CN104071820B - A kind of method that calcirm-fluoride is produced by the LCD glass etching liquid that gives up - Google Patents
A kind of method that calcirm-fluoride is produced by the LCD glass etching liquid that gives up Download PDFInfo
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Abstract
The present invention relates to a kind of method for producing calcirm-fluoride by the LCD glass etching liquid that gives up, in turn include the following steps：Take a certain amount of useless LCD glass etching liquid, add sodium fluoride solid, it is sufficiently stirred for making the hexafluorosilicic acid in waste liquid to react generation sodium hexafluorisilicate and hydrofluoric acid completely with sodium fluoride, hexafluoro aluminic acid is set to react generation hexafluoro sodium aluminate and hydrofluoric acid completely with sodium fluoride, it is subsequently adding ammoniacal liquor, reaction generation silica, sodium fluoride and ammonium acid fluoride, hexafluoro sodium aluminate and remaining sodium hexafluorisilicate is set to settle rapidly, refilter sediment, take supernatant add calcium hydroxide suspension in, stop to pH=5, calcium hydroxide is set to generate calcirm-fluoride with hydrofluoric acid reaction completely, add calcium hydroxide suspension, make sodium fluoride, ammonium acid fluoride generates calcirm-fluoride with calcium hydroxide reaction respectively, it is subsequently adding polyacrylamide solution, precipitation, filter and clean, finally carry out drying obtaining calcirm-fluoride solid.Calcirm-fluoride purity is up to more than 95%.
Description
Technical field
It is more particularly to a kind of by useless LCD glass etching liquid the present invention relates to a kind of processing method of glass etching liquid
The method for producing calcirm-fluoride.
Background technology
Reduction processing is etched to glass using hydrofluoric acid in general glass thinning operation, is produced during glass etching
The processing mode of raw useless solid and waste liquid is substantially all to be reclaimed by the qualified third-party institution, is processed after recovery,
Landfill stabilization after high-temperature calcination is disposed or carried out to sludge using land-fill method, and supernatant returns Industrial sewage treatment system and located again
Reason.
Fluorine-containing wastewater treatment method common at present is that calcic medicament is first dissolved into liquid, then in mechanical agitation
Under be added in waste water, make fluorine ion in waste water react to form water-insoluble calcirm-fluoride suspended particulate with calcium ion, it is then quiet
Layering is put, upper clear supernate outflow, bottom sludge is delivered to press filteration system and carries out press filtration treatment.Also have using calcium salt, alkali lye and wadding
Solidifying agent mixed system carries out the treatment of hydrofluoric acid.
The application for a patent for invention of Publication No. CN 1504419 discloses a kind of " hydrofluoric acid wastewater treatment method and device ",
The steam condensation procedure being concentrated by evaporation after operation, HF steam dissolving water conservancy project sequence, alkali neutralization step and de- HF using hydrofluoric acid is carried out
Hydrofluoric acid treatment scheme.
The application for a patent for invention of Publication No. CN 1559931 discloses a kind of " processing system and method for hydrofluoric acid ", adopts
Discarded object of the method for secondary calcium salt treatment hydrofluoric acid to produce the waste liquid that can be discharged He can bury is carried out with two treatment troughs.
The above method may be effective when low concentration or a small amount of hydrofluoric acid waste liquid is processed, but to a large amount of high concentration of hydrofluoric acid
Treatment then shows not economical and practical enough.
In terms of the treatment of high concentration of hydrofluoric acid, the application for a patent for invention of Publication No. CN 202072566U discloses one
" a kind of Waste Water Treatment containing high concentration of hydrofluoric acid " is planted, for processing passivation for stainless steel pickling, photovoltaic new energy etc.
The cleaning system containing high concentration of hydrofluoric acid waste water produced during industry production, is provided with air mixing in integrated reacting equipment
Device and without mechanical agitation, integrated reacting its upper side be provided with stretch into pH detection means inside consersion unit, fluorine from
Sub- detection means and white lime, calcium chloride, coagulant delivery device, delivery port is provided with integrated reacting device bottom, is gone out
The mouth of a river connects filter-pressing device by the boosted pump of pipeline.The system is added using direct siccative, saves medicament dissolution, transfer rings
Section, reducing energy consumption, and adding of agent pipeline blockage problem can be fully solved.But the system still suffers from following deficiency：1. at spent acid
The calcirm-fluoride purity for managing generation is low, generally only as the treatment of general waste reclamation, it is impossible to as resource reutilization, cause fluorine resource
Huge waste；2. direct siccative adds the slow caused peritectic reaction of the course of dissolution because precipitation reaction is fast and can cause to do
Material excessive input and produce waste, greatly increase raw material dosage and production cost.
The content of the invention
It is an object of the present invention to overcome problems of the prior art, there is provided a kind of by useless LCD glass etching
The method that liquid produces calcirm-fluoride, can be obtained the calcirm-fluoride of high-purity, used as flux and the production hydrofluoric acid of metal smelt
Raw material, is comprehensively utilized non-renewable fluorine-containing resource.
It is solution above technical problem, a kind of method that calcirm-fluoride is produced by the LCD glass etching liquid that gives up of the invention,
In turn include the following steps：(1) a certain amount of useless LCD glass etching liquid is taken, hydrogen in useless LCD glass etching liquid is determined
The content of fluoric acid, hexafluorosilicic acid and hexafluoro aluminic acid；(2) to addition sodium fluoride solid, weight ratio in useless LCD glass etching liquid
It is useless LCD glass etching liquid：Sodium fluoride=1:（0.2~0.25）, it is sufficiently stirred for hexafluorosilicic acid is reacted completely with sodium fluoride
Generation sodium hexafluorisilicate and hydrofluoric acid, make hexafluoro aluminic acid react generation hexafluoro sodium aluminate and hydrofluoric acid, reaction completely with sodium fluoride
At 15 DEG C~55 DEG C, the reaction time, at 0.5 hour~4 hours, obtains the mixed liquor A of colloidal to temperature control after reaction；To
Ammoniacal liquor is added in mixed liquor A, weight ratio is mixed liquor A ︰ ammoniacal liquor=1 ︰（0.08~0.10）, reaction temperature control is 10 DEG C~50
DEG C, the reaction time was at 0.5~2 hour；Part sodium hexafluorisilicate and hydrofluoric acid reaction generation two in the ammoniacal liquor and mixed liquor A
Silica, sodium fluoride and ammonium acid fluoride；The silica adjusts colloidal electric charge, accelerates hexafluoro sodium aluminate and remaining hexafluoro silicon
The molecule of sour sodium is reunited, and hexafluoro sodium aluminate and remaining sodium hexafluorisilicate is settled rapidly, obtains mixed liquid B；(4) by mixed liquid B
0.5~1 hour is stood, filtering precipitate removes filter cake, and filtrate is back in sedimentation supernatant, obtains solution C；(5) weight is prepared
Amount content is 30% two parts of calcium hydroxide suspension；(6) solution C is added into above-mentioned calcium hydroxide suspension under agitation
In, temperature control stops plus solution C at 30 DEG C~65 DEG C to pH=5, continues to stir and react 0.5~2 hour, makes calcium hydroxide
Calcirm-fluoride is generated with the hydrofluoric acid reaction in solution C completely, mixed liquor D is obtained；(7) added in mixed liquor D under agitation
Step calcium hydroxide suspension (5), fluorinion concentration is determined when adding, until fluorinion concentration stops when being less than 20mg/L
Add calcium hydroxide suspension, be further continued for reaction 0.5 hour, sodium fluoride, ammonium acid fluoride in mixed liquor D respectively with calcium hydroxide
Reaction generation calcirm-fluoride, obtains mixed liquor E；(8) to the polyacrylamide that addition weight content in mixed liquor E is 0.05%~0.2%
Solution, the weight ratio that adds of polyacrylamide solution is mixed liquor D ︰ polyacrylamide solution=1 ︰（0.005~0.015）, slowly
Stirring 10~30 seconds；(9) the mixed liquor standing sedimentation 0.5~1 hour by step (8), bottom sediment is filtered and filter cake is cleaned,
Finally carry out drying obtaining calcirm-fluoride solid.
Relative to prior art, the present invention achieves following beneficial effect：(1) the useless LCD glass erosion after glass thinning
Carve liquid in contain high-concentration waste hydrofluoric acid, also containing more hexafluorosilicic acid and hexafluoro aluminic acid impurity, if being directly added into hydrogen-oxygen
Change Calcium treatment, in sediment in addition to containing calcirm-fluoride, also containing the impurity such as more hexafluorosilicic acid calcium and hexafluoro calcium aluminate, so that
The purity and use value of major product calcirm-fluoride can be reduced；(2) the present invention is first to addition fluorination in useless LCD glass etching liquid
Sodium solid makes hexafluorosilicic acid react generation sodium hexafluorisilicate and hydrofluoric acid completely with sodium fluoride, makes hexafluoro aluminic acid complete with sodium fluoride
Reaction generation hexafluoro sodium aluminate and hydrofluoric acid, H2SiF6 +2NaF→Na2SiF6↓+2HF；2H3AlF6+6NaF →2Na3AlF6 ↓+
6HF；Because sodium hexafluorisilicate and hexafluoro sodium aluminate are sediment, through this reaction can first by the hexafluorosilicic acid in useless hydrofluoric acid and
Hexafluoro aluminic acid impurity is removed；Than relatively low, molecular weight is small, and reaction product contains hydrofluoric acid for sodium fluoride price, improves former useless
Hydrofluoric acid concentration in acid, is conducive to improving purity when calcirm-fluoride is prepared.(3) because sodium hexafluorisilicate and hexafluoro sodium aluminate are heavy
Shallow lake speed is relatively slow and is difficult to precipitate completely, adds insufficient amount of ammoniacal liquor, because the activity of sodium hexafluorisilicate is stronger than hexafluoro sodium aluminate,
In the case of ammoniacal liquor is insufficient amount of, ammoniacal liquor preferentially reacts with sodium hexafluorisilicate；Sodium hexafluorisilicate reaction about with 10%,
Na2SiF6+ 4HF + 4NH4OH → SiO2 + 2NaF + 4NH4HF2 + 2H2O, the silica regulation colloid electricity of generation
Lotus, accelerates hexafluoro sodium aluminate and remaining sodium hexafluorisilicate precipitation, using going the removal of impurity rapidly；(4) after removing impurity, in solution C
The hydrofluoric acid and a small amount of sodium fluoride, ammonium acid fluoride of high concentration are mainly contained, is first added into calcium hydroxide suspension to pH=5
Stop, it is ensured that the complete generation calcirm-fluoride of calcium hydroxide reaction, 2HF+Ca (OH)2 →CaF2↓+ H2O, remains a small amount of hydrofluoric acid；Again
When adding calcium hydroxide suspension to fluorinion concentration to be less than 20mg/L, make remaining hydrofluoric acid fundamental reaction complete, and sodium fluoride,
Ammonium acid fluoride further generates calcirm-fluoride, 2NaF+ Ca (OH) with calcium hydroxide reaction respectively2→2NaOH+ CaF2↓；NH4HF2+
Ca(OH)2 → CaF2↓+ NH4OH + H2O, improves the growing amount of calcirm-fluoride, and the method is whole beneficial to accurately reaction is grasped
Point, reduces the material residual in addition to major product.(5) flocculant polyacrylamide solution is subsequently added into, calcirm-fluoride is reunited rapidly
Sedimentation, cleans after being filtrated to get filter cake, washes away NaOH, NH4OH etc., then dry and obtain calcirm-fluoride solid, use GB/T
The content that 5195.1-2006 methods determine calcirm-fluoride can reach more than 95%.(6) the calcirm-fluoride of such high-purity, can be as gold
Belong to the raw material of the flux and production hydrofluoric acid smelted, be comprehensively utilized non-renewable fluorine-containing resource.
The step (1) in, it is 16.5%~18.5%, the hexafluoro silicon that the hydrofluoric acid accounts for the percentage by weight of etching solution
The percentage by weight that acid accounts for etching solution is 20%~22%, and the percentage by weight that the hexafluoro aluminic acid accounts for etching solution is 8%~9%.Glass
The content of the above-mentioned each material of useless LCD glass etching liquid after glass is thinning is within this range.
The step (3) in, the NH in the ammoniacal liquor3Weight content be 27%.
The step (5) in, the granularity of calcium hydroxide is 23 microns~45 microns.It is easy to reaction, improves reaction speed.
The step (8) in, the polyacrylamide be non-ionic or anionic, molecular weight be 3,000,000~2000
Ten thousand.
Specific embodiment
Embodiment one
The method for producing calcirm-fluoride by the LCD glass etching liquid that gives up of the invention, in turn includes the following steps：
(1) a certain amount of useless LCD glass etching liquid, determines hydrofluoric acid, hexafluoro silicon in useless LCD glass etching liquid
Acid and the content of hexafluoro aluminic acid, the percentage by weight that the hydrofluoric acid accounts for etching solution is 16.5%, and the hexafluorosilicic acid accounts for etching solution
Percentage by weight be 20%, the hexafluoro aluminic acid account for etching solution percentage by weight be 8%.
(2), to sodium fluoride solid is added in useless LCD glass etching liquid, weight ratio is useless LCD glass etching liquid：
Sodium fluoride=1:0.2, it is sufficiently stirred for hexafluorosilicic acid is reacted generation sodium hexafluorisilicate and hydrofluoric acid, H completely with sodium fluoride2SiF6 +
2NaF→Na2SiF6↓+2HF；Hexafluoro aluminic acid is set to react generation hexafluoro sodium aluminate and hydrofluoric acid, 2H completely with sodium fluoride3AlF6 +
6NaF→2Na3AlF6 ↓+6HF；At 15 DEG C, the reaction time, at 0.5 hour, obtains the mixed of colloidal after reaction for reaction temperature control
Close liquid A.
(3) to adding ammoniacal liquor, the NH in the ammoniacal liquor in mixed liquor A3Weight content be 27%, weight ratio be mixed liquor A ︰
Ammoniacal liquor=1 ︰ 0.08, reaction temperature is controlled at 10 DEG C, and the reaction time was at 0.5 hour；Because sodium hexafluorisilicate and hexafluoro sodium aluminate are heavy
Shallow lake speed is relatively slow and is difficult to precipitate completely, adds insufficient amount of ammoniacal liquor, because the activity of sodium hexafluorisilicate is stronger than hexafluoro sodium aluminate,
In the case of ammoniacal liquor is insufficient amount of, ammoniacal liquor preferentially reacts with part sodium hexafluorisilicate, the part hexafluoro silicon in ammoniacal liquor and mixed liquor A
Sour sodium and hydrofluoric acid reaction generation silica, sodium fluoride and ammonium acid fluoride, Na2SiF6+ 4HF + 4NH4OH → SiO2 +
2NaF + 4NH4HF2 + 2H2O；The silica adjusts colloidal electric charge, accelerates hexafluoro sodium aluminate and remaining hexafluorosilicic acid
The molecule of sodium is reunited, and hexafluoro sodium aluminate and remaining sodium hexafluorisilicate is settled rapidly, obtains mixed liquid B.
(4) mixed liquid B is stood 0.5 hour, filtering precipitate removes filter cake, and filtrate is back in sedimentation supernatant, obtains
To solution C, after removing impurity, the hydrofluoric acid and a small amount of sodium fluoride, ammonium acid fluoride of high concentration are mainly contained in solution C.
(5) two parts of the calcium hydroxide suspension that weight content is 30% is prepared, and the granularity of calcium hydroxide is 23 microns.
(6) in solution C being added into above-mentioned calcium hydroxide suspension under agitation, temperature control is stopped at 30 DEG C to pH=5
Only plus solution C, continue to stir and react 0.5 hour, make calcium hydroxide completely with solution C in hydrofluoric acid reaction generation fluorination
Calcium, 2HF+Ca (OH)2 →CaF2↓+ H2O, remains a small amount of hydrofluoric acid, obtains mixed liquor D.
(7) under agitation to step calcium hydroxide suspension (5) is added in mixed liquor D, determined when adding fluorine from
Sub- concentration, until stopping adding calcium hydroxide suspension when fluorinion concentration is 18mg/L, is further continued for reaction 0.5 hour, makes to remain
Remaining hydrofluoric acid fundamental reaction is complete, and sodium fluoride, ammonium acid fluoride in mixed liquor D generate with calcium hydroxide reaction be fluorinated respectively
Calcium, 2NaF+ Ca (OH)2→2NaOH+ CaF2↓； NH4HF2+ Ca(OH)2 → CaF2↓+ NH4OH + H2O, obtains mixed liquor
E。
To in mixed liquor E add weight content be 0.05% polyacrylamide solution, the polyacrylamide for it is non-from
Subtype or anionic, molecular weight are 3,000,000, and the weight ratio that adds of polyacrylamide solution is that mixed liquor D ︰ polyacrylamides are molten
Liquid=1 ︰ 0.005, is slowly stirred 10 seconds.
(9) the mixed liquor standing sedimentation 0.5 hour by step (8), bottom sediment is filtered and filter cake is cleaned, and washes away NaOH
、NH4OH etc., is finally carried out drying obtaining calcirm-fluoride solid, and the content of calcirm-fluoride is determined using GB/T 5195.1-2006 methods
Reach 95.6%.
Embodiment two
The method for producing calcirm-fluoride by the LCD glass etching liquid that gives up of the invention, in turn includes the following steps：
(1) a certain amount of useless LCD glass etching liquid, determines hydrofluoric acid, hexafluoro silicon in useless LCD glass etching liquid
Acid and the content of hexafluoro aluminic acid, the percentage by weight that the hydrofluoric acid accounts for etching solution is 17.6%, and the hexafluorosilicic acid accounts for etching solution
Percentage by weight be 21%, the hexafluoro aluminic acid account for etching solution percentage by weight be 8.4%.
(2), to sodium fluoride solid is added in useless LCD glass etching liquid, weight ratio is useless LCD glass etching liquid：
Sodium fluoride=1:0.22, it is sufficiently stirred for hexafluorosilicic acid is reacted generation sodium hexafluorisilicate and hydrofluoric acid, H completely with sodium fluoride2SiF6
+2NaF→Na2SiF6↓+2HF；Hexafluoro aluminic acid is set to react generation hexafluoro sodium aluminate and hydrofluoric acid, 2H completely with sodium fluoride3AlF6 +
6NaF→2Na3AlF6 ↓+6HF；Reaction temperature is controlled at 35 DEG C, and the reaction time, at 2 hours, obtains the mixing of colloidal after reaction
Liquid A.
(3) to adding ammoniacal liquor, the NH in the ammoniacal liquor in mixed liquor A3Weight content be 27%, weight ratio be mixed liquor A ︰
Ammoniacal liquor=1 ︰ 0.09, reaction temperature is controlled at 30 DEG C, and the reaction time was at 1 hour；Because sodium hexafluorisilicate and hexafluoro sodium aluminate are precipitated
Speed is relatively slow and is difficult to precipitate completely, adds insufficient amount of ammoniacal liquor, because the activity of sodium hexafluorisilicate is stronger than hexafluoro sodium aluminate,
In the case of ammoniacal liquor is insufficient amount of, ammoniacal liquor preferentially reacts with part sodium hexafluorisilicate, the part hexafluorosilicic acid in ammoniacal liquor and mixed liquor A
Sodium and hydrofluoric acid reaction generation silica, sodium fluoride and ammonium acid fluoride, Na2SiF6+ 4HF + 4NH4OH → SiO2 +
2NaF + 4NH4HF2 + 2H2O；The silica adjusts colloidal electric charge, accelerates hexafluoro sodium aluminate and remaining hexafluorosilicic acid
The molecule of sodium is reunited, and hexafluoro sodium aluminate and remaining sodium hexafluorisilicate is settled rapidly, obtains mixed liquid B.
(4) mixed liquid B is stood 0.8 hour, filtering precipitate removes filter cake, and filtrate is back in sedimentation supernatant, obtains
To solution C, after removing impurity, the hydrofluoric acid and a small amount of sodium fluoride, ammonium acid fluoride of high concentration are mainly contained in solution C.
(5) two parts of the calcium hydroxide suspension that weight content is 30% is prepared, and the granularity of calcium hydroxide is 35 microns.
(6) in solution C being added into above-mentioned calcium hydroxide suspension under agitation, temperature control is stopped at 45 DEG C to pH=5
Only plus solution C, continue to stir and react 1 hour, make calcium hydroxide completely with solution C in hydrofluoric acid reaction generation calcirm-fluoride,
2HF + Ca(OH)2 →CaF2↓+ H2O, remains a small amount of hydrofluoric acid, obtains mixed liquor D.
(7) under agitation to step calcium hydroxide suspension (5) is added in mixed liquor D, determined when adding fluorine from
Sub- concentration, until stopping adding calcium hydroxide suspension when fluorinion concentration is 19mg/L, is further continued for reaction 0.5 hour, makes to remain
Remaining hydrofluoric acid fundamental reaction is complete, and sodium fluoride, ammonium acid fluoride in mixed liquor D generate with calcium hydroxide reaction be fluorinated respectively
Calcium, 2NaF+ Ca (OH)2→2NaOH+ CaF2↓； NH4HF2+ Ca(OH)2 → CaF2↓+ NH4OH + H2O, obtains mixed liquor
E。
To in mixed liquor E add weight content be 0.1% polyacrylamide solution, the polyacrylamide for it is non-from
Subtype or anionic, molecular weight are 3,000,000~20,000,000, and the weight ratio that adds of polyacrylamide solution is mixed liquor D ︰ poly- third
Acrylamide solution=1 ︰ 0.01, is slowly stirred 20 seconds.
(9) the mixed liquor standing sedimentation 0.8 hour by step (8), bottom sediment is filtered and filter cake is cleaned, and washes away NaOH
、NH4OH etc., is finally carried out drying obtaining calcirm-fluoride solid, and the content of calcirm-fluoride is determined using GB/T 5195.1-2006 methods
Reach 95.8%.
Embodiment three
The method for producing calcirm-fluoride by the LCD glass etching liquid that gives up of the invention, in turn includes the following steps：
(1) a certain amount of useless LCD glass etching liquid, determines hydrofluoric acid, hexafluoro silicon in useless LCD glass etching liquid
Acid and the content of hexafluoro aluminic acid, the percentage by weight that the hydrofluoric acid accounts for etching solution is 18.5%, and the hexafluorosilicic acid accounts for etching solution
Percentage by weight be 22%, the hexafluoro aluminic acid account for etching solution percentage by weight be 9%.
(2), to sodium fluoride solid is added in useless LCD glass etching liquid, weight ratio is useless LCD glass etching liquid：
Sodium fluoride=1:0.25, it is sufficiently stirred for hexafluorosilicic acid is reacted generation sodium hexafluorisilicate and hydrofluoric acid completely with sodium fluoride,
H2SiF6 +2NaF→Na2SiF6↓+2HF；Hexafluoro aluminic acid is set to react generation hexafluoro sodium aluminate and hydrofluoric acid completely with sodium fluoride,
2H3AlF6 +6NaF→2Na3AlF6 ↓+6HF；Reaction temperature is controlled at 55 DEG C, and the reaction time, at 4 hours, obtains colloid after reaction
The mixed liquor A of shape.
(3) to adding ammoniacal liquor, the NH in the ammoniacal liquor in mixed liquor A3Weight content be 27%, weight ratio be mixed liquor A ︰
Ammoniacal liquor=1 ︰ 0.10, reaction temperature is controlled at 50 DEG C, and the reaction time was at 2 hours；Because sodium hexafluorisilicate and hexafluoro sodium aluminate are precipitated
Speed is relatively slow and is difficult to precipitate completely, adds insufficient amount of ammoniacal liquor, because the activity of sodium hexafluorisilicate is stronger than hexafluoro sodium aluminate,
In the case of ammoniacal liquor is insufficient amount of, ammoniacal liquor preferentially reacts with part sodium hexafluorisilicate, the part hexafluorosilicic acid in ammoniacal liquor and mixed liquor A
Sodium and hydrofluoric acid reaction generation silica, sodium fluoride and ammonium acid fluoride, Na2SiF6+ 4HF + 4NH4OH → SiO2 +
2NaF + 4NH4HF2 + 2H2O；The silica adjusts colloidal electric charge, accelerates hexafluoro sodium aluminate and remaining hexafluorosilicic acid
The molecule of sodium is reunited, and hexafluoro sodium aluminate and remaining sodium hexafluorisilicate is settled rapidly, obtains mixed liquid B.
(4) mixed liquid B is stood 1 hour, filtering precipitate removes filter cake, and filtrate is back in sedimentation supernatant, obtains
Solution C, after removing impurity, mainly contains the hydrofluoric acid and a small amount of sodium fluoride, ammonium acid fluoride of high concentration in solution C.
(5) two parts of the calcium hydroxide suspension that weight content is 30% is prepared, and the granularity of calcium hydroxide is 45 microns.
(6) in solution C being added into above-mentioned calcium hydroxide suspension under agitation, temperature control is stopped at 65 DEG C to pH=5
Only plus solution C, continue to stir and react 2 hours, make calcium hydroxide completely with solution C in hydrofluoric acid reaction generation calcirm-fluoride,
2HF + Ca(OH)2 →CaF2↓+ H2O, remains a small amount of hydrofluoric acid, obtains mixed liquor D.
(7) under agitation to step calcium hydroxide suspension (5) is added in mixed liquor D, determined when adding fluorine from
Sub- concentration, until stopping adding calcium hydroxide suspension when fluorinion concentration is 20mg/L, is further continued for reaction 0.5 hour, makes to remain
Remaining hydrofluoric acid fundamental reaction is complete, and sodium fluoride, ammonium acid fluoride in mixed liquor D generate with calcium hydroxide reaction be fluorinated respectively
Calcium, 2NaF+ Ca (OH)2→2NaOH+ CaF2↓； NH4HF2+ Ca(OH)2 → CaF2↓+ NH4OH + H2O, obtains mixed liquor
E。
To in mixed liquor E add weight content be 0.2% polyacrylamide solution, the polyacrylamide for it is non-from
Subtype or anionic, molecular weight are 20,000,000, and the weight ratio that adds of polyacrylamide solution is mixed liquor D ︰ polyacrylamides
Solution=1 ︰ 0.015, is slowly stirred 30 seconds.
(9) the mixed liquor standing sedimentation 1 hour by step (8), bottom sediment is filtered and filter cake is cleaned, wash away NaOH,
NH4OH etc., finally carries out drying obtaining calcirm-fluoride solid, and the content for determining calcirm-fluoride using GB/T 5195.1-2006 methods reaches
To 96.1%.
Example IV
The method for producing calcirm-fluoride by the LCD glass etching liquid that gives up of the invention, in turn includes the following steps：
(1) a certain amount of useless LCD glass etching liquid, determines hydrofluoric acid, hexafluoro silicon in useless LCD glass etching liquid
Acid and the content of hexafluoro aluminic acid, the percentage by weight that the hydrofluoric acid accounts for etching solution is 17.5%, and the hexafluorosilicic acid accounts for etching solution
Percentage by weight be 21%, the hexafluoro aluminic acid account for etching solution percentage by weight be 8.6%.
(2), to sodium fluoride solid is added in useless LCD glass etching liquid, weight ratio is useless LCD glass etching liquid：
Sodium fluoride=1:0.2, it is sufficiently stirred for hexafluorosilicic acid is reacted generation sodium hexafluorisilicate and hydrofluoric acid, H completely with sodium fluoride2SiF6 +
2NaF→Na2SiF6↓+2HF；Hexafluoro aluminic acid is set to react generation hexafluoro sodium aluminate and hydrofluoric acid, 2H completely with sodium fluoride3AlF6 +
6NaF→2Na3AlF6 ↓+6HF；Reaction temperature is controlled at 55 DEG C, and the reaction time, at 4 hours, obtains the mixing of colloidal after reaction
Liquid A.
(3) to adding ammoniacal liquor, the NH in the ammoniacal liquor in mixed liquor A3Weight content be 27%, weight ratio be mixed liquor A ︰
Ammoniacal liquor=1 ︰ 0.10, reaction temperature is controlled at 50 DEG C, and the reaction time was at 0.5 hour；Because sodium hexafluorisilicate and hexafluoro sodium aluminate are heavy
Shallow lake speed is relatively slow and is difficult to precipitate completely, adds insufficient amount of ammoniacal liquor, because the activity of sodium hexafluorisilicate is stronger than hexafluoro sodium aluminate,
In the case of ammoniacal liquor is insufficient amount of, ammoniacal liquor preferentially reacts with part sodium hexafluorisilicate, the part hexafluoro silicon in ammoniacal liquor and mixed liquor A
Sour sodium and hydrofluoric acid reaction generation silica, sodium fluoride and ammonium acid fluoride, Na2SiF6+ 4HF + 4NH4OH → SiO2 +
2NaF + 4NH4HF2 + 2H2O；The silica adjusts colloidal electric charge, accelerates hexafluoro sodium aluminate and remaining hexafluorosilicic acid
The molecule of sodium is reunited, and hexafluoro sodium aluminate and remaining sodium hexafluorisilicate is settled rapidly, obtains mixed liquid B.
(4) mixed liquid B is stood 1 hour, filtering precipitate removes filter cake, and filtrate is back in sedimentation supernatant, obtains
Solution C, after removing impurity, mainly contains the hydrofluoric acid and a small amount of sodium fluoride, ammonium acid fluoride of high concentration in solution C.
(5) two parts of the calcium hydroxide suspension that weight content is 30% is prepared, and the granularity of calcium hydroxide is 40 microns.
(6) in solution C being added into above-mentioned calcium hydroxide suspension under agitation, temperature control is stopped at 30 DEG C to pH=5
Only plus solution C, continue to stir and react 2 hours, make calcium hydroxide completely with solution C in hydrofluoric acid reaction generation calcirm-fluoride,
2HF + Ca(OH)2 →CaF2↓+ H2O, remains a small amount of hydrofluoric acid, obtains mixed liquor D.
(7) under agitation to step calcium hydroxide suspension (5) is added in mixed liquor D, determined when adding fluorine from
Sub- concentration, until stopping adding calcium hydroxide suspension when fluorinion concentration is 20mg/L, is further continued for reaction 0.5 hour, makes to remain
Remaining hydrofluoric acid fundamental reaction is complete, and sodium fluoride, ammonium acid fluoride in mixed liquor D generate with calcium hydroxide reaction be fluorinated respectively
Calcium, 2NaF+ Ca (OH)2→2NaOH+ CaF2↓； NH4HF2+ Ca(OH)2 → CaF2↓+ NH4OH + H2O, obtains mixed liquor
E。
To in mixed liquor E add weight content be 0.09% polyacrylamide solution, the polyacrylamide for it is non-from
Subtype or anionic, molecular weight are 10,000,000, and the weight ratio that adds of polyacrylamide solution is mixed liquor D ︰ polyacrylamides
Solution=1 ︰ 0.015, is slowly stirred 10 seconds.
(9) the mixed liquor standing sedimentation 0.5 hour by step (8), bottom sediment is filtered and filter cake is cleaned, and washes away NaOH
、NH4OH etc., is finally carried out drying obtaining calcirm-fluoride solid, and the content of calcirm-fluoride is determined using GB/T 5195.1-2006 methods
Reach 95.9%.
The foregoing is only the preferable possible embodiments of the present invention, non-therefore limitation patent protection model of the invention
Enclose.In addition to the implementation, the present invention can also have other embodiment.The skill that all use equivalents or equivalent transformation are formed
Art scheme, all falls within the protection domain of application claims.Technical characteristic of the present invention without description can be by or using now
There is technology to realize, will not be repeated here.
Claims (5)
1. a kind of method that calcirm-fluoride is produced by the LCD glass etching liquid of giving up, it is characterised in that：In turn include the following steps：
(1) a certain amount of useless LCD glass etching liquid is taken, hydrofluoric acid, hexafluorosilicic acid and six in useless LCD glass etching liquid is determined
The content of fluoaluminic acid；(2), to sodium fluoride solid is added in useless LCD glass etching liquid, weight ratio is useless LCD glass erosion
Carve liquid：Sodium fluoride=1:（0.2~0.25）, be sufficiently stirred for making hexafluorosilicic acid and sodium fluoride react completely generation sodium hexafluorisilicate and
Hydrofluoric acid, makes hexafluoro aluminic acid and sodium fluoride react generation hexafluoro sodium aluminate and hydrofluoric acid completely, reaction temperature control 15 DEG C~
55 DEG C, the reaction time, at 0.5 hour~4 hours, obtains the mixed liquor A of colloidal after reaction；(3) to adding ammonia in mixed liquor A
Water, weight ratio is mixed liquor A ︰ ammoniacal liquor=1 ︰（0.08~0.10）, at 10 DEG C~50 DEG C, the reaction time is 0.5 for reaction temperature control
~2 hours；Part sodium hexafluorisilicate and hydrofluoric acid reaction generation silica, sodium fluoride in the ammoniacal liquor and mixed liquor A and
Ammonium acid fluoride；The silica adjusts colloidal electric charge, accelerates the molecule of hexafluoro sodium aluminate and remaining sodium hexafluorisilicate to reunite,
Hexafluoro sodium aluminate and remaining sodium hexafluorisilicate is settled rapidly, obtain mixed liquid B；(4) mixed liquid B is stood 0.5~1 hour,
Filtering precipitate, removes filter cake, and filtrate is back in sedimentation supernatant, obtains solution C；(5) the hydrogen that weight content is 30% is prepared
Two parts of calcium oxide suspension；(6) in solution C being added into above-mentioned calcium hydroxide suspension under agitation, temperature control is at 30 DEG C
~65 DEG C, to pH=5 stop plus solution C, continue to stir and react 0.5~2 hour, make calcium hydroxide completely with solution C in hydrogen
Fluoric acid reaction generation calcirm-fluoride, obtains mixed liquor D；(7) under agitation to addition step calcium hydroxide (5) in mixed liquor D
Suspension, fluorinion concentration is determined when adding, until fluorinion concentration stops adding calcium hydroxide to suspend when being less than 20mg/L
Liquid, is further continued for reaction 0.5 hour, and the sodium fluoride, ammonium acid fluoride in mixed liquor D generate calcirm-fluoride with calcium hydroxide reaction respectively,
Obtain mixed liquor E；(8) to the polyacrylamide solution that addition weight content in mixed liquor E is 0.05%~0.2%, polyacrylamide
The weight ratio that adds of solution is mixed liquor D ︰ polyacrylamide solution=1 ︰（0.005~0.015）, it is slowly stirred 10~30 seconds；⑼
By step mixed liquor standing sedimentation (8) 0.5~1 hour, bottom sediment is filtered and filter cake is cleaned, finally carry out drying
Calcirm-fluoride solid to purity more than 95%.
2. the method that calcirm-fluoride is produced by the LCD glass etching liquid of giving up according to claim 1, it is characterised in that：Institute
In stating step (1), the percentage by weight that the hydrofluoric acid accounts for etching solution is 16.5%~18.5%, and the hexafluorosilicic acid accounts for etching solution
Percentage by weight be 20%~22%, the hexafluoro aluminic acid account for etching solution percentage by weight be 8%~9%.
3. the method that calcirm-fluoride is produced by the LCD glass etching liquid of giving up according to claim 1, it is characterised in that：Institute
In stating step (3), the NH in the ammoniacal liquor3Weight content be 27%.
4. the method for producing calcirm-fluoride by the LCD glass etching liquid of giving up according to claim 1 or 2 or 3, its feature exists
In：The step (5) in, the granularity of calcium hydroxide is 23 microns~45 microns.
5. the method for producing calcirm-fluoride by the LCD glass etching liquid of giving up according to claim 1 or 2 or 3, its feature exists
In：The step (8) in, the polyacrylamide be non-ionic or anionic, molecular weight be 3,000,000~20,000,000.
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| TWI574923B (en) * | 2016-04-06 | 2017-03-21 | 百德光電有限公司 | Method for producing calcium fluoride by wastewater comprising hydrofluoric acid, hexafluoro silicate and hexafluoro aluminate |
| CN105753220B (en) * | 2016-04-20 | 2018-05-04 | 好科（上海）环保科技有限公司 | The waste treatment method of vapor phase method quartz products manufacturing process and the waste treatment method of preform manufacturing process |
| TWI606975B (en) * | 2016-06-07 | 2017-12-01 | 達穎應材股份有限公司 | Treating and Recycling Method of Fluorine Containing Dust |
| CN106986368B (en) * | 2017-03-13 | 2018-09-04 | 李德寿 | A kind of preparation method of artificial Fluorite pellet |
| CN107540234B (en) * | 2017-09-26 | 2020-07-21 | 衢州市鼎盛化工科技有限公司 | Method for discharging glass thinning system without waste acid and glass slag |
| CN109019984A (en) * | 2018-09-13 | 2018-12-18 | 衢州市鼎盛化工科技有限公司 | A kind of method and system recycling efficient resource from glass thinning acid pickle |
| CN109721058A (en) * | 2019-02-01 | 2019-05-07 | 江西沃格光电股份有限公司 | The processing method of fluorine-containing glass etching waste liquid |
| CN110282647A (en) * | 2019-08-02 | 2019-09-27 | 辽宁星空新能源发展有限公司 | A kind of method that rapid precipitation prepares porous fluorinated calcium cube |
| CN112110589B (en) * | 2020-09-27 | 2022-09-09 | 大连东泰产业废弃物处理有限公司 | Harmless treatment method of high-concentration buffer hydrofluoric acid etching waste liquid |
| CN112357943A (en) * | 2020-11-10 | 2021-02-12 | 湖北省宏源药业科技股份有限公司 | Method for recovering cryolite from acid pickling residues of silicon-aluminum glass |
| CN113816349A (en) * | 2021-10-24 | 2021-12-21 | 会昌宏氟高新材料有限责任公司 | Method for synthesizing phosphorus pentafluoride by using fluorine-containing waste |
| CN114031304B (en) * | 2021-11-27 | 2023-05-26 | Oppo广东移动通信有限公司 | High-alumina glass etching liquid, anti-dazzle high-alumina glass, shell assembly and electronic equipment |
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