CN104071820A - Method for producing calcium fluoride by waste LCD panel glass etching liquid - Google Patents
Method for producing calcium fluoride by waste LCD panel glass etching liquid Download PDFInfo
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Abstract
The invention relates to a method for producing calcium fluoride by waste LCD panel glass etching liquid. The method sequentially comprises the following steps: weighting a certain amount of waste LCD panel glass etching liquid, adding a sodium fluoride solid, fully stirring to enable hexafluorosilicate and sodium fluoride in the waste liquid to completely react to generate sodium hexafluorosilicate and hydrofluoric acid and to enable hexafluoroaluminate and sodium fluoride to completely react to generate sodium hexafluoroaluminate and hydrofluoric acid; then adding ammonia water to react so as to generate silicon dioxide, sodium fluoride and ammonium bifluoride, and enabling the sodium hexafluoroaluminate and the remanent sodium hexafluorosilicate to settle rapidly; then filtering a precipitate, taking a supernatant to be added into a calcium hydroxide suspension, and stopping the addition of the supernatant until the pH is equal to 5 to enable calcium hydroxide to fully react with hydrofluoric acid so as to generate calcium fluoride; then adding the calcium hydroxide suspension into the former solution to enable the sodium fluoride and the ammonium bifluoride to respectively react with the calcium hydroxide so as to generate calcium fluoride; adding a polyacrylamide solution into the former solution, performing precipitation, filtering and cleaning, and finally drying to obtain the calcium fluoride solid. The purity of calcium fluoride is above 95%.
Description
Technical field
The present invention relates to a kind for the treatment of process of glass etching liquid, particularly a kind of method of producing Calcium Fluoride (Fluorspan) by useless LCD face glass etching solution.
Background technology
In general glass thinning operation, all use hydrofluoric acid to carry out etching reduction processing to glass, the processing mode useless solid and waste liquid producing in glass etching process is substantially all that the third-party institution by there being qualification reclaims, after recovery, process, after mud adopts land-fill method disposal or carries out high-temperature calcination, landfill is disposed, and supernatant liquor returns industrial sewage treatment system and processes.
At present common fluorine-containing wastewater treatment method is for to be first dissolved into liquid by calcic medicament, then under mechanical agitation, be added in waste water, make the fluorion in waste water react the water-insoluble Calcium Fluoride (Fluorspan) suspended particle of formation with calcium ion, then stratification, upper clear supernate flows out, and bottom mud is delivered to press filteration system and carries out press filtration processing.Also there are the calcium salt of employing, alkali lye and flocculation agent mixed system to carry out the processing of hydrofluoric acid.
Publication number is that the application for a patent for invention of CN 1504419 discloses a kind of " hydrofluoric acid wastewater treatment method and device ", adopts the vapor condensation operation in hydrofluoric acid evaporation concentration operation, HF steam dissolved water operation, alkali and after operation and de-HF to carry out hydrofluoric acid treatment scheme.
Publication number is that the application for a patent for invention of CN 1559931 discloses a kind of " treatment system of hydrofluoric acid and method ", adopts two treatment troughs to carry out secondary calcium salt and processes the method for the hydrofluoric acid waste liquid that can discharge with generation and the waste that can bury.
Aforesaid method may be effective in the time processing lower concentration or a small amount of hydrofluoric acid waste liquid, but aobvious economical and practical not to the processing of a large amount of high concentration of hydrofluoric acid.
Aspect the processing of high concentration of hydrofluoric acid, publication number is that the application for a patent for invention of CN 202072566U discloses a kind of " a kind of containing high concentration of hydrofluoric acid Waste Water Treatment ", for the treatment of passivation for stainless steel pickling, the purification system containing high concentration of hydrofluoric acid waste water producing in the industry production processes such as photovoltaic new forms of energy, in integrated reacting equipment, be provided with air mixing device and without mechanical stirring, be provided with the pH proofing unit that stretches into conversion unit inside in integrated reacting its upper side, fluorion proofing unit and white lime, calcium chloride, coagulating agent throwing device, be provided with water outlet in integrated reacting device bottom, water outlet connects filter-pressing device by pipeline through lift pump.This system adopts direct siccative to add, and saves medicament dissolution, conveying process, reduces energy consumption, and can solve adding of agent line clogging problem completely.But still there is following deficiency in this system: 1. the Calcium Fluoride (Fluorspan) purity that spent acid processing generates is low, and generally refuse landfill disposal of a conduct, cannot serve as resource reutilization conventionally, causes the huge waste of fluorine resource; 2. directly siccative adds that the slow caused Peritectic Reaction meeting of dissolution process causes the excessive input of siccative and produces waste because precipitin reaction is fast, greatly increases raw material consumption and production cost.
Summary of the invention
The object of the invention is to, overcome problems of the prior art, a kind of method of producing Calcium Fluoride (Fluorspan) by useless LCD face glass etching solution is provided, can make highly purified Calcium Fluoride (Fluorspan), as the fusing assistant of Metal smelting and the raw material of production hydrofluoric acid, non-renewable fluorine-containing resource is fully utilized.
For solving above technical problem, a kind of method of producing Calcium Fluoride (Fluorspan) by useless LCD face glass etching solution of the present invention, in turn include the following steps: (1) get a certain amount of useless LCD face glass etching solution, measure the content of hydrofluoric acid, hexafluorosilicic acid and hexafluoro aluminic acid in useless LCD face glass etching solution; (2) in useless LCD face glass etching solution, add Sodium Fluoride solid, weight ratio is useless LCD face glass etching solution: Sodium Fluoride=1:(0.2～0.25), fully stir and make hexafluorosilicic acid and Sodium Fluoride complete reaction generate sodium hexafluorisilicate and hydrofluoric acid, make hexafluoro aluminic acid and Sodium Fluoride complete reaction generate hexafluoro sodium aluminate and hydrofluoric acid, temperature of reaction is controlled at 15 DEG C～55 DEG C, reaction times, at 0.5 hour～4 hours, obtains the mixed liquor A of colloidal after reaction; (3) in mixed liquor A, add ammoniacal liquor, weight ratio is mixed solution A ︰ ammoniacal liquor=1 ︰ (0.08～0.10), and temperature of reaction is controlled at 10 DEG C～50 DEG C, and the reaction times was at 0.5～2 hour; Described ammoniacal liquor reacts generation silicon-dioxide, Sodium Fluoride and ammonium bifluoride with part sodium hexafluorisilicate and hydrofluoric acid in mixed liquor A; Described silicon-dioxide regulates colloidal electric charge, accelerates the molecule of hexafluoro sodium aluminate and remaining sodium hexafluorisilicate and reunites, and makes hexafluoro sodium aluminate and the rapid sedimentation of remaining sodium hexafluorisilicate, obtains mixed liquid B; (4) mixed liquid B is left standstill to 0.5～1 hour, filtering precipitate, removes filter cake, and filtrate is back in sedimentation supernatant liquor, obtains solution C; (5) prepare weight content and be two parts of 30% calcium hydroxide suspensions; (6) under agitation condition, solution C is added in above-mentioned calcium hydroxide suspension, temperature is controlled at 30 DEG C～65 DEG C, stops adding solution C to pH=5, continues stir and react 0.5～2 hour, make calcium hydroxide completely react with the hydrofluoric acid in solution C and generate Calcium Fluoride (Fluorspan), obtain mixed solution D; (7) under agitation condition, in mixed solution D, add step calcium hydroxide suspension (5), measure fluorinion concentration while adding, until fluorinion concentration stops adding calcium hydroxide suspension during lower than 20mg/L, continue again reaction 0.5 hour, Sodium Fluoride, ammonium bifluoride in mixed solution D generate Calcium Fluoride (Fluorspan) with calcium hydroxide reaction respectively, obtain mixed solution E; (8) be 0.05%～0.2% polyacrylamide solution to adding weight content in mixed solution E, the weight ratio that adds of polyacrylamide solution is mixed solution D ︰ polyacrylamide solution=1 ︰ (0.005～0.015), slowly stirs 10～30 seconds; (9) by step mixed solution standing sedimentation (8) 0.5～1 hour, bottom throw out is filtered and clean filter cake, finally dry and obtain Calcium Fluoride (Fluorspan) solid.
With respect to prior art, the present invention has obtained following beneficial effect: (1) in the useless LCD face glass etching solution after glass thinning, contain high-concentration waste hydrofluoric acid, also contain more hexafluorosilicic acid and hexafluoro aluminic acid impurity, if directly add calcium hydroxide processing, in throw out except containing Calcium Fluoride (Fluorspan), also contain the impurity such as more hexafluorosilicic acid calcium and hexafluoro calcium aluminate, thereby can reduce purity and the use value of major product Calcium Fluoride (Fluorspan); (2) the present invention first adds Sodium Fluoride solid to make hexafluorosilicic acid and Sodium Fluoride complete reaction generate sodium hexafluorisilicate and hydrofluoric acid in useless LCD face glass etching solution, makes hexafluoro aluminic acid and Sodium Fluoride complete reaction generate hexafluoro sodium aluminate and hydrofluoric acid, H
2siF
6+ 2NaF → Na
2siF
6↓+2HF; 2H
3alF
6+ 6NaF → 2Na
3alF
6↓+6HF; Because sodium hexafluorisilicate and hexafluoro sodium aluminate are throw out, can first hexafluorosilicic acid and hexafluoro aluminic acid impurity in useless hydrofluoric acid be removed through this reaction; Sodium Fluoride price comparison is low, and molecular weight is little, and resultant of reaction contains hydrofluoric acid, has improved the hydrofluoric acid concentration in former spent acid, is conducive to improve purity in the time preparing Calcium Fluoride (Fluorspan).(3) because sodium hexafluorisilicate and hexafluoro sodium aluminate sedimentation speed are slow and be difficult to precipitation completely, add ammoniacal liquor in shortage, because the specific activity hexafluoro sodium aluminate of sodium hexafluorisilicate is strong, in the situation that ammoniacal liquor is in shortage, ammoniacal liquor preferentially reacts with sodium hexafluorisilicate; Approximately react Na with 10% sodium hexafluorisilicate
2siF
6+ 4HF+4NH
4oH → SiO
2+ 2NaF+4NH
4hF
2+ 2H
2o, the silicon-dioxide of generation regulates colloidal electric charge, accelerates hexafluoro sodium aluminate and remaining sodium hexafluorisilicate precipitation, utilizes and removes rapidly impurity; (4) remove after impurity, in solution C, mainly contain the hydrofluoric acid of high density and a small amount of Sodium Fluoride, ammonium bifluoride, first add into stopping to pH=5 in calcium hydroxide suspension, ensure the complete generation Calcium Fluoride (Fluorspan) of calcium hydroxide reaction, 2HF+Ca (OH)
2→ CaF
2↓+H
2o, residual a small amount of hydrofluoric acid; Add again calcium hydroxide suspension during lower than 20mg/L, to make remaining hydrofluoric acid primitive reaction complete to fluorinion concentration, and Sodium Fluoride, ammonium bifluoride further generate Calcium Fluoride (Fluorspan) with calcium hydroxide reaction respectively, 2NaF+ Ca (OH)
2→ 2NaOH+ CaF
2↓; NH
4hF
2+ Ca (OH)
2→ CaF
2↓+NH
4oH+H
2o, has improved the growing amount of Calcium Fluoride (Fluorspan), and this method is beneficial to grasps reaction end accurately, reduces material except major product residual.(5) then add flocculation agent polyacrylamide solution, make the Calcium Fluoride (Fluorspan) sedimentation of reuniting rapidly, filter and obtain cleaning after filter cake, wash away NaOH, NH
4oH etc., then dry and obtain Calcium Fluoride (Fluorspan) solid, the content that uses GB/T 5195.1-2006 method to measure Calcium Fluoride (Fluorspan) can reach more than 95%.(6) highly purified Calcium Fluoride (Fluorspan) like this, can be used as the fusing assistant of Metal smelting and the raw material of production hydrofluoric acid, and non-renewable fluorine-containing resource is fully utilized.
Described step (1) in, the weight percent that described hydrofluoric acid accounts for etching solution is 16.5%～18.5%, the weight percent that described hexafluorosilicic acid accounts for etching solution is 20%～22%, the weight percent that described hexafluoro aluminic acid accounts for etching solution is 8%～9%.The content of the above-mentioned each material of useless LCD face glass etching solution after glass thinning is within the scope of this.
Described step (3) in, the NH in described ammoniacal liquor
3weight content be 27%.
Described step (5) in, the granularity of calcium hydroxide is 23 microns～45 microns.Be easy to reaction, improve speed of response.
Described step (8) in, described polyacrylamide is non-ionic type or anionic, molecular weight is 3,000,000～2,000 ten thousand.
Embodiment
Embodiment mono-
Method of producing Calcium Fluoride (Fluorspan) by useless LCD face glass etching solution of the present invention, in turn includes the following steps:
(1) a certain amount of useless LCD face glass etching solution, measure the content of hydrofluoric acid, hexafluorosilicic acid and hexafluoro aluminic acid in useless LCD face glass etching solution, the weight percent that described hydrofluoric acid accounts for etching solution is 16.5%, the weight percent that described hexafluorosilicic acid accounts for etching solution is 20%, and the weight percent that described hexafluoro aluminic acid accounts for etching solution is 8%.
(2) in useless LCD face glass etching solution, add Sodium Fluoride solid, weight ratio is useless LCD face glass etching solution: Sodium Fluoride=1:0.2, fully stirs and makes hexafluorosilicic acid and Sodium Fluoride complete reaction generate sodium hexafluorisilicate and hydrofluoric acid, H
2siF
6+ 2NaF → Na
2siF
6↓+2HF; Make hexafluoro aluminic acid and Sodium Fluoride complete reaction generate hexafluoro sodium aluminate and hydrofluoric acid, 2H
3alF
6+ 6NaF → 2Na
3alF
6↓+6HF; Temperature of reaction is controlled at 15 DEG C, and the reaction times, at 0.5 hour, obtains the mixed liquor A of colloidal after reaction.
(3) in mixed liquor A, add ammoniacal liquor, the NH in described ammoniacal liquor
3weight content be 27%, weight ratio is mixed solution A ︰ ammoniacal liquor=1 ︰ 0.08, temperature of reaction is controlled at 10 DEG C, the reaction times was at 0.5 hour; Because sodium hexafluorisilicate and hexafluoro sodium aluminate sedimentation speed are slow and be difficult to precipitation completely, add ammoniacal liquor in shortage, because the specific activity hexafluoro sodium aluminate of sodium hexafluorisilicate is strong, in the situation that ammoniacal liquor is in shortage, ammoniacal liquor preferentially reacts with part sodium hexafluorisilicate, ammoniacal liquor reacts generation silicon-dioxide, Sodium Fluoride and ammonium bifluoride, Na with part sodium hexafluorisilicate and hydrofluoric acid in mixed liquor A
2siF
6+ 4HF+4NH
4oH → SiO
2+ 2NaF+4NH
4hF
2+ 2H
2o; Described silicon-dioxide regulates colloidal electric charge, accelerates the molecule of hexafluoro sodium aluminate and remaining sodium hexafluorisilicate and reunites, and makes hexafluoro sodium aluminate and the rapid sedimentation of remaining sodium hexafluorisilicate, obtains mixed liquid B.
(4) mixed liquid B is left standstill to 0.5 hour, filtering precipitate, removes filter cake, and filtrate is back in sedimentation supernatant liquor, obtains solution C, removes after impurity, mainly contains the hydrofluoric acid of high density and a small amount of Sodium Fluoride, ammonium bifluoride in solution C.
(5) prepare weight content and be two parts of 30% calcium hydroxide suspensions, the granularity of calcium hydroxide is 23 microns.
(6) under agitation condition, solution C is added in above-mentioned calcium hydroxide suspension, temperature is controlled at 30 DEG C, stops adding solution C to pH=5, continues stir and react 0.5 hour, calcium hydroxide is reacted with the hydrofluoric acid in solution C completely and generate Calcium Fluoride (Fluorspan), 2HF+Ca (OH)
2→ CaF
2↓+H
2o, residual a small amount of hydrofluoric acid, obtains mixed solution D.
(7) under agitation condition, in mixed solution D, add step calcium hydroxide suspension (5), measure fluorinion concentration while adding, until fluorinion concentration stops adding calcium hydroxide suspension while being 18mg/L, continue again reaction 0.5 hour, make remaining hydrofluoric acid primitive reaction complete, and Sodium Fluoride, ammonium bifluoride in mixed solution D generate Calcium Fluoride (Fluorspan), 2NaF+ Ca (OH) with calcium hydroxide reaction respectively
2→ 2NaOH+ CaF
2↓; NH
4hF
2+ Ca (OH)
2→ CaF
2↓+NH
4oH+H
2o, obtains mixed solution E.
(8) be 0.05% polyacrylamide solution to adding weight content in mixed solution E, described polyacrylamide is non-ionic type or anionic, molecular weight is 3,000,000, and the weight ratio that adds of polyacrylamide solution is mixed solution D ︰ polyacrylamide solution=1 ︰ 0.005, slowly stirs 10 seconds.
(9) by step mixed solution standing sedimentation (8) 0.5 hour, bottom throw out is filtered and clean filter cake, wash away NaOH, NH
4oH etc., finally dry and obtain Calcium Fluoride (Fluorspan) solid, and the content that uses GB/T 5195.1-2006 method to measure Calcium Fluoride (Fluorspan) reaches 95.6%.
Embodiment bis-
Method of producing Calcium Fluoride (Fluorspan) by useless LCD face glass etching solution of the present invention, in turn includes the following steps:
(1) a certain amount of useless LCD face glass etching solution, measure the content of hydrofluoric acid, hexafluorosilicic acid and hexafluoro aluminic acid in useless LCD face glass etching solution, the weight percent that described hydrofluoric acid accounts for etching solution is 17.6%, the weight percent that described hexafluorosilicic acid accounts for etching solution is 21%, and the weight percent that described hexafluoro aluminic acid accounts for etching solution is 8.4%.
(2) in useless LCD face glass etching solution, add Sodium Fluoride solid, weight ratio is useless LCD face glass etching solution: Sodium Fluoride=1:0.22, fully stirs and makes hexafluorosilicic acid and Sodium Fluoride complete reaction generate sodium hexafluorisilicate and hydrofluoric acid, H
2siF
6+ 2NaF → Na
2siF
6↓+2HF; Make hexafluoro aluminic acid and Sodium Fluoride complete reaction generate hexafluoro sodium aluminate and hydrofluoric acid, 2H
3alF
6+ 6NaF → 2Na
3alF
6↓+6HF; Temperature of reaction is controlled at 35 DEG C, and the reaction times, at 2 hours, obtains the mixed liquor A of colloidal after reaction.
(3) in mixed liquor A, add ammoniacal liquor, the NH in described ammoniacal liquor
3weight content be 27%, weight ratio is mixed solution A ︰ ammoniacal liquor=1 ︰ 0.09, temperature of reaction is controlled at 30 DEG C, the reaction times was at 1 hour; Because sodium hexafluorisilicate and hexafluoro sodium aluminate sedimentation speed are slow and be difficult to precipitation completely, add ammoniacal liquor in shortage, because the specific activity hexafluoro sodium aluminate of sodium hexafluorisilicate is strong, in the situation that ammoniacal liquor is in shortage, ammoniacal liquor preferentially reacts with part sodium hexafluorisilicate, ammoniacal liquor reacts generation silicon-dioxide, Sodium Fluoride and ammonium bifluoride, Na with part sodium hexafluorisilicate and hydrofluoric acid in mixed liquor A
2siF
6+ 4HF+4NH
4oH → SiO
2+ 2NaF+4NH
4hF
2+ 2H
2o; Described silicon-dioxide regulates colloidal electric charge, accelerates the molecule of hexafluoro sodium aluminate and remaining sodium hexafluorisilicate and reunites, and makes hexafluoro sodium aluminate and the rapid sedimentation of remaining sodium hexafluorisilicate, obtains mixed liquid B.
(4) mixed liquid B is left standstill to 0.8 hour, filtering precipitate, removes filter cake, and filtrate is back in sedimentation supernatant liquor, obtains solution C, removes after impurity, mainly contains the hydrofluoric acid of high density and a small amount of Sodium Fluoride, ammonium bifluoride in solution C.
(5) prepare weight content and be two parts of 30% calcium hydroxide suspensions, the granularity of calcium hydroxide is 35 microns.
(6) under agitation condition, solution C is added in above-mentioned calcium hydroxide suspension, temperature is controlled at 45 DEG C, stops adding solution C to pH=5, continues stir and react 1 hour, calcium hydroxide is reacted with the hydrofluoric acid in solution C completely and generate Calcium Fluoride (Fluorspan), 2HF+Ca (OH)
2→ CaF
2↓+H
2o, residual a small amount of hydrofluoric acid, obtains mixed solution D.
(7) under agitation condition, in mixed solution D, add step calcium hydroxide suspension (5), measure fluorinion concentration while adding, until fluorinion concentration stops adding calcium hydroxide suspension while being 19mg/L, continue again reaction 0.5 hour, make remaining hydrofluoric acid primitive reaction complete, and Sodium Fluoride, ammonium bifluoride in mixed solution D generate Calcium Fluoride (Fluorspan), 2NaF+ Ca (OH) with calcium hydroxide reaction respectively
2→ 2NaOH+ CaF
2↓; NH
4hF
2+ Ca (OH)
2→ CaF
2↓+NH
4oH+H
2o, obtains mixed solution E.
(8) be 0.1% polyacrylamide solution to adding weight content in mixed solution E, described polyacrylamide is non-ionic type or anionic, molecular weight is 3,000,000～2,000 ten thousand, and the weight ratio that adds of polyacrylamide solution is mixed solution D ︰ polyacrylamide solution=1 ︰ 0.01, slowly stirs 20 seconds.
(9) by step mixed solution standing sedimentation (8) 0.8 hour, bottom throw out is filtered and clean filter cake, wash away NaOH, NH
4oH etc., finally dry and obtain Calcium Fluoride (Fluorspan) solid, and the content that uses GB/T 5195.1-2006 method to measure Calcium Fluoride (Fluorspan) reaches 95.8%.
Embodiment tri-
Method of producing Calcium Fluoride (Fluorspan) by useless LCD face glass etching solution of the present invention, in turn includes the following steps:
(1) a certain amount of useless LCD face glass etching solution, measure the content of hydrofluoric acid, hexafluorosilicic acid and hexafluoro aluminic acid in useless LCD face glass etching solution, the weight percent that described hydrofluoric acid accounts for etching solution is 18.5%, the weight percent that described hexafluorosilicic acid accounts for etching solution is 22%, and the weight percent that described hexafluoro aluminic acid accounts for etching solution is 9%.
(2) in useless LCD face glass etching solution, add Sodium Fluoride solid, weight ratio is useless LCD face glass etching solution: Sodium Fluoride=1:0.25, fully stirs and makes hexafluorosilicic acid and Sodium Fluoride complete reaction generate sodium hexafluorisilicate and hydrofluoric acid, H
2siF
6+ 2NaF → Na
2siF
6↓+2HF; Make hexafluoro aluminic acid and Sodium Fluoride complete reaction generate hexafluoro sodium aluminate and hydrofluoric acid, 2H
3alF
6+ 6NaF → 2Na
3alF
6↓+6HF; Temperature of reaction is controlled at 55 DEG C, and the reaction times, at 4 hours, obtains the mixed liquor A of colloidal after reaction.
(3) in mixed liquor A, add ammoniacal liquor, the NH in described ammoniacal liquor
3weight content be 27%, weight ratio is mixed solution A ︰ ammoniacal liquor=1 ︰ 0.10, temperature of reaction is controlled at 50 DEG C, the reaction times was at 2 hours; Because sodium hexafluorisilicate and hexafluoro sodium aluminate sedimentation speed are slow and be difficult to precipitation completely, add ammoniacal liquor in shortage, because the specific activity hexafluoro sodium aluminate of sodium hexafluorisilicate is strong, in the situation that ammoniacal liquor is in shortage, ammoniacal liquor preferentially reacts with part sodium hexafluorisilicate, ammoniacal liquor reacts generation silicon-dioxide, Sodium Fluoride and ammonium bifluoride, Na with part sodium hexafluorisilicate and hydrofluoric acid in mixed liquor A
2siF
6+ 4HF+4NH
4oH → SiO
2+ 2NaF+4NH
4hF
2+ 2H
2o; Described silicon-dioxide regulates colloidal electric charge, accelerates the molecule of hexafluoro sodium aluminate and remaining sodium hexafluorisilicate and reunites, and makes hexafluoro sodium aluminate and the rapid sedimentation of remaining sodium hexafluorisilicate, obtains mixed liquid B.
(4) mixed liquid B is left standstill to 1 hour, filtering precipitate, removes filter cake, and filtrate is back in sedimentation supernatant liquor, obtains solution C, removes after impurity, mainly contains the hydrofluoric acid of high density and a small amount of Sodium Fluoride, ammonium bifluoride in solution C.
(5) prepare weight content and be two parts of 30% calcium hydroxide suspensions, the granularity of calcium hydroxide is 45 microns.
(6) under agitation condition, solution C is added in above-mentioned calcium hydroxide suspension, temperature is controlled at 65 DEG C, stops adding solution C to pH=5, continues stir and react 2 hours, calcium hydroxide is reacted with the hydrofluoric acid in solution C completely and generate Calcium Fluoride (Fluorspan), 2HF+Ca (OH)
2→ CaF
2↓+H
2o, residual a small amount of hydrofluoric acid, obtains mixed solution D.
(7) under agitation condition, in mixed solution D, add step calcium hydroxide suspension (5), measure fluorinion concentration while adding, until fluorinion concentration stops adding calcium hydroxide suspension while being 20mg/L, continue again reaction 0.5 hour, make remaining hydrofluoric acid primitive reaction complete, and Sodium Fluoride, ammonium bifluoride in mixed solution D generate Calcium Fluoride (Fluorspan), 2NaF+ Ca (OH) with calcium hydroxide reaction respectively
2→ 2NaOH+ CaF
2↓; NH
4hF
2+ Ca (OH)
2→ CaF
2↓+NH
4oH+H
2o, obtains mixed solution E.
(8) be 0.2% polyacrylamide solution to adding weight content in mixed solution E, described polyacrylamide is non-ionic type or anionic, molecular weight is 2,000 ten thousand, and the weight ratio that adds of polyacrylamide solution is mixed solution D ︰ polyacrylamide solution=1 ︰ 0.015, slowly stirs 30 seconds.
(9) by step mixed solution standing sedimentation (8) 1 hour, bottom throw out is filtered and clean filter cake, wash away NaOH, NH
4oH etc., finally dry and obtain Calcium Fluoride (Fluorspan) solid, and the content that uses GB/T 5195.1-2006 method to measure Calcium Fluoride (Fluorspan) reaches 96.1%.
Embodiment tetra-
Method of producing Calcium Fluoride (Fluorspan) by useless LCD face glass etching solution of the present invention, in turn includes the following steps:
(1) a certain amount of useless LCD face glass etching solution, measure the content of hydrofluoric acid, hexafluorosilicic acid and hexafluoro aluminic acid in useless LCD face glass etching solution, the weight percent that described hydrofluoric acid accounts for etching solution is 17.5%, the weight percent that described hexafluorosilicic acid accounts for etching solution is 21%, and the weight percent that described hexafluoro aluminic acid accounts for etching solution is 8.6%.
(2) in useless LCD face glass etching solution, add Sodium Fluoride solid, weight ratio is useless LCD face glass etching solution: Sodium Fluoride=1:0.2, fully stirs and makes hexafluorosilicic acid and Sodium Fluoride complete reaction generate sodium hexafluorisilicate and hydrofluoric acid, H
2siF
6+ 2NaF → Na
2siF
6↓+2HF; Make hexafluoro aluminic acid and Sodium Fluoride complete reaction generate hexafluoro sodium aluminate and hydrofluoric acid, 2H
3alF
6+ 6NaF → 2Na
3alF
6↓+6HF; Temperature of reaction is controlled at 55 DEG C, and the reaction times, at 4 hours, obtains the mixed liquor A of colloidal after reaction.
(3) in mixed liquor A, add ammoniacal liquor, the NH in described ammoniacal liquor
3weight content be 27%, weight ratio is mixed solution A ︰ ammoniacal liquor=1 ︰ 0.10, temperature of reaction is controlled at 50 DEG C, the reaction times was at 0.5 hour; Because sodium hexafluorisilicate and hexafluoro sodium aluminate sedimentation speed are slow and be difficult to precipitation completely, add ammoniacal liquor in shortage, because the specific activity hexafluoro sodium aluminate of sodium hexafluorisilicate is strong, in the situation that ammoniacal liquor is in shortage, ammoniacal liquor preferentially reacts with part sodium hexafluorisilicate, ammoniacal liquor reacts generation silicon-dioxide, Sodium Fluoride and ammonium bifluoride, Na with part sodium hexafluorisilicate and hydrofluoric acid in mixed liquor A
2siF
6+ 4HF+4NH
4oH → SiO
2+ 2NaF+4NH
4hF
2+ 2H
2o; Described silicon-dioxide regulates colloidal electric charge, accelerates the molecule of hexafluoro sodium aluminate and remaining sodium hexafluorisilicate and reunites, and makes hexafluoro sodium aluminate and the rapid sedimentation of remaining sodium hexafluorisilicate, obtains mixed liquid B.
(4) mixed liquid B is left standstill to 1 hour, filtering precipitate, removes filter cake, and filtrate is back in sedimentation supernatant liquor, obtains solution C, removes after impurity, mainly contains the hydrofluoric acid of high density and a small amount of Sodium Fluoride, ammonium bifluoride in solution C.
(5) prepare weight content and be two parts of 30% calcium hydroxide suspensions, the granularity of calcium hydroxide is 40 microns.
(6) under agitation condition, solution C is added in above-mentioned calcium hydroxide suspension, temperature is controlled at 30 DEG C, stops adding solution C to pH=5, continues stir and react 2 hours, calcium hydroxide is reacted with the hydrofluoric acid in solution C completely and generate Calcium Fluoride (Fluorspan), 2HF+Ca (OH)
2→ CaF
2↓+H
2o, residual a small amount of hydrofluoric acid, obtains mixed solution D.
(7) under agitation condition, in mixed solution D, add step calcium hydroxide suspension (5), measure fluorinion concentration while adding, until fluorinion concentration stops adding calcium hydroxide suspension while being 20mg/L, continue again reaction 0.5 hour, make remaining hydrofluoric acid primitive reaction complete, and Sodium Fluoride, ammonium bifluoride in mixed solution D generate Calcium Fluoride (Fluorspan), 2NaF+ Ca (OH) with calcium hydroxide reaction respectively
2→ 2NaOH+ CaF
2↓; NH
4hF
2+ Ca (OH)
2→ CaF
2↓+NH
4oH+H
2o, obtains mixed solution E.
(8) be 0.09% polyacrylamide solution to adding weight content in mixed solution E, described polyacrylamide is non-ionic type or anionic, molecular weight is 1,000 ten thousand, and the weight ratio that adds of polyacrylamide solution is mixed solution D ︰ polyacrylamide solution=1 ︰ 0.015, slowly stirs 10 seconds.
(9) by step mixed solution standing sedimentation (8) 0.5 hour, bottom throw out is filtered and clean filter cake, wash away NaOH, NH
4oH etc., finally dry and obtain Calcium Fluoride (Fluorspan) solid, and the content that uses GB/T 5195.1-2006 method to measure Calcium Fluoride (Fluorspan) reaches 95.9%.
The foregoing is only the present invention's better possible embodiments, non-ly therefore limit to scope of patent protection of the present invention.In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop in the protection domain of requirement of the present invention.The present invention can pass through or adopt existing techniques in realizing without the technical characterictic of describing, and does not repeat them here.
Claims (5)
1. a method of producing Calcium Fluoride (Fluorspan) by useless LCD face glass etching solution, it is characterized in that: in turn include the following steps: (1) get a certain amount of useless LCD face glass etching solution, measure the content of hydrofluoric acid, hexafluorosilicic acid and hexafluoro aluminic acid in useless LCD face glass etching solution; (2) in useless LCD face glass etching solution, add Sodium Fluoride solid, weight ratio is useless LCD face glass etching solution: Sodium Fluoride=1:(0.2～0.25), fully stir and make hexafluorosilicic acid and Sodium Fluoride complete reaction generate sodium hexafluorisilicate and hydrofluoric acid, make hexafluoro aluminic acid and Sodium Fluoride complete reaction generate hexafluoro sodium aluminate and hydrofluoric acid, temperature of reaction is controlled at 15 DEG C～55 DEG C, reaction times, at 0.5 hour～4 hours, obtains the mixed liquor A of colloidal after reaction; (3) in mixed liquor A, add ammoniacal liquor, weight ratio is mixed solution A ︰ ammoniacal liquor=1 ︰ (0.08～0.10), and temperature of reaction is controlled at 10 DEG C～50 DEG C, and the reaction times was at 0.5～2 hour; Described ammoniacal liquor reacts generation silicon-dioxide, Sodium Fluoride and ammonium bifluoride with part sodium hexafluorisilicate and hydrofluoric acid in mixed liquor A; Described silicon-dioxide regulates colloidal electric charge, accelerates the molecule of hexafluoro sodium aluminate and remaining sodium hexafluorisilicate and reunites, and makes hexafluoro sodium aluminate and the rapid sedimentation of remaining sodium hexafluorisilicate, obtains mixed liquid B; (4) mixed liquid B is left standstill to 0.5～1 hour, filtering precipitate, removes filter cake, and filtrate is back in sedimentation supernatant liquor, obtains solution C; (5) prepare weight content and be two parts of 30% calcium hydroxide suspensions; (6) under agitation condition, solution C is added in above-mentioned calcium hydroxide suspension, temperature is controlled at 30 DEG C～65 DEG C, stops adding solution C to pH=5, continues stir and react 0.5～2 hour, make calcium hydroxide completely react with the hydrofluoric acid in solution C and generate Calcium Fluoride (Fluorspan), obtain mixed solution D; (7) under agitation condition, in mixed solution D, add step calcium hydroxide suspension (5), measure fluorinion concentration while adding, until fluorinion concentration stops adding calcium hydroxide suspension during lower than 20mg/L, continue again reaction 0.5 hour, Sodium Fluoride, ammonium bifluoride in mixed solution D generate Calcium Fluoride (Fluorspan) with calcium hydroxide reaction respectively, obtain mixed solution E; (8) be 0.05%～0.2% polyacrylamide solution to adding weight content in mixed solution E, the weight ratio that adds of polyacrylamide solution is mixed solution D ︰ polyacrylamide solution=1 ︰ (0.005～0.015), slowly stirs 10～30 seconds; (9) by step mixed solution standing sedimentation (8) 0.5～1 hour, bottom throw out is filtered and clean filter cake, finally dry and obtain Calcium Fluoride (Fluorspan) solid.
2. method of producing Calcium Fluoride (Fluorspan) by useless LCD face glass etching solution according to claim 1, it is characterized in that: described step (1) in, the weight percent that described hydrofluoric acid accounts for etching solution is 16.5%～18.5%, the weight percent that described hexafluorosilicic acid accounts for etching solution is 20%～22%, and the weight percent that described hexafluoro aluminic acid accounts for etching solution is 8%～9%.
3. method of being produced Calcium Fluoride (Fluorspan) by useless LCD face glass etching solution according to claim 1, is characterized in that: described step (3) in, the NH in described ammoniacal liquor
3weight content be 27%.
4. according to the method for producing Calcium Fluoride (Fluorspan) by useless LCD face glass etching solution described in claim 1 or 2 or 3, it is characterized in that: described step (5) in, the granularity of calcium hydroxide is 23 microns～45 microns.
5. according to the method for producing Calcium Fluoride (Fluorspan) by useless LCD face glass etching solution described in claim 1 or 2 or 3, it is characterized in that: described step (8) in, described polyacrylamide is non-ionic type or anionic, molecular weight is 3,000,000～2,000 ten thousand.
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