CN105063364A - Method for recycling indium from waste liquid crystal display - Google Patents
Method for recycling indium from waste liquid crystal display Download PDFInfo
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- CN105063364A CN105063364A CN201510551420.3A CN201510551420A CN105063364A CN 105063364 A CN105063364 A CN 105063364A CN 201510551420 A CN201510551420 A CN 201510551420A CN 105063364 A CN105063364 A CN 105063364A
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- liquid crystal
- indium
- crystal display
- water
- waste liquid
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 76
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 70
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002699 waste material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004064 recycling Methods 0.000 title abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011521 glass Substances 0.000 claims abstract description 30
- 239000012141 concentrate Substances 0.000 claims abstract description 22
- 238000000605 extraction Methods 0.000 claims abstract description 18
- 238000002386 leaching Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 241000252254 Catostomidae Species 0.000 abstract 1
- 230000008569 process Effects 0.000 description 17
- 239000007788 liquid Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000010922 glass waste Substances 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 230000035800 maturation Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 230000003020 moisturizing effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 1
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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 method for recycling indium from a waste liquid crystal display and belongs to the technical field of resource regeneration. The two outer side faces of the clean waste liquid crystal display are each provided with a sucker, and the waste liquid crystal display is separated by pulling the suckers outwards; a liquid crystal face of a glass sheet material with the liquid crystal face exposed is ground and scraped till a glass layer is exposed, and the ground and scraped glass sheet material is washed with high-pressure water; after part of water in a mixture composed of liquid crystals, indium concentrate and water is removed, the mixture is roasted, and the indium concentrate is obtained; the indium concentrate is subjected to leaching, extraction and aluminum row replacement so that crude indium can be obtained. The method is high in production efficiency, the resource regeneration utilization rate is high, the indium recycling rate is larger than 90%, and negative effects caused when nitric acid, acetone and acid or organic solvents high in volatility are used are avoided.
Description
Technical field
The invention belongs to resource recovery technical field, particularly to the recovery technology of the indium metal in waste liquid crystal display screen.
Background technology
Liquid-crystal display (LCD) develops rapidly from the nineties in 20th century, and progressively move to maturity, due to its have that sharpness is high, image color good, environmental protection, power saving, the frivolous and advantage such as to be easy to carry, be widely used in household electrical appliance, computer and communication products.In recent years, the output of China's LCD product increases substantially.The LCD TV annual production of China in 2004 is less than 1,000,000; Between 2004 ~ 2007 years, the output of the annual computer liquid-crystal display of China is all more than 6,000 ten thousand; Domestic flat panel Liquid Crystal panel production capacity, from 2008 from the original share less than the whole world 1%, develops into global 21% share in 2012.Along with the operation of some large scale liquid crystal panel production lines, inland of China panel production capacity will exceed China Taiwan in 2015, leap to the second in the world.A large amount of uses of LCD product become one of main source that is current and electron wastes in the future.
Current liquid crystal display is the glass substrate sealing utilizing epoxy resin two panels to be carved with indium electrode mostly, injects liquid crystal, then outside two pieces of glass substrates, overlays polaroid, thus the liquid crystal display device that formation one is complete.Therefore reclaim and to be with the key of the brilliant screen that disposes waste liquid how polaroid, glass substrate and the ito film three that is used for scribing indium electrode to be separated effectively.
Recovery for waste liquid crystal display screen has had relevant report, such as, after waste liquid crystal display panel breaks by the Qin Wenlong in Taiwan, inserts in sealed furnace and processes, be separated plated film oxide compound and sheet glass; Village's paddy profit of Japan is bright to be pulverized the useless LCD containing tin indium oxide, utilizes acid to be dissolved by tin indium oxide, adds displacement metal, indium is separated out; The scholar Kae-LongLin in Taiwan utilizes the glass waste of liquid-crystal display to replace potter's clay, produces ecological brick.
But adopt the rate of recovery of the separation method indium of the Qin Wenlong in Taiwan lower than 60%, the concentration ratio of indium concentrate is low, owing to adopting, pyrogenic process volatilizees, energy consumption is excessive, and production technique is uneconomical, cannot realize industrialization.
Village's bright separation method of paddy profit of Japan directly shields waste liquid crystal as indium raw materials for production, lack the enrichment process of leading portion, and the content of indium is only 300 ~ 600ug/g in waste liquid crystal screen, so directly acid-soluble result is exactly, indium yield is low, leach liquor indium concentration is low, production cost is too high, cannot realize industrialization.
The method that the scholar Kae-LongLin in Taiwan proposes utilizes the glass waste of indicating meter to replace potter's clay, and it is feasible for producing ecological brick, but does not design realistic plan for the recovery of indium, fails waste liquid crystal screen to realize comprehensive synthetical recovery.
Summary of the invention
Technical problem to be solved by this invention is the method for indium in synthetical recovery waste liquid crystal display screen while of proposing a kind of green separation technique.
The present invention includes following steps:
1) waste liquid crystal display screen is carried out cleaning, drying with water, obtain clean waste liquid crystal display screen;
2) at two outer sides of the waste liquid crystal display screen of cleaning, sucker is set respectively, by drawing sucker outward, waste liquid crystal display screen is separated, obtains the glass sheet of exposed liquid crystal surface;
3) carrying out mill to the liquid crystal surface of the glass sheet of exposed liquid crystal surface scrapes until after exposing glass coating, and the glass sheet after scraping with high pressure water washing mill, obtains the mixture be made up of liquid crystal, indium concentrate and water;
4) carry out roasting after the mixture be made up of liquid crystal, indium concentrate and water being removed portion of water, obtain indium concentrate; Again indium concentrate is obtained thick indium through leaching, extraction, aluminium row displacement.
The removals such as the dust that waste liquid crystal display screen surface can be pasted by step 1) by the present invention, obtain clean waste liquid crystal display screen, to make other impurity brought into without the need to consideration during subsequent disposal.
The present invention is by step 2) physical method by two sheet glass splits of compound, make liquid crystal surface wherein out exposed, so that following process.
Liquid crystal, ito film, a small amount of glass mill are scraped and are isolated glass basis from the sheet material of split by step 3) by the present invention successively, glass sheet again after high pressure water washing mill is scraped, liquid crystal, ito film and a small amount of glass and water mixing can be made, so that following process, the glass sheet after high pressure water washing mill is scraped then leaves the glass sheet that clean outer side has polaroid.
The present invention extracts more than the 4N high purity indium meeting " YS/T257-2009 " from the mixture be made up of liquid crystal, indium concentrate and water by step 4), particularly adopt the mode of roasting, due to liquid crystal because its main component is organism, at high temperature most of component is decomposed into innocuous gas, by directly discharging after drip washing, therefore the present invention adopts the mode of roasting, can liquid crystal in effective, innoxious ground decomposition of the mixture.In addition, the leached mud principal constituent obtained after leaching by indium concentrate is silicon, can be used as brick-making raw material.
To sum up, the method that present invention process adopts green physical sepn and hydrometallurgy to combine, production efficiency is high, each major parts of waste liquid crystal screen can be turned waste into wealth, resource regeneration rate is high, indium recovery is greater than 90%, whole process environmental protection, avoids the negative impact that acid or organic solvent because using nitric acid and acetone one class high volatility bring.
Further, in step 1) of the present invention, by described scavenging solution with 1.5 ~ 3kg/cm
2spray pressure flushing waste crystal display screen, the moisture after rinsing on waste aspiration crystal display screen, then the environment being placed in 70 ~ 80 DEG C is dried.This pressure flushable fall waste liquid crystal screen surfaces more than 90% dust, can not developing result be ensured lower than this pressure; Energy dissipation is caused higher than this pressure.Dry in 70 ~ 80 DEG C of environment and both ensure that drying effect, in turn ensure that waste liquid crystal screen can not be out of shape.Lower than this temperature, possible residuary water is too much, affects next procedure; Higher than this temperature, one is that energy consumption increases, and two is easily cause waste liquid crystal to shield distortion, and rear road stripping plate and nog plate operation cannot be carried out smoothly.
In described step 3), before mill is scraped, add water.Adding the wettable waste liquid crystal screen surfaces of water retting before polish-brush, one is the generation that can reduce dust when polish-brush like this, and two is that when can guarantee polish-brush, waste liquid crystal screen is ground rear temperature and raises limited, can not be out of shape in treating processes.
In described step 3), tNonwovens grinding roller is adopted to carry out polish-brush to the surface of waste liquid crystal panel glass.TNonwovens grinding roller is the nylon fiber with high-quality, abrasive material such as bonding corundum, silicon carbide etc., by nonwovens process, and the new grinding product having tridimensional network of formation.With three-dimensional tNonwovens nylon 66 fiber that is open and whippy structure be base cloth, abrasive material all should be adhered thereto, therefore there is workpiece surface of not burning, do not change workpiece size, durable, efficient, from sharp (anti-blocking), smooth finish high.TNonwovens can use under the environment of water, oil or other etching reagent, does not worry getting rusty as steel wire lump and the problem such as common sand paper drop.Consider the hardness that waste liquid crystal screen needs liquid crystal surface under polish-brush and ito film, and consider polish-brush lower glass substrate few as much as possible, consider to polaroid without polish-brush effect simultaneously, by theory deduction and experimental verification, select tNonwovens grinding roller to be optimal selection.
In described step 3), the spray pressure rinsing the high pressure water grinding the glass sheet after scraping is 10 ~ 15kg/cm
2.Owing to containing liquid crystal in the material under polish-brush, so there is certain viscosity, the glass baseplate surface after mill can be attached to, it must could be separated from glass substrate, through verification experimental verification lower than 10kg/cm by high pressure washing
2pressure, the material under polish-brush is difficult to flushing and gets off, more than 15kg/cm
2pressure, can energy dissipation be caused again; So select flushing pressure 10 ~ 15kg/cm
2both ensure that developing result reached requirement, considered energy-conservation needs again simultaneously.
Be greater than 10% in order to indium in indium concentrate is concentrated into content, in described step 4), the temperature of roasting is 400 ~ 500 DEG C.As maturing temperature decomposes not exclusively lower than 400 DEG C of liquid crystal, then cause energy dissipation higher than 500 DEG C; Material even can be caused to sinter if temperature continues to increase to over 700 ~ 800 DEG C, thus reduce the leaching yield of indium in later process.
In described step 4), for containing quality≤60% in the mixture of roasting.If water ratio is higher than 60%, greatly will increases the energy consumption of calcining process, increase the time of calcining process simultaneously; Or in specific time, roasting is incomplete, and liquid crystal decomposes not exclusively.
In described step 4), described leaching is: indium concentrate being impregnated in temperature is in the dilution heat of sulfuric acid of 85 ~ 95 DEG C, gets each solid phase respectively and pH is the liquid phase of 1 ~ 2 after dipping through cooling.As temperature is too low, leaching yield declines; As temperature is too high, one is that leaching yield increase is not obvious, and two is that energy consumption increases, and three is that acid gas volatilization increases, and environmental protection pressure becomes greatly.In reaction process as pH higher than 2 time, add dilute sulphuric acid on a small quantity.
In described step 4), dilute sulphuric acid concentration≤20% added, discontinuous adds, and initial reaction stage adds by reaction theory consumption, if use excessive concentrations sulfuric acid, then meeting very exothermic in adition process, solution causes solution to splash, and produces potential safety hazard.
In described step 4), needing the pH of the liquid phase after controlled cooling model to be 1 ~ 2, pH is 1 ~ 2, can ensure the leaching yield of indium, the conditional request of road extraction process after simultaneously ensureing; If pH is lower than 1, leaching yield increases limited, but leach liquor Free Acid increases, and also needs before extraction to add sheet alkali heightening pH value, adds cost consumption; If pH is higher than 2, leaching yield significantly reduces, and the rate of recovery of indium cannot ensure.
In the present invention, the extraction of indium can adopt maturation process, can guarantee that indium percentage extraction is greater than 99%, and ensures selectivity and the continuity optimum of extraction.
In described step 4), described aluminium row displacement is: first with pH to 2 ~ 2.5 of sodium hydroxide adjustment strip liquor, then in strip liquor, drop into aluminium, react indium concentration≤10ug/ml to liquid phase, from aluminium, row obtains thick indium.If pH value is lower than 2, acid unnecessary in solution can increase the consumption of aluminium row, produces waste; If pH is higher than 2.5, indium may be hydrolyzed to indium hydroxide in the solution, and replacement(metathesis)reaction cannot be proceeded.Reaction is the reaction end as displacement to indium concentration≤10ug/ml in liquid phase, and at this moment residual in solution indium amount is very low, can give up.
In order to make the higher indium product of purity, also thick indium can be passed through the electrolytic refining process as maturations such as electrolysis, by indium and other magazins' layout.
Embodiment
One, recovery process step:
1, pump is washed, blots, is dried: use from the beginning, rinsed, spray pressure 1.5-3Kg/cm by water pump to waste liquid crystal display screen
2, water can be recycled, as water shortage, and irregular moisturizing; Absorb most of moisture with sponge contact liquid crystal screen surfaces subsequently, by mechanical presses water outlet after using, water returns pump and washes use; Finally adopt 70 ~ 80 DEG C of hot air circulation to purge liquid crystal display surface, thoroughly remove the moisture on liquid crystal display surface.
2, delaminate: pump is washed, blot, dry after liquid crystal display upper and lower surface use after sucker sucks, lower sucker maintains static, and upper sucker upwards moves in parallel, thus is peeled off by liquid crystal display, forms upper and lower two panels half screen, sucker air pressure 8-12kg/cm
2.
3, soak: by the top and bottom two panels half screen after stripping by being sent to immersion water tank, screen is infiltrated.Soak and use ordinary tap water, water can Reusability, irregularly adds during deficiency.
4, mill screen: first use tNonwovens grinding roller to carry out polish-brush to the liquid crystal surface of the glass sheet of exposed liquid crystal surface two half screens be up and down separated, until expose glass coating, thus liquid crystal, ito film are separated with glass substrate.
5, height compresses and washes, blots, dries: first use water pump pump water to rinse two the half screen high pressure pressures up and down after polish-brush, rush the material be separated from screen to circulating water channel, spray pressure 10-15kg/cm
2, water cycle uses, as water shortage, and irregular moisturizing; Absorb most of moisture with sponge contact liquid crystal screen surfaces subsequently, by mechanical presses water outlet after using, water returns pump and washes use, finally focuses on.
6, solid-liquid separation: height is compressed and washed punching to the material of circulating water channel and carry out solid-liquid separation, adopt centrifugation or press filtration be separated all can, the water of separation returns height and compresses and washes use, and the water content of the liquid crystal obtained and indium concentrate mixture is less than 60%.
7, roasting: the mixture of liquid crystal and indium concentrate is put into stoving oven Roasting Decomposition, and first the moisture in heat-processed in material volatilized, liquid crystal because of its principal constituent be machine thing, under high temperature, most of component can be decomposed into innocuous gas, discharges through drip washing; Indium concentrate is obtained after calcining process completes.
Roasting technology condition: stoving oven 400-500 DEG C of constant temperature 4-6 hour, in the indium concentrate obtained after roasting, indium content is greater than 10%.
8, leach: put into by indium concentrate and leach pond, add that temperature is 85-95 DEG C, concentration is the dilute sulfuric acid aqueous solution of 18%, leachings solid-to-liquid ratio is 1:3, controlling leaching terminal pH is 1-2, extraction time 4-5 hour.It is to be extracted that the rear solid-liquid separation of cooling obtains leach liquor; Leached mud principal constituent is silicon, can be used as brick-making raw material.
9, extract: use the P204(di-(2-ethylhexyl)phosphoric acid ester after kerosene cutback) be indium extraction agent, be that the kerosene of 7:3 and P204 mix and form by volume ratio, in batch-type extraction tank, adopt intermittent type secondary to extract mode extract, the volume ratio of oil phase and aqueous phase is 1:2-2.5, extraction mixing-time 3 minutes; Wash the dilution heat of sulfuric acid of acid for pH:1-1.5, after washing acid, liquid and the remaining liquid of extraction return leaching operation, and acidity can not added the vitriol oil completely and improve acidity; Back extraction adopts the hydrochloric acid of 6-8mol/l as reverse-extraction agent, and the volume ratio of oil phase and aqueous phase is 5:1, back extraction reaction times 10-20 minute, the back extraction of intermittent type secondary; Strip liquor Reusability, when in strip liquor, indium concentration draws extracting system after reaching 40-80g/l, enters displacement operation, separately reconfigures new strip liquor and enters back extraction operation.
10, aluminium row displacement: first with pH to 2 ~ 2.5 of sodium hydroxide adjustment strip liquor, then drop into aluminium in strip liquor, indium concentration≤10ug/mL in replacement(metathesis)reaction to liquid phase, row obtains thick indium from aluminium.
11, electrorefining: adopt the classical electrolysis process that indium is purified, namely configure indium sulfate solution as electrolytic solution, composition is indium: 70 ~ 80g/L, and pH value is 1.5 ~ 2.5, sodium-chlor 70 ~ 100g/l; Using thick indium as anode, using titanium plate as negative electrode; Groove pressure is less than 150mv, current density 20 ~ 25A/m
2.The electrorefining turnover groove cycle is 7 days, and control flume voltage is less than 150mv.
12, casting packaging: the conditions such as casting packaging need to determine according to client.
Two, the product 4N high purity indium reclaimed meets the requirement specified in " YS/T257-2009 " standard.
Claims (10)
1. the method for recovery indium from waste liquid crystal display screen, is characterized in that comprising the following steps:
1) waste liquid crystal display screen is carried out cleaning, drying with water, obtain clean waste liquid crystal display screen;
2) at two outer sides of the waste liquid crystal display screen of cleaning, sucker is set respectively, by drawing sucker outward, waste liquid crystal display screen is separated, obtains the glass sheet of exposed liquid crystal surface;
3) carrying out mill to the liquid crystal surface of the glass sheet of exposed liquid crystal surface scrapes until after exposing glass coating, and the glass sheet after scraping with high pressure water washing mill, obtains the mixture be made up of liquid crystal, indium concentrate and water;
4) carry out roasting after the mixture be made up of liquid crystal, indium concentrate and water being removed portion of water, obtain indium concentrate; Again indium concentrate is obtained thick indium through leaching, extraction, aluminium row displacement.
2. method according to claim 1, is characterized in that in described step 1), by described water with 1.5 ~ 3kg/cm
2spray pressure flushing waste crystal display screen, the moisture after rinsing on waste aspiration crystal display screen, then the environment being placed in 70 ~ 80 DEG C is dried.
3. method according to claim 1 or 2, is characterized in that, in described step 3), before mill is scraped, adding water.
4. method according to claim 1, is characterized in that in described step 3), adopts tNonwovens grinding roller to carry out polish-brush to the surface of waste liquid crystal panel glass.
5. method according to claim 1, is characterized in that in described step 3), rinse mill scrape after the spray pressure of high pressure water of glass sheet be 10 ~ 15kg/cm
2.
6. method according to claim 1, is characterized in that in described step 4), in the mixture of roasting containing quality≤60%, the temperature of roasting is 400 ~ 500 DEG C.
7. method according to claim 1 or 6, is characterized in that, in described step 4), described leaching is: indium concentrate being impregnated in temperature is in the dilution heat of sulfuric acid of 85 ~ 95 DEG C, gets each solid phase respectively and pH is the liquid phase of 1 ~ 2 after dipping through cooling.
8. method according to claim 7, it is characterized in that in described step 4), the dilute sulphuric acid for leaching is the aqueous sulfuric acid of mass percent≤20%.
9. method according to claim 1, it is characterized in that in described step 4), described aluminium row displacement is: first with pH to 2 ~ 2.5 of sodium hydroxide adjustment strip liquor, then in strip liquor, drop into aluminium, reaction is to indium concentration≤10ug/mL in liquid phase, and from aluminium, row obtains thick indium.
10. method according to claim 1, is characterized in that, by thick indium electrorefining after step 4), obtain high purity indium.
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| CN106119550A (en) * | 2016-07-29 | 2016-11-16 | 上海交通大学 | The recovery method of indium in a kind of waste liquid crystal panel mechanical stripping product |
| CN106734107A (en) * | 2017-01-04 | 2017-05-31 | 长沙汇聚环境技术有限公司 | A kind of its recovery method as resource of waste liquid crystal display screen panel glass |
| CN107130112A (en) * | 2017-05-20 | 2017-09-05 | 合肥市惠科精密模具有限公司 | A kind of method of recovery indium in crystal display screen from waste liquid |
| WO2018072547A1 (en) * | 2016-10-17 | 2018-04-26 | 扬州宁达贵金属有限公司 | Method of recovering indium from liquid crystal-containing indium concentrate |
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| CN106119550A (en) * | 2016-07-29 | 2016-11-16 | 上海交通大学 | The recovery method of indium in a kind of waste liquid crystal panel mechanical stripping product |
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| CN107130112A (en) * | 2017-05-20 | 2017-09-05 | 合肥市惠科精密模具有限公司 | A kind of method of recovery indium in crystal display screen from waste liquid |
| CN109082527A (en) * | 2018-07-17 | 2018-12-25 | 成都中建材光电材料有限公司 | A kind of abrasion recovery and treatment method of cadmium telluride diaphragm solar battery |
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Address after: 225000 Industrial Park, Yiling Town, Jiangdu District, Yangzhou City, Jiangsu Province Patentee after: Jiangsu Ningda environmental protection Co.,Ltd. Address before: 225231 No.1 Road, industrial park, Yiling Town, Jiangdu District, Yangzhou City, Jiangsu Province Patentee before: YANGZHOU NINGDA NOBLE METAL Co.,Ltd. |
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Denomination of invention: A method for recovering indium from waste LCD screens Granted publication date: 20200107 Pledgee: Yangzhou Branch of Zheshang Bank Co.,Ltd. Pledgor: Jiangsu Ningda environmental protection Co.,Ltd. Registration number: Y2024980009363 |