium, and uranous leaching must at first 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 technology field trial example and achievements thereof
The ground dipping uranium extracting process field trial formally began on October 24th, 2006, to end of day February 25 in 2007, lasted 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 the purpose that reduces the ledge degree of mineralization of ground water by injecting tap water.This stage is lasted 36 days,, about about 20 days can be with the ledge degree of mineralization of ground water from reducing to below the 5g/L more than the 10.5g/L.Do not add any reagent in the process of the test, leachate uranium concentration＜1;
B. the no reagent of desalination soaks the uranium test.In leaching solution, add O
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.In leaching solution, add O
2And CO
2And HN
4HCO
3, this stage main purpose is in conjunction with HCO under the 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.In leaching solution, add HCl, O
2And CO
2And HN
4HCO
3, this stage is utilized above several stages achievement, works out optimum content HCO
3 -+ CO
2+ O
2Leaching condition, and soak uranium with this understanding.Last 26 days, leachate uranium content 32～38mg/L, to off-test, uranium concentration still has the trend of slow 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 to leach uranium metal 125.94Kg under the prerequisite of stopping up, 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 the basis that few reagent carries out the ground-dipping uranium extraction test.Phreatic salinity and conductivity variations such as Fig. 9 in the desalination process.
Desalination through 36 days, contain aquifer, ore deposit salinity and reduce to 34g/L by 10.5g/L, it is original 1/3rd that salinity after the desalination is about, and 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 that 10 days desalination initial stages, the desalination effect was obvious, and electrical conductivity and salinity are reduced to about 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 the electrical conductivity and the salinity range of decrease are very little, tend towards stability the about 3.9g/L of salinity, the about 6.2 μ s/cm of electrical conductivity substantially.
Saturation index is an index of judging whether chemical substance precipitates in the underground water.In the test block section desalination process in the 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; The 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 uranium leaching concentration.
2.2 desalinate no 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.Adopt no reagent leaching method, leaching solution is a fresh water, does not add any other reagent, and oxidant is a high pressure oxygen.According to different test conditionss, adopt different oxygen concentrations, to soak the optimum oxygen concentration parameter with inquiring into.Leach the result as shown in figure 11
Dissolved oxygen concentration is stabilized under the 300mg/L condition, leaches uranium concentration and stabilize to 12mg/L.
Because the adding of oxygen, ledge uranium mineral generation oxidation is increased the leachate uranium concentration, under the excessive prerequisite of oxygen, it is maximum that to leach uranium concentration be 12mg/L, illustrate the no reagent of this test block section employing (+O2) uranium concentration is restricted in the 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 because no reagent leaches, only add under the condition of oxygen not adding any reagent, the uranium concentration in the leachate only reaches 12mg/L, further improve uranium concentration in the leachate, must an amount of reagent of adding.For this reason, at desalination+O
2Soak on the basis in uranium stage, carry out few reagent extract technology test.
Desalination little-reagent (border content HCO
3 -Concentration) the leaching test stage to end of day January 30 in 2007, amounts to 34 days since on December 28th, 2007, 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 about 400mg/L by nearly 300mg/L, and uranium concentration rises to 30mg/L by 12mg/L, uranium concentration and HCO
3 -Concentration has simultaneous growth relation preferably; Then, work as HCO
3 -Concentration increases to about 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.
24HCl acidifying+optimum content HCO
3 -+ O
2+ CO
2Leaching test
Adopt hydrochloric acid to carry out acidification.Promptly the pH value of fresh water is acidified to 3～5, mixes with the solution that has dissolved high-load carbonic hydroammonium then, use the little adjust pH of carbon dioxide again, the pH value of leaching solution is reduced to below 6.8 with hydrochloric acid.This step-by-step test began on February 25th, 2007 from January 31st, 2007.Its result of the test is plotted among Fig. 6 .8, shows that dissolved oxygen concentration remains on 300～400mg/L, HCO in leachate in the leaching solution
3 -Concentration increases to 600mg/L gradually by nearly 500mg/L, and uranium concentration is risen at 35mg/L by 32.5mg/L in the leachate; HCO in leachate
3 -When-concentration increased to 800mg/L gradually by nearly 600mg/L, uranium concentration was basicly stable at 35～37mg/L in the leachate, is up to 38.2mg/L.Until off-test, average uranium concentration is stabilized in 36mg/L, even higher (Figure 13) from beginning on February 6th, 2007.
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 quickened, 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 the desalination, few reagent leaches general effect such as Figure 14 shows.
As seen from the figure, in preceding 20 days of test second stage and the phase III, the HCO of leachate
3 -Concentration is 250～280mg/L, and dissolved oxygen keeps increasing to 300～450mg/L in the leaching solution, and the uranium concentration of leachate is basicly stable at 12mg/L, 6 days stabilization time.Under no reagent leaching condition, test block section leachate uranium concentration is that low concentration leaches characteristics.
In 15 days later stages of test phase III, dissolved oxygen is controlled between 250～350mg/L in the leaching solution, by the pH value of control leaching solution, is guaranteeing to increase HCO in right amount under the minus prerequisite of calcium carbonate saturation index
3 -Concentration makes that heavy carbonic root concentration increases to 400mg/L by nearly 250mg/L in the leaching solution, and uranium concentration correspondingly is upgraded to 32mg/L by 12mg/L in the leachate;
Test the quadravalence section, dissolved oxygen keeps 300～400mg/L in the leaching solution, continues to increase HCO
3 -Concentration is to 550mg/L, and uranium concentration stabilizes to 32mg/L in the leachate; Continue to increase the HCO of leaching solution
3 -Concentration is to 850mg/L, and uranium concentration stabilizes to about 36mg/L in the leachate.
Claims (13)
1. the ground-dipping uranium extraction method of a high salinity uranium ore, this method comprises desalination underground water step, this step comprises injects ledge with desalination water, contain aquifer, ore deposit underground water with mixing and dilution, reduce the salinity that contains mineral water, wherein desalination water is and contains the water that can reduce salinity after the phreatic concentrated water in aquifer, ore deposit mixes and not produce mineral precipitation.
2. the method for claim 1, wherein desalination water is selected from the tail water in low mineralization tap water, low mineralization underground water, artificial demineralized water, distilled water and hydrometallurgy workshop.
3. the method for a desalination little-reagent ground-dipping uranium extraction comprises
A. desalinate underground water,
B. lack the molten lixiviate of reagent and get,
Desalination underground water is that desalination water is injected ore bed, and the desalination high salinity contains the phreatic step in aquifer, ore deposit; 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 also can be the circulation tail water after uranium extracts.
4. as method as described in the claim 3, this method also comprises 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.
5. as method as described in the claim 3, wherein oxidant uses oxygen, and it is 150-450mg/L that described oxygen adds concentration, preferred 250-350mg/L, preferred especially 300mg/L.
6. as method as described in the claim 3, wherein desalinating the underground water step should be reduced to 5g/L with phreatic salinity, and cosolvent HCO in the step is got in molten lixiviate
3 -Concentration be controlled at the HCO of precipitation of calcium carbonate
3 -Below the concentration of border.
7. as method as described in the claim 6, wherein, at ten red beach uranium deposits, HCO
3 -Border concentration calculated value be 1200mg/L, HCO
3 -Interpolation concentration should control HCO in the leachate
3 -Concentration at 300-900mg/L, further the concentration of preferred leachate is 500-850mg/L, preferred especially 600-800mg/L.
8. as method as described in one of claim 3-7, described B step increases calcium and pH value regulating step individually or simultaneously, the described calcium that goes is meant before uranium ore extracts the use of back circulation tail washings, when calcium ion content surpasses its border content value, reduce the step of calcium content, this step can be gone calcon, ion-exchange by interpolation, and modes such as absorption deliming are carried out; It is to be undertaken by this area pH control method commonly used that the pH value is regulated, and the boundary value when the pH value of control leachate is lower than precipitation of calcium carbonate is preferred, in the preferred pH of ten red beach uranium deposits≤6.9.
9. method as claimed in claim 8, pH regulates can add CO
2, acid or use acid from one or more modes that combine of exchanger resin carry out, preferably by adding acid and CO separately or jointly
2Carry out, wherein acid does not contain any acid that the phreatic salinity in ore deposit improves and can not cause mineral precipitation for not causing.
10. as method as described in one of claim 3-7, the wherein said HCO that contains
3 -Cosolvent comprise 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, preferred especially, carbonic hydroammonium; Described oxidising agent comprises and anyly can and not cause that salinity improves and the oxidisability reagent of mineral precipitation with the uranium oxidation, preferably oxygen, air, hydrogen peroxide, hypochlorous acid alkali metal salt, hypochlorous acid ammonium, hypochlorous acid or perchloric acid, especially preferably oxygen.
11. as method as described in the claim 8, wherein going the calcium step is the method for removing calcon by interpolation, the described calcon that goes is solvable carbonate, the alkali metal salt of preferred carbonic acid, the ammonium salt of carbonic acid, preferred especially sodium carbonate, the acid that the pH conditioning agent uses is HCl, hydrobromic acid.
12. the method for a desalination little-reagent ground-dipping uranium extraction comprises:
A1. oxidant is added desalination water,
A2. by liquid injection hole desalination water is injected underground ledge,
A3. extract underground ledge underground water by the drawing liquid hole,
A4. send the hydrometallurgy workshop to extract uranium, tail water is recycling, enters B1 as the molten base fluid that soaks,
B1. tail water removes calcium, and condition is that calcium ion content surpasses boundary value,
B2. add cosolvent HCO
3 -,
B3. regulate leaching solution pH value
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
13. as method as described in the claim 11, wherein, desalination water is the low mineralization tail water of low mineralization underground water, low mineralization tap water or A4 step; Oxidant is an oxygen, and the addition of oxygen is 250-350mg/L; Cosolvent is a carbonic hydroammonium, and addition is the HCO of control leachate
3 -Concentration less than the HCO of precipitation of calcium carbonate
3 -Border concentration; Removing calcon is the soluble carbon hydrochlorate, preferred carbonic acid alkali metal; PH regulates and uses HCl and CO
2, control pH value is at it below boundary value.
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