CN109897960A - A method of recycling gallium, phosphide element from the waste residue containing gallium, phosphide element - Google Patents
A method of recycling gallium, phosphide element from the waste residue containing gallium, phosphide element Download PDFInfo
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Abstract
The method that the present invention relates to a kind of to recycle gallium, phosphide element from the waste residue containing gallium, phosphide element, described method includes following steps: step (1), waste residue containing gallium, phosphide element is mixed with acid lixiviant, activation leaching process is carried out, the waste liquid containing gallium, phosphide element is obtained after being disposed；Step (2), contain gallium to obtained in step (1), acid lixiviant is added in the waste liquid of phosphide element and adjusts pH value to pH≤4, gallium will be contained later, the waste liquid of phosphide element passes through adsorption column, obtain adsorption column containing indium and pregnant solution containing gallium, adsorption column containing indium, which is rinsed, using eluant, eluent obtains pregnant solution containing indium, alkaline precipitating agent is added in pregnant solution containing indium and obtains indium hydroxide precipitating, pregnant solution containing gallium is electrolysed to obtain Metallic Gallium, method of the present invention can adapt to larger range of pH variation, changes in flow rate and temperature change, separative efficiency is higher, purity is higher, can in separating waste residues 96% or more gallium, phosphide element.
Description
Technical field
The present invention relates to purification technique field more particularly to it is a kind of from the waste residue containing gallium, phosphide element recycle gallium,
The method of phosphide element.
Background technique
With the product containing gallium, phosphide element, such as LED, solar panel, video screen, integrated circuit board etc. update speed
The continuous quickening of degree, China are also increasing severely year by year containing the waste residue quantity of gallium, phosphide element, and thus bring heavy metal pollution is tight
The self-regeneration of ecological environment has been influenced again.Containing gallium, phosphide element waste residue in contain a large amount of secondary resource, how to develop
Realize that its is innoxious during these secondary resources, reduction carries out processing bring environmental pollution to these waste residues and has become from now on
The great difficult problem that various countries are faced.On the other hand, containing gallium, phosphide element product in general all also contain copper, silver, Jin Denggui
Heavy metal component will cause the significant wastage of resource if these products cannot be recycled effectively after discarded.Although mesh
It is preceding containing gallium, phosphide element product abandonment after the harm of waste residue that generates do not cause enough attention also, relevant report is few, but
It is, recycled by method appropriate containing the valuable metal in gallium, phosphide element product and its poisonous and harmful element is effectively treated, for
It develops a circular economy, protect environment significant.
In the prior art for solution " high efficiente callback gallium, phosphide element from containing the waste material there are many miscellaneous element " this technology
Study on Problems is more, but not it has been proposed that more perfect technical solution solves the problems, such as this.Most commonly seen method
It is a kind of method of Ti recovery, gallium, indium from waste and old diode as disclosed in CN102951618B using high-temperature roasting method,
By crushing waste and old diode, organic principle therein is separated, for residual metallic powder after oxidizing roasting, product acid is molten
Zinc powder is added into filtrate for solution, filtering, and displacement obtains germanium, gallium, indium simple substance, simple substance is roasted at 600~700 DEG C, leads to simultaneously
Enter chlorinated with chlorine, according to the different separation for realizing germanium, gallium, phosphide element of the gas condensation temperature of chlorination metallic element, this method
Huge energy consumption, and need to use chlorine in preparation process, exhaust gas and dust emission into environment caused by environmental pollution is serious, no
It is suitable as industrial production.In contrast than advantageously passing through extraction separating metal ions, such as CN103199148B public affairs
A kind of method that gallium, indium, germanium are recycled from waste film solar battery opened, dissolves metal therein by oxidisability acid solution
Precipitating reagent is added thereto or reconciles the pH value of solution to separate miscellaneous element ion, by electrolytic separation gallium element, finally for ion
Indium ion is separated with back extraction by organic system extraction, precipitating obtains indium hydroxide, and this method will not generate dust and give up
Gas pollution, but still needs to use a large amount of water and extract liquor in extraction process, moreover, cannot to obtain purity higher for extraction
Gallium, indium ion.Other methods, a kind of recovery method of phosphide element, is obtained by leaching by hydrothermal process method as disclosed in CN103620070B
To the solution containing indium ion, indium ion absorption is added into the solution containing indium ion and uses bacterium, obtains being adsorbed in bacterial cell
The indium ion in portion, this method adsorbing metal ions efficiency is higher, and separation purity is also higher, but bacterial adsorption is slower, bacterium training
It supports and post processing cost is higher, be not suitable for large-scale production.Newest, one kind as disclosed in CN104212983A is from waste and old display
The method of recovery indium in device adjusts pH value to 1.5~2.5, filtering removal is filtered by dissolving waste liquid crystal display with acid solution
Slag, obtained filtrate are eluted by phosphoramidic acid base chelating resin splitter selective absorption indium ion, splitter through persalt
Solution containing indium ion, but in this method, it is lower using dissolving with hydrochloric acid indium ion efficiency, and chelated using phosphoramidic acid base
Resin plasma type splitter separates indium ion, and separative efficiency is affected by pH, only the separation effect when pH is 1.5~2.5
Rate can reach 90% or so, it is therefore desirable to be further improved.
To solve the above-mentioned problems, under the premise of not causing environmental pollution, this field needs a kind of from containing gallium, indium etc.
The method that gallium, phosphide element are recycled in the waste residue of metallic element, this method should apply to industrialized production, be suitable for more multiple from property
Gallium, phosphide element are recycled in miscellaneous waste residue, while process flow should not be excessively complicated, and recovery efficiency should be higher.
Summary of the invention
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of from the waste residue containing gallium, phosphide element
The method of middle recycling gallium, phosphide element, described method includes following steps:
Step (1), the waste residue containing gallium, phosphide element is mixed with acid lixiviant, is carried out activation leaching process, has been handled
The waste liquid containing gallium, phosphide element is obtained after finishing；
Step (2), to obtained in step (1) containing gallium, phosphide element waste liquid in be added acid lixiviant adjust pH value
To pH≤4, the waste liquid containing gallium, phosphide element is obtained into adsorption column containing indium and pregnant solution containing gallium by adsorption column later, using washing
De- agent rinses adsorption column containing indium and obtains pregnant solution containing indium, and it is heavy to obtain indium hydroxide for addition alkaline precipitating agent in pregnant solution containing indium
It forms sediment, pregnant solution containing gallium is electrolysed to obtain Metallic Gallium.
Under the premise of activation leaching process described in step (1) is existing for the acid lixiviant, Xiang Hanyou gallium, phosphide element
Waste residue and acid lixiviant mixture provide mechanical energy and/or irradiation can process, by containing gallium, phosphide element it is useless
Energy is introduced in the mixture of slag and acid lixiviant, causes the compound lattice mismatch containing gallium, phosphide element wherein contained, office
Portion's energy increases, and lattice defect increases, and can effectively facilitate the waste residue surface active containing gallium, phosphide element, increases gallium, indium metal
The quantity in surface-active site weakens the stability of metal oxide layer, increases effective contact surface on waste residue surface and leaching agent
Product so that gallium, phosphide element are easier to be leached agent dissolution, after overactivation leaching process, containing gallium, phosphide element waste residue in gallium,
The leaching rate of phosphide element is up to 99%.
In view of providing mechanical energy to the mixture of the waste residue containing gallium, phosphide element and acid lixiviant in practical application
And/or irradiation can the too low effect of energy it is unobvious, energy it is excessively high uneconomical and be easily converted to it is interior can, by following various to containing
Have gallium, the waste residue of phosphide element and acid lixiviant mixture provide mechanical energy and/or irradiation can method preferred embodiment into
Row activation is leached, and effect is more excellent.
Preferably, it is provided described in step (1) to the mixture of the waste residue containing gallium, phosphide element and acid lixiviant mechanical
Can and/or irradiation can by ultrasonic treatment, milled processed, microwave irradiation handle or ultraviolet irradiation handle in any one or
The combination of at least two methods is realized, described to provide machinery to the mixture of the waste residue containing gallium, phosphide element and acid lixiviant
Can and/or irradiation can process be not related to temperature-rise period, i.e., not into the waste residue containing gallium, phosphide element introduce in energy.
Preferably, the power of the ultrasonic treatment be 200~1000W, such as 210W, 250W, 300W, 350W, 450W,
550W, 750W, 850W, 950W, 980W etc., time of ultrasonic treatment are 30~100min, for example, 31min, 35min, 42min,
50min, 60min, 70min, 75min, 80min, 85min, 94min, 99min etc..
Preferably, the milled processed is any one processing method in ball milling, rod milling and column mill.
It is further preferred that the milled processed is ball milling, grinding rate is 150~200 turns/min, such as 151 turns/
Min, 154 turns/min, 160 turns/min, 170 turns/min, 180 turns/min, 190 turns/min, 198 turns/min etc., milling time is
50~150min, such as 51min, 80min, 100min, 120min, 150min, 160min, 170min, 190min, 198min
Deng.
Preferably, the power of microwave irradiation processing is 100~800W, for example, 120W, 180W, 250W, 300W,
400W, 500W, 600W, 700W, 750W, 780W, 795W etc., the time of microwave treatment are 20~120min, for example, 21min,
30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 118min etc..
Preferably, the wavelength of ultraviolet irradiation processing is 251~370nm, for example, 252nm, 262nm, 272nm,
282nm, 290nm, 300nm, 310nm, 320nm, 330nm, 340nm, 350nm, 360nm, 369nm etc., ultraviolet irradiation processing
Time be 30~240min, such as 31min, 40min, 60min, 80min, 100min, 140min, 160min, 180min,
200min, 230min, 238min etc..
Preferably, acid lixiviant described in step (1) is the mixed solution of inorganic acid and organic acid.
Preferably, the inorganic acid be hydrochloric acid, sulfuric acid, nitric acid, any one in phosphoric acid or at least two mixture.
Preferably, the organic acid is formic acid, acetic acid, oxalic acid, citric acid, any one in tartaric acid or at least two
Mixture.
Preferably, the waste residue containing gallium, phosphide element described in step (1) first passed through before activating leaching process crushing,
Sorting process obtains waste and old powder, later mixes waste and old powder with acid lixiviant, stirs, is activated while agitating
Leaching process.
Preferably, the crushing, sorting process are that the waste residue containing gallium, phosphide element is ground into powder using pulverizer,
It by sieve diameter is 20~350 μm of (such as 25 μm, 40 μm, 65 μm, 90 μm, 140 μm, 190 μm, 250 μm, 280 μ by powder
M, 320 μm, 340 μm, 345 μm etc.) sieve sieving, sieving product impregnate in water, remove the organic components bubbled through the water column,
The waste and old powder is obtained by filtration, it is further preferred that the sieve diameter of the sieve is 50~300 μm.
Preferably, the stirring rate of the stirring be 50~400 turns/min, such as 51 turns/min, 60 turns/min, 80 turns/
Min, 120 turns/min, 160 turns/min, 200 turns/min, 250 turns/min, 300 turns/min, 350 turns/min, 380 turns/min, 395
Turn/min etc., preferably 80~300 turns/min.
Preferably, the mixing time of the stirring be 10~100min, such as 11min, 20min, 30min, 40min,
50min, 60min, 70min, 80min, 90min, 95min etc., preferably 20~80min.
Preferably, the waste and old powder with 10~200g/L (such as 11g/L, 20g/L, 40g/L, 60g/L, 80g/L,
110g/L, 130g/L, 150g/L, 170g/L, 190g/L, 198g/L etc.) concentration mixed with acid lixiviant, further preferably
For 20~180g/L.
Preferably, the waste residue containing gallium, phosphide element described in step (1) is waste and old LED lamp bead.
Preferably, adsorption column described in step (2) should have excellent pH stability and stronger specificity choosing
Adsorption capacity is selected, therefore, does not consider that such as containing anions and canons type vulnerable to pH and the temperature adsorption column influenced using adsorption rate adsorbs
The adsorption column of the polymer beads filling of agent.
Preferably, adsorption column described in step (2) is cellulose grain or the tree for having solvay-type adsorbent by surface grafting
The particles filled obtained adsorption column of rouge, for hydrophilic consideration, further preferably hydrophily is preferably had by surface grafting
The adsorption column that the cellulose grain of solvay-type adsorbent is filled.
Preferably, the solvay-type adsorbent includes di-(2-ethylhexyl)phosphoric acid ester, tributyl phosphate, 2- ethylhexyl
The mono- 2- ethylhexyl of phosphoric acid, methyl iso-butyl ketone (MIBK), acetamide, cyclohexanone, Sec-octylphenoxyl acetic acid, carbon atom number 7-9
Hydroximic acid, in 5,8- diethyl -7- hydroxydodecyl -6- oxime any one or at least two combination.
Preferably, flow velocity of the waste liquid in adsorption column containing gallium, phosphide element described in step (2) is 5~100mL/
Min, such as 6mL/min, 10mL/min, 20mL/min, 30mL/min, 40mL/min, 50mL/min, 60mL/min, 70mL/
Min, 80mL/min, 90mL/min, 98mL/min etc., further preferably 10~80mL/min, flow velocity is too fast, adsorbs and does not fill
Point, then influence the operating time slowly excessively, and be easy so that other kinds of metal ion is adsorbed.
Preferably, the temperature containing gallium, the waste liquid of phosphide element described in step (2) is 5~40 DEG C, such as 6 DEG C, 8 DEG C, 12
DEG C, 18 DEG C, 24 DEG C, 30 DEG C, 34 DEG C, 38 DEG C, 39 DEG C etc., preferably 25~35 DEG C, temperature is excessively high, the enhancing of desorption effect, drop
Low certain adsorption efficiency, it is too low, adsorption column activity can be reduced to a certain extent, again such that adsorption efficiency decreases.
Preferably, the pH value containing gallium, the waste liquid of phosphide element described in step (2) be 0.3~3, such as 0.4,0.8,
1.0,1.5,2.0,2.4,2.6,2.8 etc., pH too low (such as less than 0.3) or relatively high (such as pH is 3~4) will not influence
Adsorption efficiency conciliates adsorption capacity.
Preferably, eluant, eluent described in step (2) be inorganic acid in any one or at least two mixture, preferably
For in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid any one or at least two mixture.
Preferably, described in step (2) using eluant, eluent rinse flow velocity be 5~120mL/min, such as 6mL/min,
10mL/min、20mL/min、30mL/min、40mL/min、50mL/min、60mL/min、70mL/min、80mL/min、90mL/
Min, 100mL/min, 110mL/min, 118mL/min etc., further preferably 10~100mL/min.
Preferably, described in step (2) using eluant, eluent rinse in 5~40 DEG C of temperature of eluant, eluent, such as 5 DEG C, 10 DEG C,
15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 38 DEG C etc., further preferably 25~35 DEG C.
Preferably, alkaline precipitating agent described in step (2) includes ammonium hydroxide.
Preferably, the precipitating of indium hydroxide described in step (2) obtains hydroxide by filtering, centrifuge separation, drying and processing
Indium product.
Preferably, pregnant solution containing gallium described in step (2) first passes through concentration and obtains rich Gallium solution is electrolysed again, excellent
Selection of land, it is described richness Gallium solution in gallium element concentration >=1g/L, such as 2g/L, 4g/L, 8g/L, 16g/L, 20g/L, 25g/L,
30g/L etc..
Preferably, pregnant solution containing gallium described in step (2) is in 25~80 DEG C of (such as 26 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45
DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 78 DEG C etc.) under be electrolysed, further preferably 35~60 DEG C.
Preferably, electrolysis described in step (2) is electric to be carried out using direct current, pulse current or direct current-superimposed pulses electric current
Solution.
Preferably, the decomposition voltage of electrolysis described in step (2) is 4~10V, such as 5V, 6V, 7V, 8V, 9V etc., electrolysis
Current density be 50~500mA/L, such as 60mA/L, 80mA/L, 100mA/L, 150mA/L, 200mA/L, 250mA/L,
300mA/L, 350mA/L, 400mA/L, 450mA/L, 480mA/L, 490mA/L etc., electrolysis time be 0.3~5h, such as 0.4h,
0.8h, 1.2h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 4.9h etc..
It is further preferred that the current density of electrolysis described in step (2) is 100~300mA/L.
The second object of the present invention is to provide a kind of indium hydroxide precipitating, and the indium hydroxide precipitating is by above method system
It is standby to obtain.
The third object of the present invention is to provide a kind of gallium material, and the gallium material is prepared by the above method.
Preferably, the purity of the gallium material is 99.9%.
The present invention has the advantage that
(1) it is compared with the traditional method, the present invention introduces mechanical energy into system by selecting specific activation leaching step
And/or irradiation can make containing gallium, phosphide element waste residue in gallium, phosphide element activation, can be more efficient be leached liquid
It leaches, to obtain the solution containing gallium, phosphide element of higher concentration.
(2) molten containing gallium, phosphide element by selecting the adsorption column absorption indium ion containing solvay-type adsorbent can adapt to
The larger range of pH variation of liquid, changes in flow rate and temperature change, separative efficiency is higher, can be 96% or more in separating waste residues
Gallium, phosphide element.
(3) present invention will not discharge environmentally harmful exhaust gas and dust pollution, separating technology process during the separation process
Short, elapsed time is less, is suitable for large-scale production.
(4) indium hydroxide and gallium material purity that the present invention recycles are higher, and can especially obtain purity is
99.9% gallium material.
Detailed description of the invention
Fig. 1 is the method for recycling gallium, phosphide element described in the embodiment of the present invention 1 from the waste residue containing gallium, phosphide element
Process flow chart.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
As shown in Figure 1, gallium, phosphide element are recycled from the waste residue containing gallium, phosphide element as follows:
Step (1) takes the waste and old LED lamp bead of 1kg as the waste residue containing gallium, phosphide element, wherein the gallium containing 1.01wt%
The waste residue utilization pulverizer is ground into powder by the phosphide element of element and 0.23wt%, and it is 50 μ that powder, which is passed through sieve diameter,
The sieve of m is sieved, and sieving product impregnates in water, removes the organic components bubbled through the water column, by waste and old powder is obtained by filtration,
By waste and old powder with the acetic acid acid that 1:1 is mixed to get by volume of the hydrochloric acid and 30wt% of the concentration of 20g/L and 17.5wt%
Property leaching agent mixing, using blender with the rotary speed stirring mixture 20min of 300 turns/min, make its be uniformly mixed, do not close and stir
Machine is mixed, mixture is drained into ball mill, activation leaching process is carried out with the revolving speed ball milling 50min of 200 turns/min at 25 DEG C,
Mixture after obtaining activation leaching process filters the mixture after activation leaching process, and taking filtrate is containing gallium, phosphide element
Waste liquid.
Step (2) takes the above-mentioned waste liquid containing gallium, phosphide element, be added thereto identical acid lixiviant adjust pH to
1.5, flow velocity of the waste liquid at 25 DEG C with 30mL/min is passed through the fibre that surface grafting has di-(2-ethylhexyl)phosphoric acid ester later
In the adsorption column filled of dimension crude granule, after it is all containing gallium, phosphide element waste liquid all after adsorption column, obtain inhaling containing indium
Attached column collects the waste liquid by absorption, as pregnant solution containing gallium, and by measurement, the concentration of gallium element is in pregnant solution containing gallium
0.13g/L will contain the vacuum distillation of gallium pregnant solution and carry out concentration, and obtain the rich Gallium solution that gallium element concentration is 1.5g/L, will
35 DEG C of rich Gallium solution constant temperature, the pulse direct current that frequency of use is 50Hz carry out electrolysis 0.5h, and electrolysis electrode is graphite rod electricity
Pole, decomposition voltage 10V, electrolytic current density 300mA/L, electrolysis bottom of pond portion obtain the liquid-gallium that purity is 99.9%
9.89g, at 25 DEG C using the solution 300mL that the nitric acid volume ratio 1:1 of the hydrochloric acid of 17.5wt% and 25wt% is mixed to get as
Eluant, eluent rinses adsorption column containing indium with the flow velocity of 10mL/min, and the solution obtained after flushing is to contain indium pregnant solution, to containing indium richness
Alkaline precipitating agent ammonium hydroxide is added in liquid collecting until no longer there is precipitating, collects the precipitating of generation, it will after filtering, centrifuge separation
It is dried, and indium hydroxide product 3.26g is obtained.
Embodiment 2
Difference with embodiment 1 is only that, the revolving speed of ball milling is 150 turns/min in step (1), and the time of ball milling is
50min。
Embodiment 2 obtains solid gallium 9.63g, purity 99.9%, indium hydroxide product 3.19g.
Embodiment 3
Difference with embodiment 1 is only that activation leaching process described in step (1) is to be using power by mixture
The supersonic generator of 200W is ultrasonically treated 100min, at the ultraviolet irradiation that ultrasonic treatment while is 255nm using wavelength
Manage 30min.
Embodiment 3 obtains solid gallium 9.78g, purity 99.9%, indium hydroxide product 3.24g.
Embodiment 4
Difference with embodiment 1 is only that activation leaching process described in step (1) is to be using power by mixture
The supersonic generator of 1000W is ultrasonically treated 30min, is handled after ultrasonic treatment using the ultraviolet irradiation that wavelength is 370nm
240min。
Embodiment 4 obtains solid gallium 9.95g, purity 99.9%, indium hydroxide product 3.29g.
Embodiment 5
Difference with embodiment 1 is only that activation leaching process described in step (1) is the microwave for being 100W using power
Generator generation wavelength is the microwave of 1.3cm, carries out radiation treatment 120min to mixture.
Embodiment 5 obtains solid gallium 9.68g, purity 99.9%, indium hydroxide product 3.20g.
Embodiment 6
Difference with embodiment 1 is only that activation leaching process described in step (1) is the microwave for being 800W using power
Generator generation wavelength is the microwave of 1.3cm, carries out radiation treatment 20min to mixture.
Embodiment 6 obtains solid gallium 9.91g, purity 99.9%, indium hydroxide product 3.26g.
Embodiment 7
Difference with embodiment 1 is only that, by " surface grafting has the fibre of di-(2-ethylhexyl)phosphoric acid ester in step (2)
The adsorption column filled of dimension crude granule " replaces with that " surface grafting has the cellulose grain of Sec-octylphenoxyl acetic acid to fill
The adsorption column arrived ", and flow velocity of the waste liquid in adsorption column containing gallium, phosphide element is 80mL/min.
Embodiment 7 obtains solid gallium 9.83g, purity 99.9%, indium hydroxide product 9.93g.
Embodiment 8
Difference with embodiment 1 is only that, by " surface grafting has the fibre of di-(2-ethylhexyl)phosphoric acid ester in step (2)
The adsorption column filled of dimension crude granule " replaces with that " surface grafting has the polystyrene resin beads of cyclohexanone to fill
Adsorption column ", and flow velocity of the waste liquid in adsorption column containing gallium, phosphide element is 10mL/min.
Embodiment 8 obtains solid gallium 9.93g, purity 99.9%, indium hydroxide product 3.28g.
Embodiment 9
Difference with embodiment 1 is only that, by " surface grafting has the fibre of di-(2-ethylhexyl)phosphoric acid ester in step (2)
The adsorption column filled of dimension crude granule " replaces with that " surface grafting has the poly- of 5,8- diethyl -7- hydroxydodecyl -6- oxime
The adsorption column that styrene resin particles are filled ", and temperature of the waste liquid in adsorption column containing gallium, phosphide element is 35 DEG C.
Embodiment 9 obtains solid gallium 9.89g, purity 99.9%, indium hydroxide product 3.27g.
Embodiment 10
Difference with embodiment 1 is only that leachate described in step (1) is the sulfuric acid and 5wt% of 1mol/L by concentration
Oxalic acid 1:2 is mixed to get by volume, the pH value containing gallium, the waste liquid of phosphide element be 3.8.
Embodiment 10 obtains solid gallium 9.88g, purity 99.9%, indium hydroxide product 3.24g.
Embodiment 11
Difference with embodiment 1 is only that leachate described in step (1) is the nitric acid and 25wt% of 1mol/L by concentration
Tartaric acid 2:1 is mixed to get by volume, the pH value containing gallium, the waste liquid of phosphide element be 0.5.
Embodiment 11 obtains solid gallium 9.78g, purity 99.9%, indium hydroxide product 3.25g.
Embodiment 12
Difference with embodiment 1 is only that the sieve diameter of sieve described in step (1) is 300 μm, the blender
Revolving speed is 80 turns/min, mixing time 80min.
Embodiment 12 obtains solid gallium 9.90g, purity 99.9%, indium hydroxide product 3.28g.
Embodiment 13
Difference with embodiment 1 is only that eluant, eluent described in step (2) by the phosphoric acid and 17.5wt% of 15wt% concentration
The hydrochloric acid of concentration is obtained with volume ratio 1:1 mixed preparing, and the volume of eluant, eluent is 800mL, and the flow velocity of eluant, eluent is 100mL/
Min, the temperature of eluant, eluent are 35 DEG C.
Embodiment 13 obtains solid gallium 9.85g, purity 99.9%, indium hydroxide product 3.26g.
Embodiment 14
Difference with embodiment 1 is only that pregnant solution containing gallium described in step (2) maintains concentration without concentration
0.13g/L is constant, and electrolysis carries out at 60 DEG C, decomposition voltage 4V, electrolytic current density 100mA/L, electrolysis time 5h.
Embodiment 14 obtains liquid-gallium 9.64g, purity 99.9%, indium hydroxide product 3.20g.
Reference examples 1
Difference with embodiment 1 is only that, by " surface grafting has the fibre of di-(2-ethylhexyl)phosphoric acid ester in step (2)
The adsorption column filled of dimension crude granule " replaces with that " surface grafting has the cationic granules of polystyrene of benzene sulfonic acid to fill
The adsorption column arrived ".
Reference examples 1 obtain solid gallium 9.87g, purity 99.9%, indium hydroxide product 3.04g.
Reference examples 2 and the difference of embodiment 1 are only that waste and old powder described in step (1) is mixed with acid lixiviant
Afterwards without activating leaching process, directly operation described in progress step (2).
Reference examples 2 obtain solid gallium 4.3g, purity 99.9%, indium hydroxide product 1.2g.
The concentration or content of all embodiments and gallium, phosphide element in reference examples pass through GB/T30902-2014 in the present invention
Method described in " the measurement inductively coupled plasma emission spectrography (ICP-OES) of inorganic chemical product impurity element " is surveyed
It is fixed.
In the present invention all embodiments and the purity of gallium, phosphide element in reference examples by by sample with after aqua regia dissolution,
Solution passes through GB/T 30902-2014 " the measurement inductively coupled plasma emission spectrography of inorganic chemical product impurity element
(ICP-OES) " the method measurement described in.
By gallium isolated in above-described embodiment and reference examples, phosphide element weight respectively with contain gallium, phosphide element
Gallium in waste residue, phosphide element content compare, obtain the separative efficiency of corresponding gallium, phosphide element, gained separative efficiency be listed in table
1。
The separative efficiency of gallium element and phosphide element in each embodiment of table 1 and reference examples
Through the foregoing embodiment with reference examples it can be found that being compared with the traditional method, the present invention is specific living by selecting
Change leaching step, is introduced into system mechanical energy and/or irradiate can make containing gallium, phosphide element waste residue in gallium, phosphide element
Activation, the liquid that is leached that can be more efficient leaches, so that the solution containing gallium, phosphide element of higher concentration is obtained, moreover, passing through
The adsorption column absorption indium ion containing solvay-type adsorbent is selected to can adapt to larger range of pH variation, changes in flow rate and temperature
Variation, and extraction efficiency is higher, being capable of 96% or more gallium, phosphide element in separating waste residues.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of method for recycling gallium, phosphide element from the waste residue containing gallium, phosphide element, which is characterized in that the method includes
Following steps:
Step (1), the waste residue containing gallium, phosphide element is mixed with acid lixiviant, activation leaching process is carried out, after being disposed
Obtain the waste liquid containing gallium, phosphide element；
Step (2), to obtained in step (1) containing gallium, phosphide element waste liquid in acid lixiviant be added adjust pH value to pH
≤ 4, the waste liquid containing gallium, phosphide element is obtained adsorption column containing indium and pregnant solution containing gallium, use eluant, eluent by adsorption column later
It rinses adsorption column containing indium and obtains pregnant solution containing indium, alkaline precipitating agent is added in pregnant solution containing indium and obtains indium hydroxide precipitating, it is right
Pregnant solution containing gallium is electrolysed to obtain Metallic Gallium；
The activation leaching process for the mixture of the waste residue containing gallium, phosphide element and acid lixiviant provide mechanical energy and/
Or the process of irradiation energy.
2. the method according to claim 1, wherein the activation leaching process is by being ultrasonically treated, at grinding
Reason, microwave irradiation processing or the combination of any one or at least two methods in ultraviolet irradiation processing are realized；
Preferably, the power of the ultrasonic treatment is 200~1000W, and the time of ultrasonic treatment is 30~100min；
Preferably, the milled processed is any one processing method in ball milling, rod milling and column mill；
It is further preferred that the milled processed be ball milling, grinding rate be 150~200 turns/min, milling time be 50~
150min；
Preferably, the power of the microwave irradiation processing is 100~800W, and the time of microwave treatment is 20~120min；
Preferably, the wavelength of ultraviolet irradiation processing is 251~370nm, the time of ultraviolet irradiation processing is 30~
240min。
3. method according to claim 1 or 2, which is characterized in that the acid lixiviant is inorganic acid and organic acid
Mixed solution；
Preferably, the inorganic acid be hydrochloric acid, sulfuric acid, nitric acid, any one in phosphoric acid or at least two mixture；
Preferably, the organic acid be formic acid, acetic acid, oxalic acid, citric acid, any one in tartaric acid or at least two mixing
Object.
4. method described according to claim 1~one of 3, which is characterized in that the waste residue containing gallium, phosphide element is activating
Leaching process first passes through crushing before, sorting process obtains waste and old powder, later mixes waste and old powder with acid lixiviant, stirs
It mixes, carries out activation leaching process while agitating；
The crushing, sorting process are that the waste residue containing gallium, phosphide element is ground into powder using pulverizer, and powder is passed through sieve
The sieve that bore dia is 20~350 μm is sieved, and sieving product impregnates in water, removes the organic components bubbled through the water column, and filters
Obtain the waste and old powder；
Preferably, the sieve diameter of the sieve is 50~300 μm；
Preferably, the stirring rate of the stirring is 50~400 turns/min, further preferably 80~300 turns/min；
Preferably, the mixing time of the stirring is 10~100min, further preferably 20~80min；
Preferably, the waste and old powder is mixed with the concentration of 10~200g/L with acid lixiviant, further preferably 20~
180g/L；
Preferably, the waste residue containing gallium, phosphide element is waste and old LED lamp bead.
5. method described according to claim 1~one of 4, which is characterized in that the adsorption column is to have complexing by surface grafting
The adsorption column that the cellulose grain or resin particle of type adsorbent are filled, preferably has solvay-type adsorbent by surface grafting
The adsorption column filled of cellulose grain；
Preferably, the solvay-type adsorbent includes di-(2-ethylhexyl)phosphoric acid ester, tributyl phosphate, 2- ethylhexyl phosphoric acid
Mono- 2- ethylhexyl, methyl iso-butyl ketone (MIBK), acetamide, cyclohexanone, Sec-octylphenoxyl acetic acid, the hydroxyl that carbon atom number is 7-9
Oxime acid, in 5,8- diethyl -7- hydroxydodecyl -6- oxime any one or at least two combination；
Preferably, the flow velocity of the waste liquid in adsorption column containing gallium, phosphide element is 5~100mL/min, further preferably
10~80mL/min；
Preferably, the temperature containing gallium, the waste liquid of phosphide element is 5~40 DEG C, further preferably 25~35 DEG C.
6. method described according to claim 1~one of 5, which is characterized in that the eluant, eluent is any one in inorganic acid
Kind or at least two mixture, preferably hydrochloric acid, sulfuric acid, nitric acid, in phosphoric acid any one or at least two mixture；
Preferably, the flow velocity rinsed using eluant, eluent is 5~120mL/min, further preferably 10~100mL/min；
Preferably, it is described using eluant, eluent rinse in eluant, eluent temperature be 5~40 DEG C, further preferably 25~35 DEG C.
7. method described according to claim 1~one of 6, which is characterized in that the alkaline precipitating agent includes ammonium hydroxide；
The indium hydroxide precipitating obtains indium hydroxide product by filtering, centrifuge separation, drying and processing.
8. method described according to claim 1~one of 7, which is characterized in that the pregnant solution containing gallium first passes through concentration
It obtains rich Gallium solution to be electrolysed again, it is preferable that concentration >=1g/L of gallium element in the richness Gallium solution；
Preferably, the pregnant solution containing gallium is electrolysed at 25~80 DEG C, and further preferably 35~60 DEG C；
Preferably, the electrolysis is to be electrolysed using direct current, pulse current or direct current-superimposed pulses electric current；
Preferably, the decomposition voltage of the electrolysis is 4~10V；
Preferably, the current density of the electrolysis is 50~500mA/L, further preferably 100~300mA/L；
Preferably, the electrolysis time of the electrolysis is 0.3~5h.
9. a kind of indium hydroxide precipitating, which is characterized in that the indium hydroxide precipitates the side as described in one of claim 1~8
Method is prepared.
10. a kind of gallium material, which is characterized in that gallium material method as described in one of claim 1~8 is prepared；
Preferably, the purity of the gallium material is 99.9%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440955A (en) * | 2020-05-15 | 2020-07-24 | 广东先导稀材股份有限公司 | Method for extracting gallium from gallium-containing smelting slag |
| CN112410585A (en) * | 2020-10-22 | 2021-02-26 | 上海交通大学 | Method for recovering gallium arsenide and copper from waste and old IC components containing gallium arsenide and application |
| CN113234942A (en) * | 2020-09-21 | 2021-08-10 | 合肥工业大学 | Method for leaching gallium and vanadium from coal gangue |
| CN113512651A (en) * | 2021-06-09 | 2021-10-19 | 中山智隆新材料科技有限公司 | Method for respectively recovering indium and gallium from IGZO target material |
| CN114137010A (en) * | 2021-11-05 | 2022-03-04 | 上海交通大学 | Method for measuring distribution state of trace elements in high-temperature alloy |
| CN114452940A (en) * | 2022-01-14 | 2022-05-10 | 广西大学 | Preparation method of waste resin-based secondary octyl phenoxy acetic acid composite adsorbent |
| CN115323176A (en) * | 2022-08-12 | 2022-11-11 | 昆明理工大学 | Method for efficiently separating and recycling gallium and indium from gallium-based liquid metal waste |
| TWI803261B (en) * | 2022-03-28 | 2023-05-21 | 虹京金屬股份有限公司 | Method for recycling indium |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925696A (en) * | 2012-10-29 | 2013-02-13 | 四川长虹电器股份有限公司 | Comprehensive recycling method of waste plasma screen |
| CN103074498A (en) * | 2012-12-31 | 2013-05-01 | 西部矿业集团有限公司 | Method for acid-leaching gallium from coal ash through microwave heating |
| CN103184338A (en) * | 2011-12-29 | 2013-07-03 | 广东先导稀材股份有限公司 | Recovery method of copper indium gallium selenide thin-film solar panel |
| US20140065037A1 (en) * | 2010-11-26 | 2014-03-06 | Molycorp Minerals Canada Ulc | Treatment of indium gallium alloys and recovery of indium and gallium |
| KR101528598B1 (en) * | 2014-04-01 | 2015-06-12 | 주식회사 엔코 | A selectively recovery method for indium & gallium from the mixed indium, gallium and znic scraps |
| CN105907974A (en) * | 2016-06-16 | 2016-08-31 | 北京科技大学 | Method of comprehensively recycling valuable metal from lead sulfate slag |
-
2017
- 2017-12-07 CN CN201711283603.7A patent/CN109897960A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140065037A1 (en) * | 2010-11-26 | 2014-03-06 | Molycorp Minerals Canada Ulc | Treatment of indium gallium alloys and recovery of indium and gallium |
| CN103184338A (en) * | 2011-12-29 | 2013-07-03 | 广东先导稀材股份有限公司 | Recovery method of copper indium gallium selenide thin-film solar panel |
| CN102925696A (en) * | 2012-10-29 | 2013-02-13 | 四川长虹电器股份有限公司 | Comprehensive recycling method of waste plasma screen |
| CN103074498A (en) * | 2012-12-31 | 2013-05-01 | 西部矿业集团有限公司 | Method for acid-leaching gallium from coal ash through microwave heating |
| KR101528598B1 (en) * | 2014-04-01 | 2015-06-12 | 주식회사 엔코 | A selectively recovery method for indium & gallium from the mixed indium, gallium and znic scraps |
| CN105907974A (en) * | 2016-06-16 | 2016-08-31 | 北京科技大学 | Method of comprehensively recycling valuable metal from lead sulfate slag |
Non-Patent Citations (1)
| Title |
|---|
| J. S. LIU等: "Selective Separation of In(III), Ga(III), and Zn(II) from Dilute Solution Using Solvent-Impregnated Resin Containing Di(2-ethylhexyl) Phosphoric Acid", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440955A (en) * | 2020-05-15 | 2020-07-24 | 广东先导稀材股份有限公司 | Method for extracting gallium from gallium-containing smelting slag |
| CN113234942A (en) * | 2020-09-21 | 2021-08-10 | 合肥工业大学 | Method for leaching gallium and vanadium from coal gangue |
| CN112410585A (en) * | 2020-10-22 | 2021-02-26 | 上海交通大学 | Method for recovering gallium arsenide and copper from waste and old IC components containing gallium arsenide and application |
| CN113512651A (en) * | 2021-06-09 | 2021-10-19 | 中山智隆新材料科技有限公司 | Method for respectively recovering indium and gallium from IGZO target material |
| CN114137010A (en) * | 2021-11-05 | 2022-03-04 | 上海交通大学 | Method for measuring distribution state of trace elements in high-temperature alloy |
| CN114137010B (en) * | 2021-11-05 | 2024-02-13 | 上海交通大学 | Determination method for trace element distribution state of high-temperature alloy |
| CN114452940A (en) * | 2022-01-14 | 2022-05-10 | 广西大学 | Preparation method of waste resin-based secondary octyl phenoxy acetic acid composite adsorbent |
| CN114452940B (en) * | 2022-01-14 | 2023-12-01 | 广西大学 | Preparation method of waste resin-based sec-octyl phenoxyacetic acid composite adsorbent |
| TWI803261B (en) * | 2022-03-28 | 2023-05-21 | 虹京金屬股份有限公司 | Method for recycling indium |
| CN115323176A (en) * | 2022-08-12 | 2022-11-11 | 昆明理工大学 | Method for efficiently separating and recycling gallium and indium from gallium-based liquid metal waste |
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Application publication date: 20190618 |