CN102534214A - New method for recycling gallium from Bayer mother solution by using chelate resin - Google Patents
New method for recycling gallium from Bayer mother solution by using chelate resin Download PDFInfo
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Abstract
The invention discloses a new method for recycling gallium from a Bayer mother solution by using chelate resin. The method comprises the following steps of: (1) filling a gallium extracting resin into a resin column, and allowing a gallium-containing Bayer mother solution to flow through the resin by using an intermittent dynamic column passing method to reach adsorption saturation; (2) washing the saturated gallium extracting resin with water; (3) desorbing gallium adsorbed by the resin by using an acidic eluent, performing precipitation, impurity removal and other treatment on the eluant to obtain pure concentrated gallium-containing electrolyte, and electrolyzing to obtain the gallium; and (4) washing the eluted resin with water until the pH value of a liquid at the outlet of an exchange column is 6-8. The method has the advantages of simplicity and feasibility, high resin utilization rate, high gallium recovery rate, low energy consumption and cost, high grade of the obtained gallium product, and the like.
Description
Technical field
The present invention relates to a kind of with resin absorption gallium and the gallium that resin adsorbs is washed solution from the strong alkali solution that contains gallium such as Bayer mother liquor with acid elute soln; Through obtaining the concrete applied technical procedure of gallium after edulcoration purification, the electrolysis, belong to the hydrometallurgy field afterwards.
Background technology
Gallium is a kind of dissipated metal, and important effect is arranged in semi-conductor industry, and the demand of GALLIUM metal pure is also continuing to increase year after year.The source of GALLIUM metal pure is rare, the many by products from aluminium industry etc. of its product.The common containing metal gallium of bauxite 0.002-0.008%.In the alumina producing Bayer process process, the GALLIUM metal pure in the bauxite has 70% approximately with aluminum oxide leaching together, and about 30% remains in the red mud.Along with the circulation of seed precipitation solution, the GALLIUM metal pure concentration in the Bayer-process seed-separating mother liquor can be accumulated to 100-300ppm.
Extract the production GALLIUM metal pure with resin, become the main path that from the alumina producing flow process, extracts gallium at present.In production practice, the working capacity of resin is the important factor of decision production cost.The NaOH-Na that generally uses in the industrial production at present
2The gallium of S eluent desorb resin absorption, its desorption efficiency is relatively poor.Use the initial stage at resin,, generally more than 3.5g/L reaches, use NaOH-Na because the resin loading capacity is bigger
2When the S eluent carried out drip washing to resin, its desorption efficiency only had about 60%, and the resin residue gallium content is higher, and the resin utilization ratio reduces.Along with the decay of resin, desorption efficiency increases, but still can not reach more than 90%.And owing to used Na
2S has also introduced S in stripping liquid
2-Impurity must be with oxygenant with S before carrying out electrolysis procedure
2-Remove, and need to concentrate stripping liquid, thereby improve electrolytic efficiency with raising gallium concentration.
Summary of the invention
For solving the problems referred to above that exist in the prior art, the invention provides a kind of application art that from the Bayer mother liquor, extracts gallium with resin.
Technical scheme provided by the invention is to extract resin with gallium gallium in the Bayer mother liquor is adsorbed, reach absorption saturated after, water extracts Bayer mother liquor washes clean residual in the resin with gallium; With elute soln gallium is extracted resin then and carry out desorb, must concentrate stripping liquid, but electrolysis gets GALLIUM metal pure after deposition, removal of impurities; Eluted resins is treated after export effluent pH and be 6-8, can get into next absorption-wash-out loop cycle, drops to 300mg/L until the s-adsorption of resin.
More specifically, the present invention provides a kind of and from the Bayer mother liquor, extracts the application art of gallium with resin, carries out according to following steps:
(1) absorption: resin is filled in the exchange column, adopt dynamic post or the dynamic method of crossing post of intermittent type crossed of continous way, make the liquid flow that contains gallium through resin;
(2) washing: washing remove residue in resin surface contain gallium liquid, to the pH value of exchange column spout liquid be 6-8; Adopt washing can avoid bringing impurity into subsequent step;
(3) wash-out: with eluent the adsorbed gallium of resin is carried out desorb, elute soln is handled to obtain the more purified concentrated gallium electrolyte that contains, can obtain GALLIUM metal pure through electrolysis;
(4) washing: because of change has taken place in eluted resins environmental properties of living in, so before absorption once more, need wash to the pH value of exchange column spout liquid be 6-8.So far, resin has been accomplished a loop cycle, and can get into next absorption-wash-out circulation, and so resin can use several repeatedly, drops to than low value (below the 300mg/L) up to the s-adsorption of resin.
Preferred version of the present invention is:
Adsorption process of the present invention is related, and to contain gallium liquid mainly be strong alkaline liquid such as Bayer mother liquor of containing gallium etc.Gallium of the present invention extracts the resin that resin is chosen band amidoxim functional group on the resin matrix, and the chemical structure of amidoxim functional group is following:
This resinoid has been realized commercialization, and domestic have products such as LSC-600 that Xi'an Sunresin New Materials Co., Ltd. produces and LSC-600s, the ES-346 that has U.S. Doulite company to produce abroad, and the like product produced of state such as Japan.
The post mode of crossing in the adsorption process can adopt dynamic post or the dynamic post of crossing of intermittent type crossed of continous way, the dynamic post mode of crossing of preferred intermittent type, and main purpose is the impurity of being convenient to clear up in the resin layer, makes the liquid of the resin of flowing through be unlikely to stop up and influence adsorption effect; Simultaneously can make the resin in the exchange column adsorb gallium equably, it is saturated to avoid because exchange column has the dead angle part resin being adsorbed.
In the conventional exchange column, not translator and whipping appts, resin remains static all the time, lets contain the gallium alkaline stream and carried out post through resin, and such mode is called the dynamic column method of crossing of continous way.
The dynamic exchange column that is adopted in the post mode of crossing of the intermittent type that the present invention adopted has motor and whipping appts, realizes post absorption through opening or close to stir.Stirring under the closing state; Resin remains static; Contain gallium alkali lye forward flow from top to down, the upper strata resin reaches the absorption state of saturation quickly because of contact earlier contains gallium alkali lye, after the upper strata resin absorption is saturated; Contain gallium alkali lye and can penetrate this one deck resin and get into down one deck, it is saturated that resin successively reaches absorption like this.Owing to contain in the gallium alkali lye and have suspended substance; Be mainly in the Bayer mother liquor a large amount of dissolved white lakes,, in the process that the resin of flowing through adsorbs, separate out alumine hydroxide colloid because of receiving sensitivity of factor affecting such as temperature; And along with the time of dynamic adsorption increases and increases; Thereby will cause space and the filter screen below the exchange column between the spherical resin blocked, influence contains the proper flow of gallium alkali lye, thereby has reduced adsorption efficiency., start and stir after for some time at the dynamic post of crossing, can let impurity such as alumine hydroxide colloid can be dispersed into fine particle preferably, and discharge through the filter screen of exchange column below.The dynamic post mode of crossing of intermittent type can solve blocking problem, improves adsorption efficiency, makes the resin bed redistribution simultaneously, guarantees that resin all can adsorb saturated in the exchange column.The dynamic start/stop time that stirs in the column method of crossing of intermittent type determine by the exchange column rate of discharge: when the exchange column rate of discharge for 70% when following of setting flow, should open stirring; And when the exchange column rate of discharge greater than set flow 95% the time should stop to stir.
Amidoxim functional group on the resin skeleton can carry out chelating with the gallium ion in the alkaline solution; Form firm structure; Because of having selectivity preferably, thereby can contain extraction separation gallium and then concentrated and purified gallium the Gallium solution, for the industrial production of GALLIUM metal pure provides feasibility from alkalescence.The resin of band amidoxim functional group is in the preparation process; General and the amidoxim functional group of amidoxime acid functional group accompanies; It also has certain sequestering power to gallium; Form chelate structure, but the gallium on its chelate structure is relatively poor to the selectivity of gallium ion easily by replacements such as other ion such as aluminum ions.And the amidoxime acid functional group is unstable, in use will convert acid amides gradually into, and then forms carboxylic acid and thoroughly lose the performance of chelating gallium ion.Amidoxim functional group is more stable under alkaline condition, but under acidic conditions, causes the resin absorption performance comparatively fast to descend than being easier to change the amidoxime acid functional group into.So in the duration of contact that should control acid solutions, temperature and resin and acid solution with acid solution during as elute soln (eluent) well.The pH of general elute soln should not be lower than 0.01, but can not be too high, and the solution of higher pH such as pH=6 can not effectively elute the gallium ion that adsorbs on the resin, so the pH of elute soln should not be higher than 4, and can be between 0.01-4.More preferably pH is between pH0.1-3, and preferred pH is between pH0.3-1.Temperature also should obtain control in this process, because temperature is high more, the speed of various group diffusions is fast more in the solution, and the speed of reaction also can be index variation, in order to reduce the degree that the amidoxime acid functional group is changed in amidoxim functional group, needs to reduce temperature; But temperature is too low resin matrix is had damage, production energy consumption increased when simultaneous temperature was low, and production cost raises.So the TR that the present invention adopts is 3-30 ℃, more preferably temperature is 5-20 ℃, and preferred temperature is 8-15 ℃.The time of resin contact acid is short more good more in theory; But in fact; The adsorbed gallium ion of resin just is difficult in the wash-out entering solution if resin and acid residence time are short, and the utilization ratio of resin will descend, so the resin that the present invention adopts and the duration of contact of elute soln are 5-240min.
The method of regulating elute soln pH value among the present invention is to adopt the higher acid solution of concentration that dilute acid soln is carried out dynamic conditioning to obtain.The acid of adjusting pH used in the present invention can be sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, Mono Chloro Acetic Acid etc.Certainly the present invention is to regulate the pH value with the purpose of acid, makes the elute soln gallium ion in the desorb resin effectively, so the acid that the present invention selects for use is not limited to the kind of above-mentioned listed acid.The concentration of the acid solution of the adjusting pH that the present invention is used is 10-99%, is 15-80% more preferably, is more preferably 30-70%.Why the present invention is to reduce employed acid solution volume in the elution process with the concentrated acid purpose, avoids simultaneously causing electrolytic efficiency low because of using the lower concentration acid solution to make the gallium concentration that contains the gallium elute soln lower.Regulate before the pH with concentrated acid among the present invention, needing in resin, to add pH in advance is the weakly acidic water solution between the 0.1-7, and resin is under the comparison demulcent state, and is convenient to resin and is stirred.Can contain gallium ion in the solution that adds in advance, and the amount of gallium ion is The more the better, can make follow-up raw materials cost reduce like this; Other ions, particularly heavy metal ion except that gallium ion, to be prone under alkaline condition to form sedimentary ion etc. few more good more, is advisable to be no more than 100mg/L.
Last handling process to elute soln among the present invention comprises neutralization precipitation, with operations such as alkaline solution dissolution precipitation, removal of impurities, electrolysis.Elute soln is to contain the Gallium solution that contains that the gallium resin obtains behind wash-out; Gallium content wherein is 10mg/L-40g/L; Be acidic solution, want much little because the hydrionic electrolysis of the electrolysis specific activity of gallium ion is active, so directly electrolysis; Otherwise can produce a large amount of hydrogen and not have the generation of gallium, so need carry out proper process to elute soln.
With alkaline solution elute soln is carried out neutralizing treatment, wherein the mass concentration of alkaline solution should can be selected one or more preparations in yellow soda ash, sodium hydroxide, the Pottasium Hydroxide etc. for use greater than 4%.The height of alkali concn in do not have influence with sedimentation effect, but consider the container volume of use and the factors such as complexity of aftertreatment, the present invention preferably uses the alkaline solution of high density, 30%, 50% even the alkaline solution of greater concn.The Gallium trihydroxide that is precipitated out needs to leach through filtration, and filter method can be selected for use centrifugal and Plate Filtration equipment, requires gained Gallium trihydroxide water cut few more good more, and general water cut should be controlled at below 85%.
The Gallium trihydroxide that obtains according to aforesaid way dissolves with high concentration alkali and can obtain sodium solution gallate, and gallium content wherein can reach more than the 40g/L.The Gallium trihydroxide water cut of gained is more little, and gallium content is high more in the sodium solution gallate of dissolving back.Impurity such as the vanadium, iron, copper, lead, boron, chromium, nickel, rubidium of trace are also contained in solution after dissolving the inside, and the electrolysis in later stage is had certain influence, can produce bad phenomenon such as black pole plate, sponge gallium, so before electrolysis, need remove miscellaneous operation.Vanadium mainly exists with forms such as metavanadic acid root, vanadic acid roots in basic soln, can at high temperature form co-precipitation with oxyhydroxide such as white lake, ironic hydroxide, manganous hydroxide, calcium hydroxides and is removed.The mixing of one or more in the above-mentioned oxyhydroxide of optional usefulness, total add-on needs to add the above-mentioned oxyhydroxide in about 3kg left and right sides according to the height decision of content of vanadium in general every 100L sodium solution gallate.Remove the vanadium temperature and be generally 30-110 ℃, preferred temperature is 50-100 ℃, is more preferably 60-90 ℃.The time of reaction is 4-8h.
Remove and to remove heavy metal ion such as iron, copper, lead, chromium plasma behind the vanadium once more; Because of these ions solubleness under alkaline condition own is lower, so can be through improving basicity or adding some coprecipitators or sequestrant further reduces its solubility product in alkaline solution to remove these ions.General more use sodium sulphite, sulfonium ion can form deposition with heavy metal and from solution, separate out, thereby reaches the effect of removing heavy metal ion.Less because of heavy metal ion content in basic soln, so the amount of the sodium sulphite that needs is also less, need in general every 100L solution to add 1-6kg sodium sulphite, stirring reaction 8-20h can remove the heavy metal ion in the solution under the normal temperature.
Sodium solution gallate is after removing vanadium and heavy metal ion; Existence because of sulfonium ion in the solution; Need be removed with oxygenant; The general ydrogen peroxide 50 of selecting environmental protection adds hydrogen peroxide solution and is advisable to be no more than 10kg in the 100L sodium solution gallate, oxidizing reaction 2-6h can obtain more purified electrolytic solution.In electrolyzer, using the volts DS of 1-5V to carry out electrolysis finally can obtain purity and be 3N-4N even the purity gallium metal as 5N.
In sum, need to add removal of impurities raw material 3-15kg in every 100L sodium solution gallate.
The invention provides and a kind ofly from the Bayer mother liquor, extract gallium, then gallium adsorbed on the resin is eluted to elute soln and carries out concentrating and impurity removing and obtain electrolytic solution, can obtain the technological process of GALLIUM metal pure through electrolysis with resin.The eluent that adopts among the present invention is an acid solution, has the elution efficiency height, resin utilization ratio advantages of higher; Later stage adopts the electrolytic solution that precipitates elute soln, dissolves, obtains through removal of impurities at last with alkali to have the gallium content height, can reach the above concentration of 40g/L, thereby reduce electrolytic energy consumption, has improved electrolytic efficiency and gallium product gas purity.That method provided by the present invention has is simple, the resin utilization ratio high, the gallium recovery is high, cut down the consumption of energy and the grade advantages of higher of cost, products obtained therefrom gallium metal.
Embodiment
Embodiment 1
Get LSC-600 resin 500L and be contained in the exchange column, let 25m
3Gallium content is that the Bayer mother liquor of 252mg/L adopts the dynamic post mode of crossing of intermittent type to adsorb.Flow rate control is at 3m
3/ h is when the exchange column exit velocity is 1.8m
3During/h (be set flow velocity 60%), open and stir, at this moment exit velocity slowly recovers, when flow velocity reaches 2.88m
3During/h (be set flow velocity 96%), stop to stir, the dynamic time that crosses post absorption of whole intermittent type is 13h.Adsorb saturated after washing to pH be 6, add the deionized water of 300LpH7, open and stir, the chloroacetic acid solution with 10% is regulated pH to 3, and controlled temperature is 30 ℃, keeps stirring 5min, leaches elute soln 360L, the gallium content that records in this solution is 376mg/L.Again the elute soln 360L that leaches is joined in the resin; Open and stir; Regulate pH to 1 with 15% hydrochloric acid, keep stirring 240min and use 15% hydrochloric acid soln to keep pH 1 not change, leaching filtrating afterwards and obtaining the 550L elute soln; The gallium content of measuring wherein is 3.4g/L, and then calculating resin adsorptive capacity is 3.74g/L.Adding 10% sodium hydroxide solution 167L to the 550L elutriant, to be adjusted to pH be between the 6-8, throw out separated obtaining Gallium trihydroxide deposition 13.89Kg with whizzer, and recording moisture in the Gallium trihydroxide is 78%.Use 30% NaOH dissolving to obtain the sodium solution gallate 42L of basicity as 5N, wherein gallium content is 41.95g/L.In sodium solution gallate, add 0.4KgMn (OH)
2, 0.2Kg Na
2S is warming up to 110 ℃ of reaction 1h, is cooled to 100 ℃ of reaction 4h, filters out post precipitation, and adding 0.66Kg concentration is 50% ydrogen peroxide 50 in filtrating, is controlled at 30 ℃ of reaction 2h down, promptly obtains electrolytic solution.Obtain gallium 1.75Kg through electrolysis 20h, calculate the recovery s%=1.75/ (0.55*3.4)=93.6% of gallium.Repeatable operation like this, resin moved for 10 cycles continuously, and the s-adsorption of resin promptly need be changed resin to 500mg/L.
Embodiment 2:
Get LSC-900 resin 250L and be contained in the exchange column, let 40m
3Gallium content is that the Bayer mother liquor of 252mg/L adopts the dynamic post mode of crossing of intermittent type to adsorb.Flow rate control is at 4m
3/ h is when the exchange column exit velocity is 2.8m
3During/h (be set flow velocity 70%), open and stir, at this moment exit velocity slowly recovers, when flow velocity reaches 3.8m
3During/h (be set flow velocity 95%), stop to stir, the dynamic time that crosses post absorption of whole intermittent type is 12.5h.Adsorb saturated after washing to pH be 7, add pH and be 7 deionized water 300L, open and stir, the vitriol oil with 98% is regulated pH to 4, and controlled temperature is 20 ℃, keeps stirring 15min, leaches elute soln 348L, the gallium content that records in this solution is 175mg/L.Again the elute soln 348L that leaches is joined in the resin; Controlled temperature is 8 ℃; Open to stir, the nitric acid with 30% is regulated pH to 2.5, keeps stirring 30min and uses 30% salpeter solution maintenance pH 2.5 not change; Leach filtrating afterwards and obtain the 442L elute soln, the gallium content of measuring wherein is 1.6g/L; The elutriant 442L that leaches is joined in the resin again, open and stir, controlled temperature is 15 ℃; After sulfuric acid with 80% is regulated pH to 0.3, keep stirring 40min, leach elute soln 475L; The mensuration gallium content is 12.27g/L, and calculating not, the adsorptive capacity of swollen resin is that (LSC-900 has bigger rate of expansion to 23.31g/L, absorption saturated resin volume: do not adsorb between saturated resin volume=1.8-2.0; The adsorptive capacity here is with original resinite product representation, below all with).Adding 30% sodium hydroxide solution 50L to the 475L elutriant, to be adjusted to pH be between the 6-8, throw out separated obtaining Gallium trihydroxide deposition 36.15Kg with whizzer, and recording moisture in the Gallium trihydroxide is 73%.Use 50% NaOH dissolving to obtain the sodium solution gallate 96L of basicity as 4.4N, wherein gallium content is 58.57g/L.In sodium solution gallate, add 3.7KgMn (OH)
2, 1.9Kg Fe (OH)
3, 1.8Kg Na
2S is warming up to 90 ℃ of reaction 6h, filters out post precipitation, in considering liquid, adds 50% ydrogen peroxide 50 7Kg, and reaction 1h promptly obtains electrolytic solution.Obtain GALLIUM metal pure 5.57Kg through electrolysis 15h, calculate the recovery s%=5.57/ (0.475*12.27)=95.57% of gallium.Repeatable operation like this, resin can move for 36 cycles, and the last adsorptive capacity of resin is that 300mg/L is replaceable resin.
Embodiment 3
The practical implementation method is the same with embodiment 2, and difference is:
(1) will adsorb saturated resin wash be 8 to pH after, add the deionized water 300L of pH=7, the phosphoric acid with 70% is with pH regulator to 0.1, controlled temperature is 5 ℃, stirring 10min obtains the 360L elute soln, gallium content 14.7g/L; Above-mentioned elutriant is squeezed in the exchange column again, and controlled temperature is 3 ℃, and the sulfuric acid with 98% is regulated pH to 0.01, obtains the 371L stripping liquid, and the mensuration gallium content is 15.6g/L.
(2) removal of impurities process: adding 2.86Kg white lake, 2.59Kg quicklime, 2.35Kg sodium sulphite, concentration are 50% ydrogen peroxide 50 7.5Kg in the 102L sodium solution gallate, and total amount is 15.3Kg.Concrete operations are following: after white lake and quicklime adding, stir and be warming up to 105 ℃ of insulation 3h, be cooled to 50 ℃; Filtered while hot adds sodium sulphite in gained filtrating, 50 ℃ are reacted 8h down; Filter cleaner adds ydrogen peroxide 50 in gained filtrating, behind 35 ℃ of following reaction 5h; Carry out electrolysis, it is 99.99% GALLIUM metal pure 5.64Kg that electrolysis 12h obtains purity, and calculating the gallium recovery is s%=97.45%.
Adopt this method resin can use for 34 cycles, the 250L resin can produce gallium 80Kg.
Embodiment 4
The practical implementation method is identical with embodiment 3, and difference is:
(1) removing cleaner that miscellaneous operation adds is 50% ydrogen peroxide 50 1.5Kg for the 0.57Kg hydrogen-oxygen contains aluminium, 0.52Kg quicklime, 0.47Kg sodium sulphite, concentration;
(2) temperature is controlled at 60 ℃ of reaction 6h behind the adding sodium sulphite;
(3) to obtain purity be 99.9% GALLIUM metal pure 5.13Kg to electrolysis 20h, and calculating the gallium recovery is s%=88.64%.
Adopt this method 250L resin can produce gallium 75Kg.
Embodiment 5
Adsorption process is with embodiment 2.Adsorb saturated after washing to pH be 7, add pH and be 7 deionized water 300L, open and stir, the phosphoric acid solution with 60% is regulated pH to 1, and controlled temperature is 13 ℃, keeps stirring 30min, leaches elute soln 336L, the gallium content that records in this solution is 3.6g/L.Again the elute soln 336L that leaches is joined in the resin; Controlled temperature is 13 ℃; Open to stir, the phosphoric acid with 60% is regulated pH to 0.8, keeps stirring 10min and uses 60% phosphoric acid solution adjusting pH 0.8 not change; Leach filtrating afterwards and obtain the 423L elute soln, the gallium content of measuring wherein is 9.6g/L; The elutriant 423L that leaches is joined in the resin again, open and stir, controlled temperature is 13 ℃; After phosphoric acid adjusting pH to 0.6 with 60% is also stable, keep stirring 5min, leach elute soln 458L; The mensuration gallium content is 12.7g/L, and calculating not, the adsorptive capacity of swollen resin is 23.31g/L.Adding 30% sodium hydroxide solution 38L to the 458L elutriant, to be adjusted to pH be between the 6-8, throw out separated obtaining Gallium trihydroxide deposition 38.59Kg with whizzer, and recording moisture in the Gallium trihydroxide is 74.2%.Use 50% NaOH dissolving to obtain the sodium solution gallate 94L of basicity as 4.2N, wherein gallium content is 60.52g/L.In sodium solution gallate, add 4.7Kg Al (OH)
3, 3.9Kg CaO, 1.6Kg Na
2S is warming up to 90 ℃ of reaction 6h, filters out post precipitation, in considering liquid, adds 50% ydrogen peroxide 50 3Kg, and reaction 1h promptly obtains electrolytic solution.Obtain GALLIUM metal pure 5.71Kg through electrolysis 14h, calculate the recovery s%=5.71/ (0.458*12.7)=98.17% of gallium.Repeatable operation like this, resin can move for 38 cycles, and the 250L resin can obtain gallium 82Kg altogether.
Claims (26)
1. one kind is extracted the application art of gallium with resin, it is characterized in that may further comprise the steps:
(1) absorption: resin is filled in the exchange column, adopt the dynamic method of crossing post, make to contain the gallium liquid flow through resin;
(2) washing: washing remove residue in resin surface contain gallium liquid, to the pH value of exchange column spout liquid be 6-8;
(3) wash-out: separate with the eluent gallium that resin is adsorbed and to be drawn onto in the solution, elute soln is handled to obtain more purified concentrating and contain gallium electrolyte, can obtain GALLIUM metal pure through electrolysis;
(4) washing: eluted resins is washed, to the pH value of exchange column spout liquid be 6-8, so far; Resin has been accomplished a loop cycle; And can get into next absorption-wash-out circulation, resin like this can use repeatedly, drops to below the 300mg/L up to the s-adsorption of resin.
2. application art according to claim 1 is characterized in that, said gallium extracts the resin that resin is a band amidoxim functional group on the resin matrix, and its chemical structure is shown in the following figure:
3. application art according to claim 2; It is characterized in that: it can be LSC-600 and the LSC-900 that Xi'an Sunresin New Materials Co., Ltd. produces that said gallium extracts resin; The ES-346 that U.S. Doulite company produces, and the like product of Japan's production.
4. application art according to claim 1 is characterized in that the employed gallium liquid that contains is that strong basicity contains gallium liquid.
5. application art according to claim 4 is characterized in that it is the Bayer mother liquor that strong basicity contains gallium liquid.
6. application art according to claim 1 is characterized in that, the eluent solution that elution process is adopted in the step (3) is an acid solution.
7. application art according to claim 6 is characterized in that, the used acid solution of wash-out is formulated by in sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid or the Mono Chloro Acetic Acid one or more.
8. application art according to claim 6 is characterized in that, the pH value of elute soln is 0.01-4.
9. application art according to claim 8 is characterized in that, the pH value of elute soln is 0.1-3.
10. according to claims 9 described application art, it is characterized in that the pH value of elute soln is 0.3-1.
11. application art according to claim 6; It is characterized in that; The compound method of used elute soln is in exchange column, to add weakly acidic water solution in advance, opens and stirs, and uses concentration as the acid solution of 10-99% the pH value of liquid in the exchange column to be regulated again.
12. application art according to claim 11 is characterized in that, the concentration of the acid solution that the preparation elute soln is used is 15-80%.
13. application art according to claim 12 is characterized in that, the used acid solutions of preparation elute soln is 30-70%.
14. application art according to claim 11 is characterized in that, fluid temperature is 3-30 ℃ in the needs maintenance exchange column in the process of preparation elute soln.
15. application art according to claim 14 is characterized in that, fluid temperature is 5-20 ℃ in the needs maintenance exchange column in the process of preparation elute soln.
16. application art according to claim 15 is characterized in that, fluid temperature is 8-15 ℃ in the needs maintenance exchange column in the process of preparation elute soln; Be 5-240min the duration of contact of resin and elute soln.
17. application art according to claim 11; It is characterized in that; The weakly acidic solution that in exchange column, adds in advance is that the pH value is the solution that 0.1-7, concentration of heavy metal ion are lower than 100mg/L, can contain gallium ion in the solution and also can not contain gallium ion.
18. application art according to claim 1 is characterized in that, the treatment process of elute soln is obtained Gallium trihydroxide for elute soln is carried out neutralization precipitation, obtains electrolytic solution with alkaline solution dissolved hydrogen gallium oxide and removal of impurities then.
19. application art according to claim 18 is characterized in that, used alkaline solution is by one or more the formulated solution in yellow soda ash, sodium hydroxide, the Pottasium Hydroxide, and the concentration of solution is greater than 4%.
20. application art according to claim 18 is characterized in that, removal of impurities the main raw material that adopts be ironic hydroxide, manganous hydroxide, white lake, quicklime, sodium sulphite and ydrogen peroxide 50.
21. application art according to claim 20 is characterized in that, in every 100L solution, the add-on of the raw material that removal of impurities is used is 3-15kg.
22. application art according to claim 19 is characterized in that, the temperature of removal of impurities manipulation require is 30-110 ℃.
23. application art according to claim 22 is characterized in that, the temperature of removal of impurities manipulation require is between 50-100 ℃.
24. application art according to claim 23 is characterized in that, the temperature of removal of impurities manipulation require is 60-90 ℃, and the time of reaction is 4-8h.
25., it is characterized in that the dynamic post of crossing described in the step (1) is to adopt dynamic post or the dynamic post of crossing of intermittent type crossed of continous way according to the described application art of arbitrary claim among the claim 1-24.
26. application art according to claim 25, it is characterized in that the described dynamic post of crossing is to adopt the dynamic post of crossing of intermittent type: the exchange column of employing has motor and whipping appts, realizes post absorption through opening or close to stir; The start/stop time that stirs determine by the exchange column rate of discharge: when the exchange column rate of discharge for setting 70% when following of flow, unlatching stirring; When the exchange column rate of discharge greater than set flow 95% the time stop to stir.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923738A (en) * | 2012-11-15 | 2013-02-13 | 吉首大学 | Method for recovering water soluble manganese and magnesium from electrolytic manganese residue |
| CN103382531A (en) * | 2012-05-04 | 2013-11-06 | 中国科学院过程工程研究所 | Method for enriching gallium from mother-liquor in technology for producing alumina from high-alumina fly ash |
| CN103833057A (en) * | 2014-03-24 | 2014-06-04 | 连云港乐园新材料科技有限公司 | Production method for high-purity aluminum oxide |
| CN104292383A (en) * | 2014-09-16 | 2015-01-21 | 陕西华电树脂股份有限公司 | Gallium-adsorbing chelating resin and preparation method thereof |
| TWI488684B (en) * | 2013-05-14 | 2015-06-21 | Inst Nuclear Energy Res | A Method for Purification of Gallium - 69 Isotopes |
| CN109179467A (en) * | 2018-09-30 | 2019-01-11 | 中铝山东有限公司 | A method of gallium is removed to the low pregnant Bayer process liquor of concentration containing gallium |
| CN110184483A (en) * | 2019-06-25 | 2019-08-30 | 广西大学 | A method of enrichment and gallium-purifying from alkaline solution |
| CN110316793A (en) * | 2019-08-05 | 2019-10-11 | 嘉兴长润线业有限公司 | A method of the adsorption stripping antimony from stibium-containing wastewater |
| CN113698031A (en) * | 2021-08-10 | 2021-11-26 | 广西贵港市蓝月亮水处理环保科技有限公司 | Method and equipment for recovering precious metals from comprehensive wastewater |
| CN115109951A (en) * | 2022-06-28 | 2022-09-27 | 郑州轻工业大学 | Comprehensive utilization method for sulfuric acid desorption gallium-containing liquid in alumina production |
| CN115612864A (en) * | 2022-11-10 | 2023-01-17 | 中铝矿业有限公司 | Process for reducing content of suspended matters in metal gallium adsorption mother liquor |
| CN115652112A (en) * | 2022-11-22 | 2023-01-31 | 中铝矿业有限公司 | Reduce S in metal gallium adsorption mother liquor 2- Content process method |
| EP3998363A4 (en) * | 2019-07-12 | 2023-07-19 | Obshchestvo s Ogranichennoy Otvetstvennost'yu "Obedinennaya Kompaniya Rusal Inzhenerno- Tekhnologicheskiy Tsentr" | Method for producing gallate solution |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5849620A (en) * | 1981-09-17 | 1983-03-23 | Sumitomo Chem Co Ltd | Recovery of gallium |
| JPS60215721A (en) * | 1984-04-06 | 1985-10-29 | Unitika Ltd | Method for recovering gallium |
| US5424050A (en) * | 1986-10-24 | 1995-06-13 | Rhone-Poulenc Chimie | Process for extracting gallium from bayer liquors using an impregnated absorbent resin |
| CN1454706A (en) * | 2003-04-22 | 2003-11-12 | 万荣联丰特种树脂材料有限公司 | Chelating resin special for adsorbing gallium and preparing method thereof |
| CN101195872A (en) * | 2007-05-31 | 2008-06-11 | 黄昌海 | Desorbent of ion exchange resin |
| CN101962713A (en) * | 2010-10-29 | 2011-02-02 | 西安蓝晓科技有限公司 | Continuous ion exchange device and method for extracting gallium from Bayer mother solution |
| CN102021334A (en) * | 2010-12-15 | 2011-04-20 | 中国铝业股份有限公司 | Method for extracting gallium and vanadium from seed precipitation mother liquor of Bayer process |
-
2012
- 2012-02-01 CN CN201210022213.5A patent/CN102534214B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5849620A (en) * | 1981-09-17 | 1983-03-23 | Sumitomo Chem Co Ltd | Recovery of gallium |
| JPS60215721A (en) * | 1984-04-06 | 1985-10-29 | Unitika Ltd | Method for recovering gallium |
| US5424050A (en) * | 1986-10-24 | 1995-06-13 | Rhone-Poulenc Chimie | Process for extracting gallium from bayer liquors using an impregnated absorbent resin |
| CN1454706A (en) * | 2003-04-22 | 2003-11-12 | 万荣联丰特种树脂材料有限公司 | Chelating resin special for adsorbing gallium and preparing method thereof |
| CN101195872A (en) * | 2007-05-31 | 2008-06-11 | 黄昌海 | Desorbent of ion exchange resin |
| CN101962713A (en) * | 2010-10-29 | 2011-02-02 | 西安蓝晓科技有限公司 | Continuous ion exchange device and method for extracting gallium from Bayer mother solution |
| CN102021334A (en) * | 2010-12-15 | 2011-04-20 | 中国铝业股份有限公司 | Method for extracting gallium and vanadium from seed precipitation mother liquor of Bayer process |
Non-Patent Citations (2)
| Title |
|---|
| 苏玉芹等: "大孔偕胺肟树脂的合成及其对镓的吸附性能", 《过程工程学报》 * |
| 谢访友等: "用离子交换法从拜耳法生产Al_2O_3的种分母液中回收镓", 《轻金属》 * |
Cited By (14)
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|---|---|---|---|---|
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| CN110184483A (en) * | 2019-06-25 | 2019-08-30 | 广西大学 | A method of enrichment and gallium-purifying from alkaline solution |
| EP3998363A4 (en) * | 2019-07-12 | 2023-07-19 | Obshchestvo s Ogranichennoy Otvetstvennost'yu "Obedinennaya Kompaniya Rusal Inzhenerno- Tekhnologicheskiy Tsentr" | Method for producing gallate solution |
| CN110316793A (en) * | 2019-08-05 | 2019-10-11 | 嘉兴长润线业有限公司 | A method of the adsorption stripping antimony from stibium-containing wastewater |
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| CN115612864A (en) * | 2022-11-10 | 2023-01-17 | 中铝矿业有限公司 | Process for reducing content of suspended matters in metal gallium adsorption mother liquor |
| CN115652112A (en) * | 2022-11-22 | 2023-01-31 | 中铝矿业有限公司 | Reduce S in metal gallium adsorption mother liquor 2- Content process method |
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