CN103805794B - Recovery method for extracting gallium from aluminum oxide coarse-fine liquid by using acid-process fly ash - Google Patents
Recovery method for extracting gallium from aluminum oxide coarse-fine liquid by using acid-process fly ash Download PDFInfo
- Publication number
- CN103805794B CN103805794B CN201310746812.6A CN201310746812A CN103805794B CN 103805794 B CN103805794 B CN 103805794B CN 201310746812 A CN201310746812 A CN 201310746812A CN 103805794 B CN103805794 B CN 103805794B
- Authority
- CN
- China
- Prior art keywords
- gallium
- solution
- extration resin
- concentration
- adsorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a recovery method for extracting gallium from aluminum oxide coarse-fine liquid by using acid-process fly ashes. The method comprises the following steps: a separating step, namely carrying out ion adsorption on aluminum oxide coarse-fine liquid which is extracted by an acid process through CL-TBP extraction resin to obtain primary adsorption extraction resin and eluting the primary adsorption extraction resin to obtain a solution containing gallium; a purifying step, adding a first alkaline solution to the solution containing gallium to obtain a sediment containing gallium; a recovering step, namely recovering metal gallium from the sediment containing gallium. Gallium ions are separated from aluminum ions in the coarse-fine liquid by utilizing selective adsorption of the CL-TBP extraction resin, and the gallium ions form gallium hydroxide sediment by using the first alkaline solution. Therefore, the purity and the recovery rate of the metal gallium obtained in the recovering step can be ensured and meanwhile, the method is simple to operate and low in recovery cost.
Description
Technical field
The present invention relates to gallium and extract field, extract the recovery method of gallium in the thick seminal fluid of aluminum oxide in particular to a kind of acid system flyash.
Background technology
Gallium is a kind of important semiconductor basis material, and its series compound is if gallium arsenide, gallium phosphide and gallium aluminum arsenide etc. are in field widespread uses such as high speed integrated circuit, LED and photosensors.The consumption of current global gallium is 200 tons/year, and increases with the amplitude more than 20% every year.One of new high-tech material that gallium Ye Shi China gives priority to.
Gallium element is enriched in bauxite, at present, the gallium of China about more than 90% comes from and carries out traditional alkaline process to bauxite and produce the gallium that the circulation liquid caustic in alumina process carries out and reclaim, and the system of mainly producing aluminum oxide for Bayer process and sintering process carries out gallium recovery.And research finds, also containing a large amount of gallium elements in the flyash in some areas, and acid system flyash extracts the thick seminal fluid produced in the process of aluminum oxide, and the content of its gallium element is also rich.Therefore, how Footwall drift gallium from the related process system of flyash and flyash, has become a study hotspot.
From flyash, extract the method for gallium at present, its cardinal principle is the absorption adopting macroporous type cationic resin column to carry out gallium, then by resin column wash-out, obtains the elutriant containing gallium.In elutriant, add sodium hydroxide solution react, after filtering-depositing, obtain the sodium aluminate solution containing gallium.Pass into appropriate carbonic acid gas to this sodium aluminate solution again and carry out carbonating process, gallium aluminium is separated, the mass ratio obtaining gallium and aluminum oxide is greater than the gallium aluminium double salt of 1: 340.Finally gallium aluminium double salt is added in sodium hydroxide solution and react, and the electrolytic solution that evaporation concentration obtains gallium carries out electrolysis, obtains gallium.In the method, to having carried out absorption containing Gallium solution, reaction, carbon have divided, double salt dissolves and the step such as electrolysis, and its operating procedure complexity, production cost is high.Based on this, be necessary to design that a kind of technique is simple, the method for production cost is lower from flyash Footwall drift gallium.
Summary of the invention
The present invention aims to provide the recovery method that a kind of acid system flyash extracts gallium in the thick seminal fluid of aluminum oxide, to solve the problem of the method complex operation of Footwall drift gallium from flyash in prior art.
To achieve these goals, according to an aspect of the present invention, provide the recovery method that a kind of acid system flyash extracts gallium in the thick seminal fluid of aluminum oxide, it comprises the following steps: separating step: thick for acidity extraction aluminum oxide seminal fluid is carried out ionic adsorption by CL-TBP extration resin, obtains primary sorption extration resin; Wash-out is carried out to primary sorption extration resin, obtains containing Gallium solution; Purification step: add the first basic solution to containing in Gallium solution, obtains containing gallium precipitation; Recycling step: Footwall drift gallium from precipitate containing gallium.
Further, to containing before adding the step of the first basic solution in Gallium solution in above-mentioned purification step, the step to carrying out deironing containing Gallium solution is also comprised; The step of carrying out deironing containing Gallium solution is comprised: add iron powder to containing in Gallium solution, after reaction, obtain reaction solution; By reaction solution by CL-TBP extration resin, carry out secondary ions absorption, obtain second adsorption extration resin; Carry out secondary wash-out to second adsorption extration resin, what obtain deironing contains Gallium solution.
Further, before the step of primary sorption extration resin being carried out to ion elution and/or second adsorption extration resin being carried out to secondary ions wash-out, also comprise the step of cleaning primary sorption extration resin or second adsorption extration resin with the hydrochloric acid that concentration is 28 ~ 36wt%, scavenging period is 5 ~ 10min.
Further, to containing before adding iron powder in Gallium solution, by be concentrated into containing Gallium solution volume be containing Gallium solution volume 1/3 ~ 1/2.
Further, in above-mentioned separating step, during by thick for acidity extraction aluminum oxide seminal fluid by CL-TBP extration resin, the flow velocity of the thick seminal fluid of acidity extraction aluminum oxide is 10 ~ 15ml/min; When carrying out wash-out to primary sorption extration resin, eluent is deionized water or concentration is the hydrochloric acid of 0.1 ~ 0.5wt%, and the consumption of eluent is 100 ~ 120ml, and elution time is 10 ~ 12min.
Further, in above-mentioned purification step, to containing when adding iron powder in Gallium solution, the quality of iron powder is 1 ~ 5g; During by reaction solution by CL-TBP extration resin, the flow velocity of reaction solution is 10 ~ 15ml/min; When carrying out again wash-out to second adsorption extration resin, eluent is deionized water or concentration is the hydrochloric acid of 0.1 ~ 0.5wt%, and elution time is 10 ~ 15min.
Further, above-mentioned recycling step comprises: will join in the second basic solution containing gallium precipitation, and make resolution of precipitate, obtain lysate; Lysate is carried out electrolysis, obtains gallium.
Further, before lysate being carried out in above-mentioned recycling step to the step of electrolysis, also comprise the step of lysate being carried out to removal of impurities; The step of lysate being carried out to removal of impurities comprises: cleaner is added lysate, filters, carries out ozone Oxidation Treatment, obtain the lysate of removal of impurities to filtrate; Preferred cleaner is sodium sulphite and/or sodium oxalate, and the consumption of preferred cleaner is 1 ~ 2g.
Further, in the step of above-mentioned electrolysis, electrolysis temperature is 40 ~ 60 DEG C, and current density is 200 ~ 400A/m
2, electrolysis voltage is 3 ~ 4V, and pole span is 20 ~ 50mm.
Further, in above-mentioned purification step, the first basic solution and the second basic solution neutral and alkali material are respectively lithium hydroxide, potassium hydroxide or sodium hydroxide; Preferably the concentration of the second basic solution is greater than the concentration of the first alkaline matter; Preferably the first basic solution and the second basic solution are the aqueous solution of sodium hydroxide; The concentration of the first basic solution is 20 ~ 30wt%, and the concentration of the second basic solution is 45 ~ 50wt%.
Apply the recovery method that acid system flyash of the present invention extracts gallium in the thick seminal fluid of aluminum oxide, utilize the Selective adsorption of CL-TBP extration resin, effectively the gallium ion in thick seminal fluid can be separated with aluminum ion, thus the rate of recovery of gallium ion can be improved, and obtain the higher gallium ion of purity.Meanwhile, utilize the first basic solution to make gallium ion form gallium hydroxide precipitation, the purity of gallium ion can be improved further.The effect of above two aspects, can ensure purity and the rate of recovery of the gallium obtained through recycling step.In addition, in above-mentioned method, only have passed through the step of gallium ion absorption, wash-out, precipitation and recovery, compared to recovery method of the prior art, it is simple to operate, and cost recovery is low.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.The present invention is described in detail below in conjunction with embodiment.
For solving the problem of the method complex operation of Footwall drift gallium from flyash in prior art, inventor provides the recovery method of gallium in the thick seminal fluid of a kind of acidity extraction aluminum oxide, it comprises the following steps: separating step: thick for acidity extraction aluminum oxide seminal fluid is carried out ionic adsorption by CL-TBP extration resin, obtains primary sorption extration resin; Wash-out is carried out to primary sorption extration resin, obtains containing Gallium solution; Purification step: add the first basic solution to containing in Gallium solution, obtains containing gallium precipitation; Recycling step: Footwall drift gallium from precipitate containing gallium.
In the above-mentioned methods, utilize the first alkaline matter can to form gallium hydroxide and precipitate with reacting containing the gallium in Gallium solution, to make the object of Ga Element and other element sepatation, under the teachings of the present invention, those skilled in the art have the ability to select suitable basic solution.Preferably this first basic solution is strong base solution, and it includes but not limited to the aqueous solution of lithium hydroxide, potassium hydroxide or sodium hydroxide, is preferably the aqueous solution of sodium hydroxide.
The CL-TBP extration resin that aforesaid method provided by the present invention have employed take styrene-divinylbenzene as skeleton, and interpolymerized cure neutral phosphorus-dased extractant tributyl phosphate is prepared from.In acidic medium, tributyl phosphate can be formed with gallium ion generation ion and act on.In the thick seminal fluid of acidity extraction aluminum oxide, thick seminal fluid is acid state, and containing abundant aluminum ion, gallium ion.And when adopting CL-TBP extration resin to carry out ionic adsorption to it, can, to the gallium ion selective adsorption in thick seminal fluid, make gallium ion depart from thick seminal fluid, stick to CL-TBP extration resin inner, form primary sorption extration resin.Subsequently, carry out wash-out to primary sorption extration resin, gallium ion is deviate from from extration resin, define gallium ion concentration higher containing Gallium solution.Add the first basic solution to this containing in Gallium solution, gallium ion can be separated out with the precipitated form of gallium hydroxide.In above-mentioned method, utilize the Selective adsorption of CL-TBP extration resin, effectively the gallium ion in thick seminal fluid can be separated with aluminum ion, thus the rate of recovery of gallium ion can be improved, and obtain the higher gallium ion of purity.Meanwhile, utilize the first basic solution to make gallium ion form gallium hydroxide precipitation, the purity of gallium ion can be improved further.The effect of above two aspects, can ensure purity and the rate of recovery of the gallium obtained through recycling step.In addition, in above-mentioned method, only have passed through the step of gallium ion absorption, wash-out, precipitation and recovery, compared to recovery method of the prior art, it is simple to operate, and cost recovery is low.
In the above-mentioned methods, by adopting CL-TBP extration resin to carry out ionic adsorption in separating step, then wash-out just can obtain containing Gallium solution, the requirement that its processing parameter is not special, as long as meet the application requiring of CL-TBP extration resin.In a preferred embodiment, in above-mentioned separating step, during by thick for acidity extraction aluminum oxide seminal fluid by CL-TBP extration resin, the flow velocity of the thick seminal fluid of acidity extraction aluminum oxide is 10 ~ 15ml/min; When carrying out wash-out to primary sorption extration resin, eluent includes but not limited to that deionized water or concentration are the hydrochloric acid of 0.1 ~ 0.5wt%, and the consumption of eluent is 100 ~ 120ml/min, and elution time is 10 ~ 12min.In separating step, the flow velocity of thick seminal fluid, the consumption of eluent and elution time are controlled for above-mentioned scope, the gallium ion in thick seminal fluid can be made fully to adsorb and wash-out.Using deionized water or concentration be 0.1 ~ 0.5wt% compared with the eluent of dilute hydrochloric acid as gallium ion, adsorbed gallium ion can be made fully to resolve.Preferably using deionized water as eluent, the use of deionized water can not introduce other foreign ions on the one hand, improves the purity of the gallium reclaimed, better to the elute effect of gallium ion on the other hand, improves the rate of recovery of gallium.
In the above-mentioned methods, as long as thick seminal fluid is carried out above-mentioned ionic adsorption, wash-out, precipitation and recycling step, the higher gallium of purity just can be obtained.In a preferred embodiment, before the step of primary sorption extration resin being carried out to ion elution, also comprise the step of cleaning primary sorption extration resin with the hydrochloric acid that concentration is 28 ~ 36wt%, preferred scavenging period is 5 ~ 10min.Utilize concentration to be the comparatively concentrated hydrochloric acid of 28 ~ 36wt%, while can forming not affecting gallium ion and tributyl phosphate and act on, the thick seminal fluid cleaning that will remain in CL-TBP extration resin inside be removed.This just can reduce the foreign ion containing coming from residual thick seminal fluid in Gallium solution, ensures the purity of the gallium reclaimed further.
As long as aforesaid method carries out ionic adsorption with CL-TBP extration resin to thick seminal fluid, and carry out gallium ion precipitation with the first basic solution, just can ensure purity and the rate of recovery of gallium to a certain extent.In a preferred embodiment, to containing before adding the step of the first basic solution in Gallium solution in above-mentioned purification step, also comprise the step to carrying out deironing containing Gallium solution, this step comprises: add iron powder to containing in Gallium solution, obtain reaction solution after reaction; By reaction solution by CL-TBP extration resin, carry out secondary ions absorption, obtain second adsorption extration resin; Carry out secondary wash-out to second adsorption extration resin, what obtain deironing contains Gallium solution.
Extract in the thick seminal fluid of aluminum oxide, often containing some a small amount of ferric ions at acid system flyash.These ferric ions also can by CL-TBP Adsorption by Extracting Resins.And in the above-mentioned methods, due to these ferric ions adsorbed with gallium ion, wash-out, make containing in Gallium solution also containing a small amount of ferric ion.To containing before adding the step of the first basic solution in Gallium solution in above-mentioned purification step, adding iron powder containing in Gallium solution, iron powder and ferric ion generation redox reaction can be made, change ferric ion into ferrous ion.In secondary ions adsorption process subsequently, this ferrous ion then can not be adsorbed in CL-TBP extration resin.Based on this, the deironing obtained through secondary wash-out containing in Gallium solution, the content of ferro element declines greatly, thus the gallium reclaimed can be made to have higher purity.Preferably, add excess iron powder above-mentioned containing in Gallium solution, the content containing ferric ion in Gallium solution can be reduced to a greater degree, ensure the gallium purity reclaimed further.
In the purification step of aforesaid method, the requirement that involved processing condition are not special, as long as the first basic solution can be utilized and carries out reacting being formed containing Gallium solution precipitate the object that just can realize Footwall drift gallium containing gallium, by adding iron powder to containing in Gallium solution, and the step of carrying out second adsorption and secondary wash-out just can realize removing the object containing the ferric ion in Gallium solution.In a preferred embodiment, in above-mentioned purification step, to containing when adding iron powder in Gallium solution, the quality of iron powder is 1 ~ 5g; During by reaction solution by CL-TBP extration resin, the flow velocity of reaction solution is 10 ~ 15ml/min; When carrying out again wash-out to second adsorption extration resin, eluent is deionized water or concentration is the hydrochloric acid of 0.1 ~ 0.5wt%, and elution time is 10 ~ 15min.Adopt above-mentioned purifying technique, can make to be purified fully containing the gallium ion in Gallium solution, and then the purity of reclaimed gallium can be ensured.
In the above-mentioned methods, as long as thick seminal fluid is carried out above-mentioned ionic adsorption, wash-out, precipitation and recycling step, the higher gallium of purity just can be obtained.In a preferred embodiment, before the step of second adsorption extration resin being carried out to secondary ions wash-out, also comprise the step of cleaning second adsorption extration resin with the hydrochloric acid that concentration is 28 ~ 36wt%, preferred scavenging period is 5 ~ 10min.Utilize concentration to be the comparatively concentrated hydrochloric acid of 28 ~ 36wt%, while can forming not affecting gallium ion and tributyl phosphate and act on, the impure reaction solution cleaning that will remain in CL-TBP extration resin inside be removed.This just can reduce the foreign ion containing coming from residual thick seminal fluid in Gallium solution, ensures the purity of the gallium reclaimed further.
In aforesaid method provided by the present invention, directly adding iron powder containing in Gallium solution, neutralization is removed containing the Fe3+ in Gallium solution, just can reach the object of the gallium purity that raising is reclaimed.In a preferred embodiment, to containing before adding described iron powder in Gallium solution, be described containing 1/3 ~ 1/2 of Gallium solution volume by being concentrated into volume containing Gallium solution.Utilize concentrated after carry out deironing, precipitin reaction and recycling step containing Gallium solution, gallium ion can be reduced and carried by a large amount of solvent in the process of sedimentation and filtration and the loss that causes, thus improve the rate of recovery of gallium further.
According to instruction of the present invention, those skilled in the art have the ability to select suitable mode to reclaim containing the gallium in gallium precipitation.In a preferred embodiment, above-mentioned recycling step comprises: will join in the second basic solution containing in gallium precipitation, and make resolution of precipitate, obtain lysate; Lysate is carried out electrolysis, obtains gallium.
When aforesaid purification step, add the first basic solution to containing in Gallium solution, gallium ion can be made with the Precipitation of gallium hydroxide.After obtaining this gallium hydroxide precipitation, added in the second basic solution ,-OH the ion in gallium hydroxide and solution can be made to continue to react, formed [GaO
2]
-(inclined gallic acid radical ion) is dissolved in the second basic solution; Electrolysis is carried out to this lysate, can under the condition not introducing foreign ion, make gallium be adsorbed on electrode, the rate of recovery and the purity of gallium can be ensured further.
In aforesaid method provided by the present invention, particular requirement be there is no to the second adopted basic solution, make it dissolve as long as it can react with gallium hydroxide.In the preferred mode of one, in above-mentioned purification step, the second basic solution neutral and alkali material is lithium hydroxide, potassium hydroxide or sodium hydroxide.As the gallium hydroxide of amphoteric hydroxide, all can with above-mentioned strong base substance generation redox reaction, generate the inclined gallate of solubility.Preferably the concentration of the second basic solution is greater than the concentration of the first alkaline matter.Adopt the second basic solution that concentration is higher, can, under the prerequisite not introducing multi-solvent, gallium hydroxide rapid reaction be dissolved.Preferably the second basic solution is the aqueous solution of sodium hydroxide; The concentration of the first basic solution is 20 ~ 30wt%, and the concentration of the second basic solution is 45 ~ 50wt%.Adopt aqueous sodium hydroxide solution as the first basic solution and the second basic solution simultaneously, can ensure, under the prerequisite that precipitin reaction and redox reaction are carried out smoothly, to reduce adding of other active metallic ions.And in the electrolytic process in later stage, because sodium ion is different from the electrolytic potential of gallium ion, the existence of sodium ion can not affect the electrolysis precipitation of gallium ion.
According to instruction of the present invention, those skilled in the art can select concrete cleaner.Preferably, cleaner includes but not limited to sodium sulphite and/or sodium oxalate, and the consumption of preferred cleaner is 1 ~ 2g.Using sodium sulphite and/or sodium oxalate as cleaner, the foreign metal ionic reaction of trace can be made to separate out, and meanwhile, the existence of sodium ion can not affect follow-up electrolytic process.Reclaimed gallium is made to have higher purity.
According to instruction of the present invention, those skilled in the art have the ability to select suitable electrolysis process.Preferably, in the step of above-mentioned electrolysis, electrolysis temperature is 40 ~ 60 DEG C, and current density is 200 ~ 400A/m
2, electrolysis voltage is 3 ~ 4V, and pole span is 20 ~ 50mm.Different metal ions has different deposition potentials.Under above-mentioned electrolysis process, gallium ion can be made fully to separate out, meanwhile, other trace impurity metal ion electrolysis can also be avoided to separate out, and then ensure purity and the rate of recovery of gallium.
In aforesaid method provided by the present invention, according to conventional means, electrolysis is carried out to lysate, just can obtain gallium.In a preferred embodiment, before lysate being carried out in above-mentioned recycling step to the step of electrolysis, also comprise the step of lysate being carried out to removal of impurities; The step of lysate being carried out to removal of impurities comprises: cleaner is added described lysate, filters, carries out ozone Oxidation Treatment, obtain the lysate of removal of impurities to filtrate.Ozone oxidation passes into ozone in lysate, and those skilled in the art have the ability to select to pass into according to the consumption of concrete thick ejaculate volume and cleaner amount and the oxidization time of ozone.In lysate, add cleaner, the foreign metal ion of trace in lysate can be removed, as Co, Zn ion etc., and then these foreign metal ions can be avoided to separate out in ionization process, affect the purity of gallium.Meanwhile, the filtrate of filtration is carried out ozone oxidation, the impurity anions in excessive cleaner can be removed, ensure the purity of gallium further.
Be described in further detail the present invention below in conjunction with specific embodiment, these embodiments can not be interpreted as restriction the present invention scope required for protection.
Embodiment 1
The thick seminal fluid of 1000ml acidity extraction aluminum oxide (gallium ion concentration is 8mg/L) is carried out ionic adsorption by the resin column (resin column capacity is 400ml) that CL-TBP extration resin is housed of three series connection successively, the flow velocity of thick seminal fluid is 10ml/min, obtains primary sorption extration resin; By concentration be 36% concentrated hydrochloric acid primary sorption extration resin is cleaned, scavenging period is 10min; Carry out wash-out with 120ml deionized water to primary sorption extration resin, elution time is 12min, obtains containing Gallium solution;
Make its volume be down to 1/3 of original volume by containing Gallium solution heating is concentrated, add 5g iron powder wherein, fully obtain reaction solution after reaction; Reaction solution is carried out secondary ions absorption by the resin column that CL-TBP extration resin is housed of three series connection again, and the flow velocity of reaction solution is 10ml/min, obtains second adsorption extration resin; Carry out wash-out with deionized water to second adsorption extration resin, elution time is 15min, and what obtain deironing contains Gallium solution;
Is the aqueous sodium hydroxide solution of 20wt% to deironing containing Gallium solution dropping concentration, to precipitation is no longer separated out, filters, dries and precipitate; In precipitation, add the aqueous sodium hydroxide solution that concentration is 50wt%, dissolve completely to precipitation, obtain lysate;
In lysate, add the sodium sulphite of 1g and the sodium oxalate of 1g respectively, filter; In filtrate, pass into the ozone of 2L, reaction 10min, filters, obtains liquid to be electrolysed;
Do anode and cathode with stainless steel substrates, liquid temp to be electrolysed is 40 DEG C, and current density is 400A/m
2, bath voltage is 3V, and pole span is treat electrolytic solution under the condition of 50mm to carry out electrolysis, and obtain gallium 2.8g, purity is 99.9%, and the rate of recovery is 80%.
Embodiment 2
The thick seminal fluid of 1000ml acidity extraction aluminum oxide (gallium ion concentration is 8mg/L) is carried out ionic adsorption by the resin column (resin column capacity is 400ml) that CL-TBP extration resin is housed of three series connection successively, the flow velocity of thick seminal fluid is 12ml/min, obtains primary sorption extration resin; By concentration be 32% hydrochloric acid primary sorption extration resin is cleaned, scavenging period is 8min; Carry out wash-out with 110ml deionized water to primary sorption extration resin, elution time is 11min, obtains containing Gallium solution;
After making its volume be down to 1/2 of original volume containing Gallium solution heating is concentrated, add 1g iron powder wherein, fully obtain reaction solution after reaction; Reaction solution is carried out secondary ions absorption by the resin column that CL-TBP extration resin is housed of three series connection again, and the flow velocity of reaction solution is 12ml/min, obtains second adsorption extration resin; Carry out wash-out with deionized water to second adsorption extration resin, elution time is 12min, and what obtain deironing contains Gallium solution;
Is the aqueous sodium hydroxide solution of 25wt% to deironing containing Gallium solution dropping concentration, to precipitation is no longer separated out, filters, dries and precipitate; In precipitation, add the aqueous sodium hydroxide solution that concentration is 48wt%, dissolve completely to precipitation, obtain lysate;
In lysate, add the sodium sulphite of 0.8g and the sodium oxalate of 0.8g respectively, filter; In filtrate, pass into the ozone of 2L, reaction 10min, filters, obtains liquid to be electrolysed;
Do anode and cathode with stainless steel substrates, liquid temp to be electrolysed is 40 DEG C, and current density is 300A/m
2, bath voltage is 4V, and pole span is treat electrolytic solution under the condition of 40mm to carry out electrolysis, and obtain gallium 2.7g, purity is 99.1%, and the rate of recovery is 77%.Embodiment 3
The thick seminal fluid of 1000ml acidity extraction aluminum oxide (gallium ion concentration is 8mg/L) is carried out ionic adsorption by the resin column (resin column capacity is 400ml) that CL-TBP extration resin is housed of three series connection successively, the flow velocity of thick seminal fluid is 15ml/min, obtains primary sorption extration resin; By concentration be 28% hydrochloric acid primary sorption extration resin is cleaned, scavenging period is 5min; Carry out wash-out with 100ml deionized water to primary sorption extration resin, elution time is 10min, obtains containing Gallium solution;
Make its volume be down to 1/2 of original volume by containing Gallium solution heating is concentrated, add 5g iron powder wherein, fully obtain reaction solution after reaction; Reaction solution is carried out secondary ions absorption by the resin column that CL-TBP extration resin is housed of three series connection again, and the flow velocity of reaction solution is 15ml/min, obtains second adsorption extration resin; Carry out wash-out with deionized water to second adsorption extration resin, elution time is 10min, and what obtain deironing contains Gallium solution;
Is the aqueous sodium hydroxide solution of 30wt% to deironing containing Gallium solution dropping concentration, to precipitation is no longer separated out, filters, dries and precipitate; In precipitation, add the aqueous sodium hydroxide solution that concentration is 45wt%, dissolve completely to precipitation, obtain lysate;
In lysate, add the sodium sulphite of 0.5g and the sodium oxalate of 0.5g respectively, filter; In filtrate, pass into the ozone of 2L, reaction 10min, filters, obtains liquid to be electrolysed;
Do anode and cathode with stainless steel substrates, liquid temp to be electrolysed is 60 DEG C, and current density is 200A/m
2, bath voltage is 4V, and pole span is treat electrolytic solution under the condition of 20mm to carry out electrolysis, and obtain gallium 2.5g, purity is 99.2%, and the rate of recovery is 71%.
Embodiment 4
The thick seminal fluid of 1000ml acidity extraction aluminum oxide (gallium ion concentration is 8mg/L) is carried out ionic adsorption by the resin column (resin column capacity is 400ml) that CL-TBP extration resin is housed of three series connection successively, the flow velocity of thick seminal fluid is 18ml/min, obtains primary sorption extration resin; By concentration be 32% hydrochloric acid primary sorption extration resin is cleaned, scavenging period is 8min; Carry out wash-out with 90ml deionized water to primary sorption extration resin, elution time is 5min, obtains containing Gallium solution;
To being the aqueous sodium hydroxide solution of 18wt% containing Gallium solution dropping concentration, to precipitation is no longer separated out, filtering, drying and precipitate; In precipitation, add the aqueous sodium hydroxide solution that concentration is 40wt%, dissolve completely to precipitation, obtain lysate;
Do anode and cathode with stainless steel substrates, lysate temperature is 15 DEG C, and current density is 500A/m
2, bath voltage is 1V, and pole span is treat electrolytic solution under the condition of 60mm to carry out electrolysis, and obtain gallium 2.6g, purity is 80.2%, and the rate of recovery is 60%.
Embodiment 5
The thick seminal fluid of 1000ml acidity extraction aluminum oxide (gallium ion concentration is 8mg/L) is carried out ionic adsorption by the resin column (resin column capacity is 400ml) that CL-TBP extration resin is housed of three series connection successively, the flow velocity of thick seminal fluid is 20ml/min, obtains primary sorption extration resin; Carry out wash-out with 150ml deionized water to primary sorption extration resin, elution time is 16min, obtains containing Gallium solution;
To being the aqueous sodium hydroxide solution of 32wt% containing Gallium solution dropping concentration, to precipitation is no longer separated out, filtering, drying and precipitate; In precipitation, add the aqueous sodium hydroxide solution that concentration is 55wt%, dissolve completely to precipitation, obtain lysate;
Do anode and cathode with stainless steel substrates, lysate temperature is 70 DEG C, and current density is 150A/m
2, bath voltage is 5V, and pole span is treat electrolytic solution under the condition of 15mm to carry out electrolysis, and obtain gallium 2.8g, purity is 75.4%, and the rate of recovery is 62%.
From above data, can find out, adopt the gallium that the method in the above embodiments of the present invention reclaims from flyash, its purity is higher, the rate of recovery is higher, the method especially in embodiment 1 ~ 3, and the purity of its gallium reclaimed is higher, the rate of recovery is higher.Meanwhile, simple to operate, be convenient to scale operation.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. acid system flyash extracts a recovery method for gallium in the thick seminal fluid of aluminum oxide, it is characterized in that, comprises the following steps:
Separating step: thick for acidity extraction aluminum oxide seminal fluid is carried out ionic adsorption by CL-TBP extration resin, obtains primary sorption extration resin; Wash-out is carried out to described primary sorption extration resin, obtains containing Gallium solution;
Purification step: add the first basic solution containing in Gallium solution to described, obtains containing gallium precipitation;
Recycling step: reclaim described gallium containing gallium precipitation from described; In described purification step to described containing before adding the step of described first basic solution in Gallium solution, also comprise described step of carrying out deironing containing Gallium solution; Described step of carrying out deironing containing Gallium solution is comprised:
Add iron powder to described containing in Gallium solution, the quality of described iron powder is 1 ~ 5g; Reaction solution is obtained after reaction;
By described reaction solution by described CL-TBP extration resin, the flow velocity of described reaction solution is 10 ~ 15ml/min; Carry out secondary ions absorption, obtain second adsorption extration resin;
Carry out secondary wash-out to described second adsorption extration resin, the hydrochloric acid of eluent to be concentration be 0.1 ~ 0.5wt%, elution time is 10 ~ 15min; Obtain the described containing Gallium solution of deironing;
Before described primary sorption extration resin being carried out to ion elution and/or the step of secondary ions wash-out is carried out to described second adsorption extration resin, also comprise the step of cleaning described primary sorption extration resin or described second adsorption extration resin with the hydrochloric acid that concentration is 28 ~ 36wt%, scavenging period is 5 ~ 10min;
In described separating step, during by the thick seminal fluid of described acidity extraction aluminum oxide by described CL-TBP extration resin, the flow velocity of the thick seminal fluid of described acidity extraction aluminum oxide is 10 ~ 15ml/min; When carrying out wash-out to described primary sorption extration resin, the hydrochloric acid of eluent to be concentration be 0.1 ~ 0.5wt%, the consumption of described eluent is 100 ~ 120ml, and elution time is 10 ~ 12min.
2. method according to claim 1, is characterized in that, to described containing before adding described iron powder in Gallium solution, to be concentrated into volume containing Gallium solution be described containing 1/3 ~ 1/2 of Gallium solution volume by described.
3. method according to claim 1 and 2, is characterized in that, described recycling step comprises:
Join described in the second basic solution containing gallium precipitation, make described resolution of precipitate, obtain lysate;
Described lysate is carried out electrolysis, obtains described gallium.
4. method according to claim 3, is characterized in that, before described lysate being carried out in described recycling step to the step of electrolysis, also comprises the step of described lysate being carried out to removal of impurities; The step of described lysate being carried out to removal of impurities comprises: cleaner is added described lysate, filters, carries out ozone Oxidation Treatment, obtain the described lysate of removal of impurities to filtrate; Described cleaner is sodium sulphite and/or sodium oxalate, and the consumption of described cleaner is 1 ~ 2g.
5. method according to claim 3, is characterized in that, in the step of described electrolysis, electrolysis temperature is 40 ~ 60 DEG C, and current density is 200 ~ 400A/m
2, electrolysis voltage is 3 ~ 4V, and pole span is 20 ~ 50mm.
6. method according to claim 3, is characterized in that, described first basic solution and described second basic solution neutral and alkali material are respectively lithium hydroxide, potassium hydroxide or sodium hydroxide;
The concentration of described second basic solution is greater than the concentration of described first basic solution; The concentration of described first basic solution is 20 ~ 30wt%, and the concentration of described second basic solution is 45 ~ 50wt%.
7. method according to claim 6, is characterized in that, described first basic solution and described second basic solution are the aqueous solution of sodium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310746812.6A CN103805794B (en) | 2013-12-30 | 2013-12-30 | Recovery method for extracting gallium from aluminum oxide coarse-fine liquid by using acid-process fly ash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310746812.6A CN103805794B (en) | 2013-12-30 | 2013-12-30 | Recovery method for extracting gallium from aluminum oxide coarse-fine liquid by using acid-process fly ash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103805794A CN103805794A (en) | 2014-05-21 |
| CN103805794B true CN103805794B (en) | 2015-04-08 |
Family
ID=50703175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310746812.6A Active CN103805794B (en) | 2013-12-30 | 2013-12-30 | Recovery method for extracting gallium from aluminum oxide coarse-fine liquid by using acid-process fly ash |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103805794B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018012A (en) * | 2014-06-16 | 2014-09-03 | 中国神华能源股份有限公司 | Method of extracting gallium from aluminum chloride solution |
| CN105753026B (en) * | 2016-04-11 | 2018-05-04 | 北京世纪地和控股有限公司 | A kind of method for recycling aluminium oxide from flyash with sulfuric acid |
| CN108374091B (en) * | 2018-03-30 | 2020-01-03 | 中国科学院过程工程研究所 | Method for recovering gallium from waste containing insoluble gallium compound and gallium obtained by method |
| CN108396149A (en) * | 2018-04-09 | 2018-08-14 | 太原理工大学 | The preenrichment heavy-fluid and preprocess method of aluminium lithium gallium are extracted from flyash |
| RU2712162C1 (en) * | 2019-07-12 | 2020-01-24 | Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" | Method of producing gallate solution |
| CN111020198B (en) * | 2019-12-12 | 2021-07-23 | 广西大学 | Method for purifying gallium from acid solution based on silicon-based tributyl phosphate solid adsorbent |
| CN114855222A (en) * | 2022-04-25 | 2022-08-05 | 珠海经济特区方源有限公司 | Method for recovering gallium from magnet powder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4193968A (en) * | 1978-10-03 | 1980-03-18 | The Anaconda Company | Process for recovering gallium |
| CN101838738A (en) * | 2010-04-27 | 2010-09-22 | 中国神华能源股份有限公司 | Method for extracting gallium from flyash |
| 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 |
-
2013
- 2013-12-30 CN CN201310746812.6A patent/CN103805794B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4193968A (en) * | 1978-10-03 | 1980-03-18 | The Anaconda Company | Process for recovering gallium |
| CN101838738A (en) * | 2010-04-27 | 2010-09-22 | 中国神华能源股份有限公司 | Method for extracting gallium from flyash |
| 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 (1)
| Title |
|---|
| CL-TBP萃淋树脂吸附镓的性能及应用研究;刘建等;《稀有金属》;20000331;第24卷(第02期);第157～160页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103805794A (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103805794B (en) | Recovery method for extracting gallium from aluminum oxide coarse-fine liquid by using acid-process fly ash | |
| JP7031263B2 (en) | Lithium recovery method | |
| CN103145187B (en) | Production technology of harmless high-purity vanadium pentoxide | |
| CN103205570B (en) | Bone coal navajoite and pyrolusite together produce the method for Vanadium Pentoxide in FLAKES by-product manganese sulfate | |
| CN105384195B (en) | Method for recovering rhenium from molybdenum smelting waste acid | |
| CN103820646B (en) | A kind of method extracting gallium from flyash | |
| CN108707748B (en) | Method for purifying stone coal pickle liquor and recovering aluminum, potassium and iron | |
| CN110510648B (en) | Method for separating and recovering aluminum, potassium and ammonium from mixed solution containing aluminum sulfate, potassium sulfate and ammonium sulfate | |
| CN104099483A (en) | Preparation method of highly pure vanadium pentoxide | |
| CN103818969B (en) | Red iron oxide and preparation method thereof | |
| CN104018012A (en) | Method of extracting gallium from aluminum chloride solution | |
| CN103805785A (en) | Method for recovering gallium from fly ash | |
| CN105950865B (en) | A method of the separation and Extraction vanadium chromium from high-chromic vanadium leachate | |
| CN107902855B (en) | Recovery process of waste zinc ions in viscose fiber production | |
| WO2004099079A1 (en) | A method for producing an electrolytic solution containing vanadium | |
| CN110760689B (en) | Method for removing iron in precious metal rhodium recovery process | |
| CN108609661B (en) | Method for preparing iron oxide red, aluminum oxide and gallium by using iron-removing resin eluent | |
| CN104017993B (en) | The method that vanadium oxide prepared by the sodium roasting leachate of tailings is refined with titanium tetrachloride | |
| CN103864254B (en) | The method of the deleading zinc process of steel cable acid washing phosphorization acid waste liquid and comprehensive utilization | |
| CN112194154B (en) | Method for extracting rubidium chloride from rubidium-containing high-salt brine in short process | |
| CN112239221B (en) | Method for extracting rubidium chloride from rubidium-containing high-salinity brine | |
| CN109173340B (en) | Method for removing chlorine from strong acidic solution by adsorption | |
| CN103572062A (en) | Method for recovering vanadium from desilication slag | |
| CN109626414B (en) | Method for recovering thallium and rhenium from smelting waste acid | |
| CN106244807A (en) | A kind of method reclaiming purification rare earth from ion adsorption type rare earth ore waste water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |