CN103805794A - 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
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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 foundation 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 to exceed 20% amplitude every year.One of new high-tech material that gallium Ye Shi China gives priority to.
Gallium element is enriched in bauxite, at present, about more than 90% gallium of China comes from and bauxite is carried out to traditional alkaline process produces the gallium that the circulation liquid caustic in alumina process carries out and reclaim, and is mainly that the system of producing aluminum oxide for Bayer process and sintering process is carried out gallium recovery.And research is found, in some regional flyash, also contain a large amount of gallium elements, and the thick seminal fluid producing in the process of acid system flyash extraction aluminum oxide, the content of its gallium element is also rich.Therefore, how from the related process system of flyash and flyash, to reclaim gallium, become a study hotspot.
From flyash, extract at present the method for gallium, its cardinal principle is to adopt macroporous type cationic resin column to carry out the absorption of gallium, then by resin column wash-out, obtains the elutriant containing gallium.In elutriant, add sodium hydroxide solution to 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 processing, gallium aluminium is separated, the mass ratio that obtains 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 reacted, and the electrolytic solution that evaporation concentration obtains gallium carries out electrolysis, obtain gallium.In the method, to having carried out containing Gallium solution that absorption, reaction, carbon divide, double salt dissolves and the step such as electrolysis, its operating procedure complexity, production cost is high.Based on this, be necessary to design a kind of method that reclaims gallium from flyash that technique is simple, production cost is lower.
Summary of the invention
The present invention aims to provide the recovery method of gallium in the thick seminal fluid of a kind of acid system flyash extraction aluminum oxide, to solve the problem of the method complex operation that reclaims gallium in prior art from flyash.
To achieve these goals, according to an aspect of the present invention, provide a kind of acid system flyash to extract the recovery method of gallium in the thick seminal fluid of aluminum oxide, it comprises the following steps: separating step: acid system is extracted to the thick seminal fluid of aluminum oxide and carry out ionic adsorption by CL-TBP extration resin, obtain primary sorption extration resin; Primary sorption extration resin is carried out to wash-out, obtain containing Gallium solution; Purification step: to adding the first basic solution containing in Gallium solution, obtain containing gallium precipitation; Recycling step: reclaim gallium from precipitate containing gallium.
Further, in above-mentioned purification step, to containing before adding the step of the first basic solution in Gallium solution, also comprise the step to carrying out deironing containing Gallium solution; The step of carrying out deironing containing Gallium solution is comprised: to adding iron powder containing in Gallium solution, after reaction, obtain reaction solution; Reaction solution, by CL-TBP extration resin, is carried out to secondary ions absorption, obtain second adsorption extration resin; Second adsorption extration resin is carried out to secondary wash-out, obtain the Gallium solution that contains of deironing.
Further, before primary sorption extration resin being carried out to ion wash-out and/or second adsorption extration resin being carried out to the step of secondary ions wash-out, the step that the hydrochloric acid that also to comprise by concentration be 28～36wt% cleans primary sorption extration resin or second adsorption extration resin, scavenging period is 5～10min.
Further, to containing before adding iron powder in Gallium solution, be containing 1/3～1/2 of Gallium solution volume by be concentrated into volume containing Gallium solution.
Further, in above-mentioned separating step, when acid system is extracted to the thick seminal fluid of aluminum oxide by CL-TBP extration resin, the flow velocity that acid system extracts the thick seminal fluid of aluminum oxide is 10～15ml/min; When primary sorption extration resin is carried out to wash-out, eluent is the hydrochloric acid that deionized water or concentration are 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 when adding iron powder in Gallium solution, the quality of iron powder is 1～5g; When reaction solution is passed through to CL-TBP extration resin, the flow velocity of reaction solution is 10～15ml/min; When second adsorption extration resin is carried out again to wash-out, eluent is the hydrochloric acid that deionized water or concentration are 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, and obtain lysate; Lysate is carried out to electrolysis, obtain gallium.
Further, before lysate being carried out to the step of electrolysis in above-mentioned recycling step, 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 to lysate, filter, filtrate is carried out to ozone Oxidation Treatment, obtain the lysate of removal of impurities; Preferably cleaner is sodium sulphite and/or sodium oxalate, and preferably the consumption of cleaner is 1～2g.
Further, in the step of above-mentioned electrolysis, electrolysis temperature is 40～60 ℃, and current density is 200～400A/m
2, electrolysis voltage is 3～4V, 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, can effectively the gallium ion in thick seminal fluid be separated with aluminum ion, thereby can improve the rate of recovery of gallium ion, and obtain the gallium ion that purity is higher.Meanwhile, utilize the first basic solution to make gallium ion form gallium hydroxide precipitation, can further improve the purity of gallium ion.The effect of above two aspects, can guarantee purity and the rate of recovery of the gallium obtaining through recycling step.In addition, in above-mentioned method, only passed through the step of gallium ion absorption, wash-out, precipitation and recovery, than recovery method of the prior art, it is simple to operate, and cost recovery is low.
Embodiment
It should be noted that, in the situation that not conflicting, the feature in embodiment and embodiment in the application can combine mutually.Describe the present invention in detail below in conjunction with embodiment.
For solving the problem that reclaims the method complex operation of gallium in prior art from flyash, inventor provides a kind of acid system to extract the recovery method of gallium in the thick seminal fluid of aluminum oxide, it comprises the following steps: separating step: acid system is extracted to the thick seminal fluid of aluminum oxide and carry out ionic adsorption by CL-TBP extration resin, obtain primary sorption extration resin; Primary sorption extration resin is carried out to wash-out, obtain containing Gallium solution; Purification step: to adding the first basic solution containing in Gallium solution, obtain containing gallium precipitation; Recycling step: reclaim gallium from precipitate containing gallium.
In aforesaid method, to utilize the first alkaline matter to precipitate with the formation gallium hydroxide that reacts containing the gallium in Gallium solution, with the object that Ga Element is separated with other elements, under instruction 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 the aqueous solution that it includes but not limited to 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 has adopted is take vinylbenzene-divinylbenzene as skeleton, and copolymerization is solidified neutral phosphonic extraction agent tributyl phosphate and is prepared from.In acidic medium, tributyl phosphate can be formed and act on gallium ion generation ion.Extract in the thick seminal fluid of aluminum oxide at acid system, thick seminal fluid is acid state, and contains abundant aluminum ion, gallium ion.And while adopting CL-TBP extration resin to carry out ionic adsorption to it, can be to the gallium ion selective adsorption in thick seminal fluid, make gallium ion depart from thick seminal fluid, stick to CL-TBP extration resin inside, form primary sorption extration resin.Subsequently, primary sorption extration resin is carried out to wash-out, gallium ion is deviate from from extration resin, formed 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 precipitation state of gallium hydroxide.In above-mentioned method, utilize the Selective adsorption of CL-TBP extration resin, can effectively the gallium ion in thick seminal fluid be separated with aluminum ion, thereby can improve the rate of recovery of gallium ion, and obtain the gallium ion that purity is higher.Meanwhile, utilize the first basic solution to make gallium ion form gallium hydroxide precipitation, can further improve the purity of gallium ion.The effect of above two aspects, can guarantee purity and the rate of recovery of the gallium obtaining through recycling step.In addition, in above-mentioned method, only passed through the step of gallium ion absorption, wash-out, precipitation and recovery, than recovery method of the prior art, it is simple to operate, and cost recovery is low.
In aforesaid method, in separating step, by adopting CL-TBP extration resin to carry out ionic adsorption, then wash-out just can obtain containing Gallium solution, and its processing parameter does not have special requirement, as long as meet the application requiring of CL-TBP extration resin.One preferred embodiment in, in above-mentioned separating step, acid system is extracted to the thick seminal fluid of aluminum oxide when the CL-TBP extration resin, the flow velocity that acid system extracts the thick seminal fluid of aluminum oxide is 10～15ml/min; When primary sorption extration resin is carried out to wash-out, eluent includes but not limited to the hydrochloric acid that deionized water or concentration are 0.1～0.5wt%, and the consumption of eluent is 100～120ml/min, and elution time is 10～12min.In separating step, be above-mentioned scope by the consumption of the flow velocity of thick seminal fluid, eluent and elution time control, can make the gallium ion in thick seminal fluid fully adsorb and wash-out.Using deionized water or concentration as the eluent as gallium ion compared with dilute hydrochloric acid of 0.1～0.5wt%, can make adsorbed gallium ion fully resolve.Preferably, using deionized water as eluent, the use of deionized water can not introduced other foreign ions on the one hand, improves the purity of the gallium reclaiming, better to the elute effect of gallium ion on the other hand, improves the rate of recovery of gallium.
In aforesaid method, as long as thick seminal fluid is carried out to above-mentioned ionic adsorption, wash-out, precipitation and recycling step, just can obtain the gallium that purity is higher.One preferred embodiment in, before primary sorption extration resin is carried out to the step of ion wash-out, the step that the hydrochloric acid that also to comprise by concentration be 28～36wt% cleans primary sorption extration resin, preferably scavenging period is 5～10min.Utilize concentration be 28～36wt% compared with concentrated hydrochloric acid, can be in not affecting gallium ion and tributyl phosphate and forming and act on, the thick seminal fluid that will remain in CL-TBP extration resin inside cleans to be removed.This just can reduce containing the foreign ion that comes from residual thick seminal fluid in Gallium solution, further guarantees the purity of the gallium reclaiming.
Aforesaid method needs only, with CL-TBP extration resin, thick seminal fluid is carried out to ionic adsorption, and carries out gallium ion precipitation with the first basic solution, just can guarantee to a certain extent purity and the rate of recovery of gallium.One preferred embodiment in, in above-mentioned purification step, to containing before adding the step of the first basic solution in Gallium solution, also comprise the step to carrying out deironing containing Gallium solution, this step comprises: to adding iron powder containing in Gallium solution, obtain reaction solution after reaction; Reaction solution, by CL-TBP extration resin, is carried out to secondary ions absorption, obtain second adsorption extration resin; Second adsorption extration resin is carried out to secondary wash-out, obtain the Gallium solution that contains of deironing.
Extract in the thick seminal fluid of aluminum oxide at acid system flyash, often contain some a small amount of ferric ions.These ferric ions also can be by CL-TBP Adsorption by Extracting Resins.And in aforesaid method, due to these ferric ions with gallium ion be adsorbed, wash-out, make containing also containing a small amount of ferric ion in Gallium solution.In above-mentioned purification step, to containing before adding the step of the first basic solution in Gallium solution, adding iron powder containing in Gallium solution, can make iron powder and ferric ion generation redox reaction, change ferric ion into ferrous ion.In secondary ions adsorption process subsequently, this ferrous ion can not be adsorbed in CL-TBP extration resin.Based on this, the deironing obtaining through secondary wash-out containing in Gallium solution, the content of ferro element declines greatly, thereby can make the gallium reclaiming have higher purity.Preferably, add excess iron powder above-mentioned containing in Gallium solution, can reduce to a greater degree the content containing ferric ion in Gallium solution, further guarantee the gallium purity reclaiming.
In the purification step of aforesaid method, related processing condition do not have special requirement, as long as can utilize the first basic solution to form the object that just can realize recovery gallium containing gallium precipitation with react containing Gallium solution, by to containing adding iron powder in Gallium solution, and the step of carrying out second adsorption and secondary wash-out just can realize the object removing containing the ferric ion in Gallium solution.One preferred embodiment in, in above-mentioned purification step, to when adding iron powder in Gallium solution, the quality of iron powder is 1～5g; When reaction solution is passed through to CL-TBP extration resin, the flow velocity of reaction solution is 10～15ml/min; When second adsorption extration resin is carried out again to wash-out, eluent is the hydrochloric acid that deionized water or concentration are 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 can guarantee the purity of reclaimed gallium.
In aforesaid method, as long as thick seminal fluid is carried out to above-mentioned ionic adsorption, wash-out, precipitation and recycling step, just can obtain the gallium that purity is higher.One preferred embodiment in, before second adsorption extration resin is carried out to the step of secondary ions wash-out, the step that the hydrochloric acid that also to comprise by concentration be 28～36wt% cleans second adsorption extration resin, preferably scavenging period is 5～10min.Utilize concentration be 28～36wt% compared with concentrated hydrochloric acid, can be in not affecting gallium ion and tributyl phosphate and forming and act on, the impure reaction solution that will remain in CL-TBP extration resin inside cleans to be removed.This just can reduce containing the foreign ion that comes from residual thick seminal fluid in Gallium solution, further guarantees the purity of the gallium reclaiming.
In aforesaid method provided by the present invention, directly containing adding iron powder in Gallium solution, neutralization is removed containing the Fe3+ in Gallium solution, just can reach the object of the gallium purity that raising reclaims.One preferred embodiment in, to containing before adding described iron powder in Gallium solution, be described containing 1/3～1/2 of Gallium solution volume by be concentrated into volume containing Gallium solution.Utilize and carry out deironing, precipitin reaction and recycling step containing Gallium solution after concentrated, can reduce that gallium ion is carried by a large amount of solvents in the process of sedimentation and filtration and the loss that causes, thereby further improve the rate of recovery of gallium.
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.One preferred embodiment in, above-mentioned recycling step comprises: will join in the second basic solution containing in gallium precipitation, make resolution of precipitate, and obtain lysate; Lysate is carried out to electrolysis, obtain gallium.
In the time of aforesaid purification step, to adding the first basic solution containing in Gallium solution, can make the Precipitation of gallium ion with gallium hydroxide.Obtain, after this gallium hydroxide precipitation, being added in the second basic solution, can make gallium hydroxide with in solution-OH ion continues to react, formation [GaO
2]
-(gallic acid radical ion partially) is dissolved in the second basic solution; This lysate is carried out to electrolysis, can under the condition of not introducing foreign ion, make gallium be adsorbed on electrode, can further guarantee the rate of recovery and the purity of gallium.
In aforesaid method provided by the present invention, the second adopted basic solution is not had to particular requirement, as long as it can react with gallium hydroxide, it is dissolved.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 highly basic material generation redox reaction, generate the inclined to one side gallate of solubility.Preferably the concentration of the second basic solution is greater than the concentration of the first alkaline matter.Adopt the second higher basic solution of concentration, can not introduce under the prerequisite of multi-solvent, gallium hydroxide rapid reaction is 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 guarantee, 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 of gallium ion and separate out.
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 preferably the consumption of cleaner is 1～2g.Using sodium sulphite and/or sodium oxalate as cleaner, can make micro-foreign metal ionic reaction separate out, meanwhile, the existence of sodium ion can not affect follow-up electrolytic process.Make reclaimed gallium there is 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 ℃, and current density is 200～400A/m
2, electrolysis voltage is 3～4V, pole span is 20～50mm.Different metal ions has different deposition potentials.Under above-mentioned electrolysis process, can make gallium ion fully separate out, meanwhile, can also avoid other trace impurity metal ion electrolysis to separate out, and then guarantee purity and the rate of recovery of gallium.
In aforesaid method provided by the present invention, according to conventional means, lysate is carried out to electrolysis, just can obtain gallium.One preferred embodiment in, before lysate being carried out to the step of electrolysis in above-mentioned recycling step, 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 to described lysate, filter, filtrate is carried out to ozone Oxidation Treatment, obtain the lysate of removal of impurities.Ozone oxidation is to pass into ozone in lysate, capable amount and the oxidization time of selecting to pass into ozone according to the consumption of concrete thick seminal fluid volume and cleaner of those skilled in the art.In lysate, add cleaner, can remove the foreign metal ion of trace in lysate, as Co, Zn ion etc., and then can avoid these foreign metal ions to separate out in ionization process, affect the purity of gallium.Meanwhile, the filtrate of filtration is carried out to ozone oxidation, can remove the impurity negatively charged ion in excessive cleaner, further guarantee the purity of gallium.
Below in conjunction with specific embodiment, the present invention is described in further detail, these embodiment can not be interpreted as restriction the present invention scope required for protection.
Embodiment 1
1000ml acid system is extracted to the thick seminal fluid of aluminum oxide (gallium ion concentration is 8mg/L) and carry out ionic adsorption by the resin column that CL-TBP extration resin is housed (resin column capacity is 400ml) of three series connection successively, the flow velocity of thick seminal fluid is 10ml/min, obtains primary sorption extration resin; The concentrated hydrochloric acid that is 36% by concentration cleans primary sorption extration resin, and scavenging period is 10min; Primary sorption extration resin is carried out to wash-out with 120ml deionized water, elution time is 12min, obtains containing Gallium solution;
By making its volume be down to 1/3 of original volume containing Gallium solution heating is concentrated, add wherein 5g iron powder, fully after reaction, obtain reaction solution; Reaction solution is carried out to 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; Second adsorption extration resin is carried out to wash-out with deionized water, elution time is 15min, obtain deironing containing Gallium solution;
To the aqueous sodium hydroxide solution that is 20wt% containing Gallium solution dropping concentration of deironing, till no longer separating out to precipitation, filter, dry and precipitate; In precipitation, adding concentration is the aqueous sodium hydroxide solution of 50wt%, dissolves completely to precipitation, obtains lysate;
In lysate, add respectively the sodium sulphite of 1g and the sodium oxalate of 1g, filter; To the ozone that passes into 2L in filtrate, reaction 10min, filters, and obtains treating electrolytic solution;
Do anode and cathode with stainless steel substrates, treat that electrolyte temperature is 40 ℃, current density is 400A/m
2, bath voltage is 3V, treats electrolytic solution and carry out electrolysis under the condition that pole span is 50mm, obtains gallium 2.8g, and purity is 99.9%, and the rate of recovery is 80%.
Embodiment 2
1000ml acid system is extracted to the thick seminal fluid of aluminum oxide (gallium ion concentration is 8mg/L) and carry out ionic adsorption by the resin column that CL-TBP extration resin is housed (resin column capacity is 400ml) of three series connection successively, the flow velocity of thick seminal fluid is 12ml/min, obtains primary sorption extration resin; The hydrochloric acid that is 32% by concentration cleans primary sorption extration resin, and scavenging period is 8min; Primary sorption extration resin is carried out to wash-out with 110ml deionized water, elution time is 11min, obtains containing Gallium solution;
By containing Gallium solution heating concentrated make its volume be down to original volume 1/2 after, add wherein 1g iron powder, fully after reaction, obtain reaction solution; Reaction solution is carried out to 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; Second adsorption extration resin is carried out to wash-out with deionized water, elution time is 12min, obtain deironing containing Gallium solution;
To the aqueous sodium hydroxide solution that is 25wt% containing Gallium solution dropping concentration of deironing, till no longer separating out to precipitation, filter, dry and precipitate; In precipitation, adding concentration is the aqueous sodium hydroxide solution of 48wt%, dissolves completely to precipitation, obtains lysate;
In lysate, add respectively the sodium sulphite of 0.8g and the sodium oxalate of 0.8g, filter; To the ozone that passes into 2L in filtrate, reaction 10min, filters, and obtains treating electrolytic solution;
Do anode and cathode with stainless steel substrates, treat that electrolyte temperature is 40 ℃, current density is 300A/m
2, bath voltage is 4V, treats electrolytic solution and carry out electrolysis under the condition that pole span is 40mm, obtains gallium 2.7g, and purity is 99.1%, and the rate of recovery is 77%.Embodiment 3
1000ml acid system is extracted to the thick seminal fluid of aluminum oxide (gallium ion concentration is 8mg/L) and carry out ionic adsorption by the resin column that CL-TBP extration resin is housed (resin column capacity is 400ml) of three series connection successively, the flow velocity of thick seminal fluid is 15ml/min, obtains primary sorption extration resin; The hydrochloric acid that is 28% by concentration cleans primary sorption extration resin, and scavenging period is 5min; Primary sorption extration resin is carried out to wash-out with 100ml deionized water, elution time is 10min, obtains containing Gallium solution;
By making its volume be down to 1/2 of original volume containing Gallium solution heating is concentrated, add wherein 5g iron powder, fully after reaction, obtain reaction solution; Reaction solution is carried out to 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; Second adsorption extration resin is carried out to wash-out with deionized water, elution time is 10min, obtain deironing containing Gallium solution;
To the aqueous sodium hydroxide solution that is 30wt% containing Gallium solution dropping concentration of deironing, till no longer separating out to precipitation, filter, dry and precipitate; In precipitation, adding concentration is the aqueous sodium hydroxide solution of 45wt%, dissolves completely to precipitation, obtains lysate;
In lysate, add respectively the sodium sulphite of 0.5g and the sodium oxalate of 0.5g, filter; To the ozone that passes into 2L in filtrate, reaction 10min, filters, and obtains treating electrolytic solution;
Do anode and cathode with stainless steel substrates, treat that electrolyte temperature is 60 ℃, current density is 200A/m
2, bath voltage is 4V, treats electrolytic solution and carry out electrolysis under the condition that pole span is 20mm, obtains gallium 2.5g, and purity is 99.2%, and the rate of recovery is 71%.
Embodiment 4
1000ml acid system is extracted to the thick seminal fluid of aluminum oxide (gallium ion concentration is 8mg/L) and carry out ionic adsorption by the resin column that CL-TBP extration resin is housed (resin column capacity is 400ml) of three series connection successively, the flow velocity of thick seminal fluid is 18ml/min, obtains primary sorption extration resin; The hydrochloric acid that is 32% by concentration cleans primary sorption extration resin, and scavenging period is 8min; Primary sorption extration resin is carried out to wash-out with 90ml deionized water, elution time is 5min, obtains containing Gallium solution;
To dripping containing Gallium solution the aqueous sodium hydroxide solution that concentration is 18wt%, till no longer separating out to precipitation, filter, dry precipitation; In precipitation, adding concentration is the aqueous sodium hydroxide solution of 40wt%, dissolves completely to precipitation, obtains lysate;
Do anode and cathode with stainless steel substrates, lysate temperature is 15 ℃, and current density is 500A/m
2, bath voltage is 1V, treats electrolytic solution and carry out electrolysis under the condition that pole span is 60mm, obtains gallium 2.6g, and purity is 80.2%, and the rate of recovery is 60%.
Embodiment 5
1000ml acid system is extracted to the thick seminal fluid of aluminum oxide (gallium ion concentration is 8mg/L) and carry out ionic adsorption by the resin column that CL-TBP extration resin is housed (resin column capacity is 400ml) of three series connection successively, the flow velocity of thick seminal fluid is 20ml/min, obtains primary sorption extration resin; Primary sorption extration resin is carried out to wash-out with 150ml deionized water, elution time is 16min, obtains containing Gallium solution;
To dripping containing Gallium solution the aqueous sodium hydroxide solution that concentration is 32wt%, till no longer separating out to precipitation, filter, dry precipitation; In precipitation, adding concentration is the aqueous sodium hydroxide solution of 55wt%, dissolves completely to precipitation, obtains lysate;
Do anode and cathode with stainless steel substrates, lysate temperature is 70 ℃, and current density is 150A/m
2, bath voltage is 5V, treats electrolytic solution and carry out electrolysis under the condition that pole span is 15mm, obtains gallium 2.8g, and purity is 75.4%, and the rate of recovery is 62%.
From above data, can find out the gallium that adopts the method in the above embodiments of the present invention to reclaim from flyash, its purity is higher, the rate of recovery is higher, the especially method in embodiment 1～3, and the purity of the gallium of its recovery 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 modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
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: described acid system is extracted to the thick seminal fluid of aluminum oxide and carry out ionic adsorption by CL-TBP extration resin, obtain primary sorption extration resin; Described primary sorption extration resin is carried out to wash-out, obtain containing Gallium solution;
Purification step: add the first basic solution to described containing in Gallium solution, obtain containing gallium precipitation;
Recycling step: reclaim described gallium from described containing gallium precipitation.
2. method according to claim 1, is characterized in that, in described purification step to described containing before adding the step of described the first basic solution in Gallium solution, also comprise the step of carrying out deironing containing Gallium solution to described; Described step of carrying out deironing containing Gallium solution is comprised:
Add iron powder to described containing in Gallium solution, after reaction, obtain reaction solution;
Described reaction solution, by described CL-TBP extration resin, is carried out to secondary ions absorption, obtain second adsorption extration resin;
Described second adsorption extration resin is carried out to secondary wash-out, obtain the described containing Gallium solution of deironing.
3. method according to claim 2, it is characterized in that, before described primary sorption extration resin being carried out to ion wash-out and/or described second adsorption extration resin is carried out to the step of secondary ions wash-out, the step that the hydrochloric acid that also to comprise by concentration be 28～36wt% cleans described primary sorption extration resin or described second adsorption extration resin, scavenging period is 5～10min.
4. method according to claim 2, 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.
5. according to the method described in any one in claim 1 to 4, it is characterized in that, in described separating step, when described acid system is extracted to the thick seminal fluid of aluminum oxide by described CL-TBP extration resin, the flow velocity that described acid system extracts the thick seminal fluid of aluminum oxide is 10～15ml/min; When described primary sorption extration resin is carried out to wash-out, eluent is the hydrochloric acid that deionized water or concentration are 0.1～0.5wt%, and the consumption of described eluent is 100～120ml, and elution time is 10～12min.
6. according to the method described in any one in claim 2 to 4, it is characterized in that, in described purification step, to described, when adding iron powder in Gallium solution, the quality of described iron powder is 1～5g; When described reaction solution is passed through to described CL-TBP extration resin, the flow velocity of described reaction solution is 10～15ml/min; When described second adsorption extration resin is carried out again to wash-out, eluent is the hydrochloric acid that deionized water or concentration are 0.1～0.5wt%, and elution time is 10～15min.
7. according to the method described in any one in claim 1 to 6, it is characterized in that, described recycling step comprises:
Join in the second basic solution containing gallium precipitation described, make described resolution of precipitate, obtain lysate;
Described lysate is carried out to electrolysis, obtain described gallium.
8. method according to claim 7, is characterized in that, before described lysate being carried out to the step of electrolysis in described recycling step, 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 to described lysate, filter, filtrate is carried out to ozone Oxidation Treatment, obtain the described lysate of removal of impurities; Preferred described cleaner is sodium sulphite and/or sodium oxalate, and the consumption of preferred described cleaner is 1～2g.
9. according to the method described in claim 6 or 7, it is characterized in that, in the step of described electrolysis, electrolysis temperature is 40～60 ℃, and current density is 200～400A/m
2, electrolysis voltage is 3～4V, pole span is 20～50mm.
10. method according to claim 7, is characterized in that, in described purification step, described the first basic solution and described the second basic solution neutral and alkali material are respectively lithium hydroxide, potassium hydroxide or sodium hydroxide;
Preferably the concentration of described the second basic solution is greater than the concentration of described the first alkaline matter;
Preferably described the first basic solution and described the second basic solution are the aqueous solution of sodium hydroxide;
The concentration of described the first basic solution is 20～30wt%, and the concentration of described the second basic solution is 45～50wt%.
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| 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 |
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| CN111020198A (en) * | 2019-12-12 | 2020-04-17 | 广西大学 | Method for purifying gallium from acid solution based on silicon-based tributyl phosphate solid adsorbent |
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| 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 |
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| CN108374091A (en) * | 2018-03-30 | 2018-08-07 | 中国科学院过程工程研究所 | A kind of gallium for recycling the method for gallium in waste material from the gallium compound containing indissoluble and being obtained by this method |
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| 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 |
| EP3998363A4 (en) * | 2019-07-12 | 2023-07-19 | Obshchestvo s Ogranichennoy Otvetstvennost'yu "Obedinennaya Kompaniya Rusal Inzhenerno- Tekhnologicheskiy Tsentr" | Method for producing gallate solution |
| CN111020198A (en) * | 2019-12-12 | 2020-04-17 | 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 |
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