CN110040707A - A kind of preparation method of high-purity optical glass additive metaphosphoric acid copper - Google Patents
A kind of preparation method of high-purity optical glass additive metaphosphoric acid copper Download PDFInfo
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- CN110040707A CN110040707A CN201910394811.7A CN201910394811A CN110040707A CN 110040707 A CN110040707 A CN 110040707A CN 201910394811 A CN201910394811 A CN 201910394811A CN 110040707 A CN110040707 A CN 110040707A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/44—Metaphosphates
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
It is difficult to meet the technical issues of cutoff filter preparation requires to solve the metaphosphoric acid copper purity of existing preparation method production, the present invention provides a kind of preparation methods of high-purity optical glass additive metaphosphoric acid copper, comprising steps of 1, purification of sulphuric acids copper raw material；2, carbonic acid sodium raw materials are purified；3, carbonate synthesis copper；4, biphosphate copper is synthesized；5, metaphosphoric acid copper is synthesized.1, the metaphosphoric acid copper purity being prepared using method of the invention can reach 99.95% or more, can reach 99.99%, elementary metal impurities Fe, Ni, Cr, Co, Mn, Ti, V, Pb content is respectively less than 1.5ppm.
Description
Technical field
The present invention relates to a kind of high-purity metaphosphoric acid copper (Cu (PO3)2) preparation method, be used for cutoff filter glass
Additive in glass.
Background technique
CCD and CMOS photosensor chip element is different from the photosensitive sensitivity spectrum of human eye, therefore, what human eye cannot identify
Infrared light can interfere the image quality of CCD and CMOS photosensor chip element.By the way that infrared section is added in imaging systems
Only optical filter stops the infrared light of part interference image quality, imaging can be made to be more in line with the best perception of human eye.
Main additive ingredient of the metaphosphoric acid copper as cutoff filter, the requirement to purity and metals content impurity
It is very high, it is desirable that purity is 99% or more, and metal impurities Fe, Ni, Cr, Co, Mn, Ti, V, Pb content are at ppm grades, and existing system
Preparation Method is difficult to meet the requirement.
Summary of the invention
It is difficult to meet cutoff filter preparation requirement to solve the metaphosphoric acid copper purity of existing preparation method production
The technical issues of, the present invention provides a kind of preparation methods of high-purity optical glass additive metaphosphoric acid copper.
Technical solution of the present invention:
A kind of preparation method of high-purity optical glass additive metaphosphoric acid copper, is characterized in that, including following step
It is rapid:
Step 1, purification of sulphuric acids copper raw material:
1.1) it takes technical grade sulfuric acid copper raw material to be placed in enamel reaction still, deionized water is added to be heated to 80-90 DEG C of dissolution sulphur
Sour copper cools the temperature to 35 DEG C hereinafter, micro hydrogen peroxide is added, stirs evenly until copper-bath specific gravity is 1.1~1.15
Afterwards, after standing 30 minutes or more, the barium hydroxide solution that concentration is 10-12% is added, adjusts pH value to 3.5~4.2, sufficiently stirs
After mixing, stand 4 hours or more；
1.2) solution for obtaining step 1.1) is filled into another container, and high purity reagent sulfuric acid adjustment pH value is added extremely
After 2.5~3, it is 1.28~1.3 that solution heating, which is concentrated to specific gravity, then decaptitating is filtered in another container；
1.3) the high purity reagent sulfuric acid is added into filtrate obtained by step 1.2), adjusting pH value is 1~2, is then heated dense
Being reduced to specific gravity is 1.48~1.50, is discharged, cooling, obtains cupric sulphate crystal；
1.4) it when being cooled to 25-30 DEG C, pulls cupric sulphate crystal out, enters centrifuge solid-liquor separation, during solid-liquor separation, use
Deionized water washes away the free acid on cupric sulphate crystal surface to 200ppm hereinafter, centrifugal drying -60 minutes 30 minutes, takes out after purification
Cupric sulphate crystal；
1.5) it is sampled from cupric sulphate crystal, detects GOLD FROM PLATING SOLUTION category element of Fe, Ni, Cr, Co, Mn, Ti, V, Pb through ICP
Content, if Fe be less than 2.5ppm, Ni, Cr, Co, Mn, Ti, V, Pb are respectively less than 1ppm, then show the sulfuric acid that step 1.4) obtains
Copper crystallization purifying is qualified, meets subsequent preparation requirement, enters step 2)；If the Fe content in the metallic element is less than
2.5ppm, but other either element contents are more than or equal to 1ppm, then return step 1.2)；If the Fe content in the metallic element
More than or equal to 2.5ppm, then return step 1.1)；
Step 2, purifying carbonic acid sodium raw materials:
2.1) industrial sodium carbonate is put into another container, the deionized water that temperature is 80~90 DEG C is added, sufficiently dissolves
It is 1.1~1.15 to specific gravity, obtains sodium carbonate liquor；
2.2) sodium carbonate liquor is cooled to 30 DEG C hereinafter, micro hydrogen peroxide is added after mixing evenly, stand 30 minutes and
More than；
2.3) sodium sulfide solution that concentration is 1.5~3% is added into step 2.2) acquired solution, after being sufficiently stirred, rises
Temperature is to 90~95 DEG C, and after heat preservation 2 hours, decaptitating is filtered in another container, and sodium carbonate filtered fluid after purification is obtained；Vulcanized sodium is molten
The volume ratio of liquid and step 2.2) acquired solution is 1.5-3:1000；
2.4) sampled from sodium carbonate filtered fluid, through ICP detection GOLD FROM PLATING SOLUTION category element of Fe, Cu, Ni, Cr, Co, Mn, Ti,
V, the content of Pb, if respectively less than 0.3ppm, the sodium carbonate filtered fluid purifying for showing that step 2.3) obtains is qualified, meets subsequent system
It is standby to require, enter step 3；If Fe content in the metallic element is less than 0.3ppm, but other either element contents are greater than etc.
In 0.3ppm, then return step 2.3)；If the Fe content in the metallic element is more than or equal to 0.3ppm, return step
2.2)；Step 3, carbonate synthesis copper:
3.1) step 1 is purified into qualified cupric sulphate crystal and adds deionized water, dissolve by heating to gravity be 1.02~
1.04；
3.2) step 2 is purified qualified sodium carbonate liquor to be added in enamel reaction still, in 50~60 DEG C of temperature and is stirred
In the state of, it is slowly added into the copper-bath that specific gravity is 1.02~1.04 and is reacted, reaction temperature is controlled 70
After~80 DEG C, reaction 5-10 minutes, reactant precipitating obtains peacock green copper carbonate；In entire reaction process, pH value should be protected
It holds 7.5~8；
3.3) reactant of step 3.2) is entered into plate and frame filter press, is washed in copper carbonate with 80~90 DEG C of deionized water
Sulfate ion, until sulfate ion content be 20-40ppm；
Step 4, synthesis biphosphate copper:
4.1) the high purity reagent grade phosphoric acid that concentration is 85% is added in enamel reaction still, then plus suitable deionized water
Dilution is evenly stirred until that concentration is 45-50%, 80~85 DEG C are warming up to, the carbonic acid that step 3.3) has been washed slowly is added portionwise
Copper, after adding material, continuing heat preservation reacts it completely in 30-45 minutes, and synthetic end point pH value is 2~3；Entire reaction process is kept
Temperature is 80~85 DEG C；
4.2) the resulting reaction solution of step 4.1) is warming up to 105~120 DEG C to be concentrated, crystalline film or ratio occurs in concentration
When weight is 1.46-1.48, blowing enters cooling container, is cooled to temperature at 55~60 DEG C, can stir once every 30min, until
It is cooled to room temperature, obtains the crystallization of biphosphate copper；
4.3) it pulls the crystallization of biphosphate copper out, enters centrifuge separation solid-liquor separation；
4.4) the biphosphate copper being centrifuged out is crystallized, it is 1.5~3 hours dry in 150~160 DEG C of baking oven；
Step 5, synthesis metaphosphoric acid copper:
5.1) the biphosphate copper crystallization after step 4.4) drying is packed into silica crucible and is calcined, calcination temperature 1400~
1500 DEG C, so that the crystallization of biphosphate copper is gradually aggregated into the metaphosphoric acid copper material of glass liquid, pour into
In the container for filling cooling deionized water, the metaphosphoric acid copper of disintegrating slag shape is formed；
5.2) the metaphosphoric acid copper of disintegrating slag shape and cooling deionized mixture are put into centrifuge, after solid-liquor separation, taken out
Metaphosphoric acid copper enters drying oven and is dried, and drying temperature is 120~125 DEG C, dries 4-6 hours to get metaphosphoric acid copper finished product.
Further, in step 1.4), during solid-liquor separation, mother liquor is collected, then using the side of step 1.1-1.3)
Method extracts cupric sulphate crystal from mother liquor, is used as the raw material of industry.
Further, in step 4.3), during solid-liquor separation, mother liquor is collected, then using the side of step 4.1-4.2)
Method extracts the crystallization of dihydrogen sulfate copper from the mother liquor of collection.
Further, add deionized water in step 1.1) into technical grade sulfuric acid copper raw material, be heated to 80-90 DEG C of dissolution sulphur
Sour copper, until copper-bath specific gravity is 1.12.
Further, the volume ratio of the hydrogen peroxide and copper-bath that are added in step 1.1) is 1-3:1000-1500.
Further, in step 1.2), high purity reagent sulfuric acid, adjustment pH value to 2.7 is added.
Further, the volume ratio of the hydrogen peroxide and sodium carbonate liquor that are added in step 2.2) is 1-1.5:1000-1500.
Further, sodium sulfide solution concentration described in step 2.3) is 2%.
Further, in step 4.2), reaction solution is warming up to 108 DEG C and is concentrated, crystalline film or specific gravity occurs in concentration
When being 1.47, blowing enters cooling container.
Further, calcination temperature is 1430 DEG C in step 5.1).
The invention has the advantages that
1, the metaphosphoric acid copper purity being prepared using method of the invention can reach 99.95% or more, can reach
99.99%, elementary metal impurities Fe, Ni, Cr, Co, Mn, Ti, V, Pb content is respectively less than 1.5ppm.
2, calcination temperature is set as 1400~1500 when the calcining of biphosphate copper is aggregated into metaphosphoric acid copper by the present invention
DEG C, calcination time 3~5 avoids cupric pyrophosphate by-product, ensure that the purity of metaphosphoric acid copper.
3, the present invention purifies carbonic acid sodium raw materials using the sodium sulfide solution that concentration is 2%, makes the metallic element in sodium carbonate
Impurity content Fe, Ni, Cr, Co, Mn, Ti, V, Pb most low energy drop to 0.3ppm, establish for subsequent preparation high-purity metaphosphoric acid copper
Basis.
4, preparation method of the present invention is simple to operate, and the yield and disposing mother liquor rate of product are high, and mother liquor is purified through concentrating
After processing, the rate of recovery is recycled and reuses, further improve economic benefit, reduce preparation cost up to 95% or more.
5, at 1430 DEG C, biphosphate copper is polymerized to metaphosphoric acid copper completely, samples at this time and obtains sample through XRD
Map is as shown in Figure 1, it will be seen from figure 1 that the standard diagram of metaphosphoric acid copper peak value prepared by the present invention and metaphosphoric acid copper is complete
It coincide, illustrates the stability of the made metaphosphoric acid crystalline quality of the present invention.
Detailed description of the invention
Fig. 1 is the present invention when aggregating into metaphosphoric acid copper to the calcining of biphosphate copper, takes metaphosphoric acid copper sample at 1430 DEG C
By the map of the obtained metaphosphoric acid copper sample of XRD.
Specific embodiment
The principle of preparation method of the present invention is as follows:
First purify technical grade sulfuric acid copper raw material (CuSO4·5H2) and carbonic acid sodium raw materials (Na O2CO3), then the two reacts shape
At high-purity copper carbonate (CuCO3) after, high-purity copper carbonate (CuCO3) again with high purity reagent grade phosphoric acid (H3PO4 it) reacts, preparation
Biphosphate copper (Cu (the H of high-purity out2PO4)2), plate compression forms the crystallization of biphosphate copper, finally enters stringent temperature control area
It bakes, to be prepared into the metaphosphoric acid copper (Cu (PO of high-purity3)2)。
Chemical equation is as follows:
1、CuSO4·5H2The purifying of O:
H2SO4+2FeSO4→Fe2(SO4)3+2H2O
Fe2(SO4)3+3Ba(OH)2→3BaSO4↓+2Fe(OH)3↓
Fe+++e→Fe+++、Fe+3+3OH-→Fe(OH)3↓
2, carbonate synthesis copper:
CuSO4·5H2O+Na2CO3→CuCO3+Na2SO4+5H2O
CuCO3+2H3PO4→Cu(H2PO4)2+CO2↑+H2O
Embodiment 1:
The preparation method of high-purity optical glass additive metaphosphoric acid copper:
Step 1, purification of sulphuric acids copper raw material:
1.1) it takes technical grade sulfuric acid copper raw material to be placed in enamel reaction still, deionized water is added to be heated to 80 DEG C of dissolution sulfuric acid
Copper, until copper-bath specific gravity is 1.12 (if specific gravity is too big, being unfavorable for sorption-coprecipitation Fe, Ni, Cr, Co, Mn, Ti, V, Pb), it will
Temperature is down to 35 DEG C, and hereinafter, hydrogen peroxide is added, (volume ratio of hydrogen peroxide and copper-bath is 3:1500), after mixing evenly, quiet
It sets 30 minutes, by the divalent ferrous ions in copper-bath at ferric ion, the hydroxide that concentration is 10% is added
Barium solution adjusts pH value to 3.5, after being sufficiently stirred, stands 4 hours；
1.2) solution for obtaining step 1.1) is filled into another container, and high purity reagent sulfuric acid is added, and adjusts pH value
To after 2.7, it is 1.28 that solution heating, which is concentrated to specific gravity, then decaptitating is filtered in another container；High purity reagent sulfuric acid, which refers to, to be contained
Amount is 99.99%, and elementary metal impurities Fe, Ni, Cr, Co, Mn, Ti, V, Pb content is respectively less than the sulfuric acid of 0.5ppm；
1.3) the high purity reagent sulfuric acid is added into filtrate obtained by step 1.2), adjusting pH value is 2, and then heating is concentrated to
Specific gravity is 1.48, is discharged, cooling, obtains cupric sulphate crystal；
1.4) it when being cooled to 30 DEG C, pulls cupric sulphate crystal out, enters centrifuge solid-liquor separation, during solid-liquor separation, spend
Ionized water washes away the free acid on cupric sulphate crystal surface to 200ppm hereinafter, centrifugal drying 30-60 minutes, takes out sulfuric acid after purification
Copper crystallization；For reduce production cost, during solid-liquor separation, can be recycled mother liquor, then use step 1.1-1.3) method, from
Cupric sulphate crystal is extracted in the mother liquor of recycling, the cupric sulphate crystal of extraction can be used as industrial sulphuric acid copper raw material.
1.5) it is sampled from cupric sulphate crystal, belongs to member through ICP (icp ms) detection GOLD FROM PLATING SOLUTION
The content of plain Fe, Ni, Cr, Co, Mn, Ti, V, Pb, if Fe is less than 2.5ppm, Ni, Cr, Co, Mn, Ti, V, Pb are respectively less than 1ppm,
The cupric sulphate crystal purifying for then showing that step 1.4) obtains is qualified, meets subsequent preparation requirement, enters step 2)；If Fe content is small
In 2.5ppm, but in Ni, Cr, Co, Mn, Ti, V, Pb, either element content is more than or equal to 1ppm, then return step 1.2)；If Fe
Content is more than or equal to 2.5ppm, then return step 1.1)；
Step 2, purifying carbonic acid sodium raw materials:
2.1) industrial sodium carbonate is put into another container, the deionized water that temperature is 80 DEG C is added, is sufficiently dissolved to ratio
The sodium carbonate liquor that weight is 1.15；
2.2) sodium carbonate liquor is cooled to 30 DEG C hereinafter, the hydrogen peroxide (volume ratio of hydrogen peroxide and sodium carbonate liquor is added
After mixing evenly for 1.5:1500), 40 minutes are stood；Here plus the purpose of hydrogen peroxide is that the divalent in sodium carbonate liquor is ferrous
Ionic oxide formation is coprecipitated convenient for subsequent adsorbtion at trivalent ferrous ion；
2.3) sodium sulfide solution that concentration is 2% is added into step 2.2) acquired solution, after being sufficiently stirred, is warming up to 95
DEG C, after heat preservation 2 hours, sulfide precipitation, decaptitating are converted by metallic element Fe, Ni, Cr, Co, Mn, Ti, V, Pb in solution
It filters in another container, obtains sodium carbonate filtered fluid after purification；The volume ratio of sodium sulfide solution and step 2.2) acquired solution
For 3:1000；
2.4) sampled from sodium carbonate filtered fluid, through ICP detection GOLD FROM PLATING SOLUTION category element of Fe, Ni, Cr, Co, Mn, Ti, V,
The content of Pb, if respectively less than 0.3ppm, the sodium carbonate filtered fluid purifying for showing that step 2.3) obtains is qualified, meets subsequent preparation
It is required that entering step 3；If Fe content is less than 0.3ppm, but either element content is more than or equal in Ni, Cr, Co, Mn, Ti, V, Pb
0.3ppm, then return step 2.3)；If Fe content is more than or equal to 0.3ppm, return step 2.2)；Step 3, carbonate synthesis copper:
3.1) step 1 is purified into qualified cupric sulphate crystal and adds deionized water, dissolving by heating to gravity is 1.02
Copper-bath；
3.2) step 2 is purified qualified sodium carbonate liquor to be added in enamel reaction still, in 60 DEG C of temperature and the shape of stirring
Under state, it is slowly added into the copper-bath that specific gravity is 1.02 and is reacted, reaction temperature is controlled at 80 DEG C, (if temperature
It is excessively high, be also easy to produce cupric oxide by-product, influence the purity of the metaphosphoric acid copper finished product of preparation), it reacts after ten minutes, reactant
Precipitating, obtains peacock green copper carbonate；In entire reaction process, pH value should be maintained at 7.5~8, because pH value is less than 7.5,
Sulfate ion in copper carbonate is not easy to wash off；
3.3) reactant of step 3.2) is entered into plate and frame filter press, the sulphur in copper carbonate is washed with 80 DEG C of deionized water
Acid ion, until sulfate ion content is 20-40ppm；
Step 4, synthesis biphosphate copper:
4.1) by concentration be 85% high purity reagent phosphoric acid be added in enamel reaction still, then plus suitable deionized water it is dilute
It releases and is evenly stirred until that concentration is 45%, be warming up to 80 DEG C, the copper carbonate that step 3.3) has been washed slowly is added portionwise, adds material
Afterwards, continuing heat preservation reacts it completely in 45 minutes, and synthetic end point pH value is 3；It is 80 DEG C that entire reaction process, which keeps temperature,；And begin
It keeps reaction solution clear and transparent eventually, keeps solution clear if it find that solution muddiness can supplement the high purity reagent phosphoric acid that concentration is 85%
It is bright；During the reaction, a large amount of water volatilizees, it can appropriate moisturizing according to the actual situation；High purity reagent phosphoric acid refers to metal member
Plain impurity F e, Ni, Cr, Co, Mn, Ti, V, Pb content is respectively less than the phosphoric acid of 0.5ppm；
4.2) the resulting reaction solution of step 4.1) is warming up to 108 DEG C to be concentrated, concentration crystalline film occurs or specific gravity is
When 1.47, blowing enters cooling container, is cooled to temperature at 55 DEG C, can be primary every stirring in 30 minutes, until being cooled to room temperature, obtains
The crystallization of biphosphate copper；
4.3) it pulls the crystallization of biphosphate copper out, enters centrifuge separation solid-liquor separation；To reduce production cost, in solid-liquor separation
Mother liquor can be recycled in period, after qualified to mother liquor purification process, then using the method for step 4.1-4.2), from the mother liquor of recycling
Middle extraction biphosphate copper crystallization, again crystallizes the biphosphate copper into centrifuge solid-liquor separation；
The step of to mother liquor purification process: (1) being added deionized water into mother liquor, after mixing evenly, adjusts specific gravity to 1.10-
1.15；(2) metastannic acid for adding 0.5-1% into mother liquor, heats 80-90 degree, keeps the temperature 2-3 hours, decaptitating is filtered into another container
It is interior；(3) sampling carries out ICP detection GOLD FROM PLATING SOLUTION category element of Fe from mother liquor filtered fluid, Ni, Cr, Co, Mn, Ti, V, Pb contain
Amount, if respectively less than 0.3ppm, the mother liquor filtered fluid purifying for showing that step (2) obtains is qualified, meets subsequent preparation requirement.
4.4) the biphosphate copper being centrifuged out is crystallized, it is 2 hours dry in 150~160 DEG C of baking oven；
Step 5, synthesis metaphosphoric acid copper:
5.1) the biphosphate copper crystallization after step 4.4) drying is packed into calcining, calcination temperature 1430 in silica crucible
DEG C, it calcines 5 hours, the crystallization of biphosphate copper is made gradually to aggregate into the metaphosphoric acid copper material of glass liquid, pour into and fill cooling
In the container of ionized water, the metaphosphoric acid copper of disintegrating slag shape is formed；
5.2) the metaphosphoric acid copper of disintegrating slag shape and cooling deionized mixture are put into centrifuge, after solid-liquor separation, taken out
Metaphosphoric acid copper enters drying oven and is dried, and drying temperature is 120 DEG C, dries 6 hours to get metaphosphoric acid copper finished product.
Embodiment 2:
The preparation method of high-purity optical glass additive metaphosphoric acid copper:
Step 1, purification of sulphuric acids copper raw material:
1.1) it takes technical grade sulfuric acid copper raw material to be placed in enamel reaction still, deionized water is added to be heated to 90 DEG C of dissolution sulfuric acid
Copper, until copper-bath specific gravity is 1.1, cooling the temperature to 35 DEG C, (hydrogen peroxide is molten with copper sulphate hereinafter, micro hydrogen peroxide is added
The volume ratio of liquid is 1:1000), it after mixing evenly, stands after forty minutes, the barium hydroxide solution that concentration is 12% is added, adjust PH
Value after being sufficiently stirred, stands 4 hours to 4.2；
1.2) solution for obtaining step 1.1) is filled into another container, and high purity reagent sulfuric acid is added, and adjusts pH value
To after 3, it is 1.3 that solution heating, which is concentrated to specific gravity, then decaptitating is filtered in another container；High purity reagent sulfuric acid refers to that content is
99.99%, elementary metal impurities Fe, Ni, Cr, Co, Mn, Ti, V, Pb content is respectively less than the sulfuric acid of 0.5ppm；
1.3) the high purity reagent sulfuric acid is added into filtrate obtained by step 1.2), adjusting pH value is 1, and then heating is concentrated to
Specific gravity is 1.50, is discharged, cooling, obtains cupric sulphate crystal；
1.4) it when being cooled to 25 DEG C, pulls cupric sulphate crystal out, enters centrifuge solid-liquor separation, during solid-liquor separation, spend
Ionized water washes away the free acid on cupric sulphate crystal surface to 200ppm hereinafter, centrifugal drying 40 minutes, takes out copper sulphate after purification
Crystallization；
1.5) it is sampled from cupric sulphate crystal, belongs to member through ICP (icp ms) detection GOLD FROM PLATING SOLUTION
The content of plain Fe, Ni, Cr, Co, Mn, Ti, V, Pb, if Fe is less than 2.5ppm, Ni, Cr, Co, Mn, Ti, V, Pb are respectively less than 1ppm,
The cupric sulphate crystal purifying for then showing that step 1.4) obtains is qualified, meets subsequent preparation requirement, enters step 2)；If Fe content is small
In 2.5ppm, but in Ni, Cr, Co, Mn, Ti, V, Pb, either element content is more than or equal to 1ppm, then return step 1.2)；If Fe
Content is more than or equal to 2.5ppm, then return step 1.1)；
Step 2, purifying carbonic acid sodium raw materials:
2.1) industrial sodium carbonate is put into another container, deionized water at a temperature of 90 °C is added, be sufficiently dissolved to ratio
The sodium carbonate liquor that weight is 1.1；
2.2) sodium carbonate liquor is cooled to 30 DEG C hereinafter, the micro hydrogen peroxide (body of hydrogen peroxide and sodium carbonate liquor is added
Product is than being 1:1000) after mixing evenly, stand 30 minutes；
2.3) sodium sulfide solution that concentration is 3% is added into step 2.2) acquired solution, after being sufficiently stirred, is warming up to 90
DEG C, after heat preservation 2 hours, sulfide precipitation, decaptitating are converted by metallic element Fe, Ni, Cr, Co, Mn, Ti, V, Pb in solution
It filters in another container, obtains sodium carbonate filtered fluid after purification；The volume ratio of sodium sulfide solution and step 2.2) acquired solution
For 2:1000；
2.4) sampled from sodium carbonate filtered fluid, through ICP detection GOLD FROM PLATING SOLUTION category element of Fe, Ni, Cr, Co, Mn, Ti, V,
The content of Pb, if respectively less than 0.3ppm, the sodium carbonate filtered fluid purifying for showing that step 2.3) obtains is qualified, meets subsequent preparation
It is required that entering step 3；If Fe content is less than 0.3ppm, but either element content is more than or equal in Ni, Cr, Co, Mn, Ti, V, Pb
0.3ppm, then return step 2.3)；If Fe content is more than or equal to 0.3ppm, return step 2.2)；Step 3, carbonate synthesis copper:
3.1) step 1 is purified into qualified cupric sulphate crystal and adds deionized water, dissolving by heating to gravity is 1.04；
3.2) step 2 is purified qualified sodium carbonate liquor to be added in enamel reaction still, in 50 DEG C of temperature and the shape of stirring
It under state, is slowly added into the copper-bath that specific gravity is 1.04 and is reacted, reaction temperature is controlled at 75 DEG C, reaction 10
After minute, reactant precipitating obtains peacock green copper carbonate；In entire reaction process, pH value should be maintained at 7.5~8；
3.3) reactant of step 3.2) is entered into plate and frame filter press, the sulphur in copper carbonate is washed with 90 DEG C of deionized water
Acid ion, until sulfate ion content is 20-40ppm；
Step 4, synthesis biphosphate copper:
4.1) by concentration be 85% high purity reagent phosphoric acid be added in enamel reaction still, then plus suitable deionized water it is dilute
It releases and is evenly stirred until that concentration is 50%, be warming up to 85 DEG C, the copper carbonate that step 3.3) has been washed slowly is added portionwise, adds material
Afterwards, continuing heat preservation reacts it completely in 45 minutes, and synthetic end point pH value is 3；It is 85 DEG C that entire reaction process, which keeps temperature,；And begin
It keeps reaction solution clear and transparent eventually, keeps solution clear if it find that solution muddiness can supplement the high purity reagent phosphoric acid that concentration is 85%
It is bright；During the reaction, a large amount of water volatilizees, it can appropriate moisturizing according to the actual situation；High purity reagent phosphoric acid refers to metal member
Plain impurity F e, Ni, Cr, Co, Mn, Ti, V, Pb content is respectively less than the phosphoric acid of 0.5ppm；
4.2) the resulting reaction solution of step 4.1) is warming up to 120 DEG C to be concentrated, concentration crystalline film occurs or specific gravity is
When 1.48, blowing enters cooling container, is cooled to temperature at 60 DEG C, can stir once every 30min, until being cooled to room temperature, obtain
The crystallization of biphosphate copper；
4.3) it pulls the crystallization of biphosphate copper out, enters centrifuge separation solid-liquor separation；
4.4) the biphosphate copper being centrifuged out is crystallized, it is 3 hours dry in 150~160 DEG C of baking oven；
Step 5, synthesis metaphosphoric acid copper:
5.1) the biphosphate copper crystallization after step 4.4) drying is packed into calcining, calcination temperature 1500 in silica crucible
DEG C, it calcines 3 hours, the crystallization of biphosphate copper is made gradually to aggregate into the metaphosphoric acid copper material of glass liquid, pour into and fill cooling
In the container of ionized water, the metaphosphoric acid copper of disintegrating slag shape is formed；
5.2) the metaphosphoric acid copper of disintegrating slag shape and cooling deionized mixture are put into centrifuge, after solid-liquor separation, taken out
Metaphosphoric acid copper enters drying oven and is dried, and drying temperature is 125 DEG C, dries 5 hours to get metaphosphoric acid copper finished product.
The testing result difference of above-described embodiment 1-2 preparation gained metaphosphoric acid copper products is as follows:
Embodiment 1:
Purity 99.99%, elementary metal impurities Fe, Cu, Ni, Cr, Co, Mn, Ti, V, Pb content are respectively less than 1.5ppm.
Embodiment 2:
Purity 99.95%, elementary metal impurities Fe, Cu, Ni, Cr, Co, Mn, Ti, V, Pb content are respectively less than 1.5ppm.
Claims (10)
1. a kind of preparation method of high-purity optical glass additive metaphosphoric acid copper, which comprises the following steps:
Step 1, purification of sulphuric acids copper raw material:
1.1) it takes technical grade sulfuric acid copper raw material to be placed in enamel reaction still, deionized water is added to be heated to 80-90 DEG C of dissolution copper sulphate,
It is 1.1~1.15 to copper-bath specific gravity, cools the temperature to 35 DEG C hereinafter, micro hydrogen peroxide is added, it is after mixing evenly, quiet
After setting 30 minutes or more, the barium hydroxide solution that addition concentration is 10-12%, tune pH value to 3.5~4.2, after being sufficiently stirred,
Stand 4 hours or more；
1.2) solution for obtaining step 1.1) is filled into another container, and high purity reagent sulfuric acid is added and adjusts pH value to 2.5
After~3, it is 1.28~1.3 that solution heating, which is concentrated to specific gravity, then decaptitating is filtered in another container；
1.3) the high purity reagent sulfuric acid is added into filtrate obtained by step 1.2), adjusting pH value is 1~2, and then heating is concentrated to
Specific gravity is 1.48~1.50, is discharged, cooling, obtains cupric sulphate crystal；
1.4) when being cooled to 25-30 DEG C, pull cupric sulphate crystal out, enter centrifuge solid-liquor separation, during solid-liquor separation, spend from
Son washing goes the free acid of copper sulphate crystal surface to 200ppm hereinafter, centrifugal drying -60 minutes 30 minutes, takes out sulphur after purification
Sour copper crystallization；
1.5) it samples from cupric sulphate crystal, contains through ICP detection GOLD FROM PLATING SOLUTION category element of Fe, Ni, Cr, Co, Mn, Ti, V, Pb
Amount, if Fe is less than 2.5ppm, Ni, Cr, Co, Mn, Ti, V, Pb are respectively less than 1ppm, then show the copper sulphate knot that step 1.4) obtains
Crystalline substance purifying is qualified, meets subsequent preparation requirement, enters step 2)；If the Fe content in the metallic element is less than 2.5ppm, but
Other either element contents are more than or equal to 1ppm, then return step 1.2)；If the Fe content in the metallic element is more than or equal to
2.5ppm, then return step 1.1)；
Step 2, purifying carbonic acid sodium raw materials:
2.1) industrial sodium carbonate is put into another container, the deionized water that temperature is 80~90 DEG C is added, is sufficiently dissolved to ratio
Weight is 1.1~1.15, obtains sodium carbonate liquor；
2.2) sodium carbonate liquor is cooled to 30 DEG C hereinafter, micro hydrogen peroxide is added after mixing evenly, stand 30 minutes or more；
2.3) sodium sulfide solution that concentration is 1.5~3% is added into step 2.2) acquired solution, after being sufficiently stirred, is warming up to
After 90~95 DEG C, heat preservation 2 hours, decaptitating is filtered in another container, and sodium carbonate filtered fluid after purification is obtained；Sodium sulfide solution with
The volume ratio of step 2.2) acquired solution is 1.5-3:1000；
2.4) it is sampled from sodium carbonate filtered fluid, detects GOLD FROM PLATING SOLUTION category element of Fe, Cu, Ni, Cr, Co, Mn, Ti, V, Pb through ICP
Content show that the sodium carbonate filtered fluid purifying that step 2.3) obtains is qualified if respectively less than 0.3ppm, meet subsequent preparation and want
It asks, enters step 3；If the Fe content in the metallic element is less than 0.3ppm, but other either element contents are more than or equal to
0.3ppm, then return step 2.3)；If the Fe content in the metallic element is more than or equal to 0.3ppm, return step 2.2)；
Step 3, carbonate synthesis copper:
3.1) step 1 is purified into qualified cupric sulphate crystal and adds deionized water, dissolving by heating to gravity is 1.02~1.04；
3.2) step 2 is purified qualified sodium carbonate liquor to be added in enamel reaction still, in 50~60 DEG C of temperature and the shape of stirring
Under state, it is slowly added into the copper-bath that specific gravity is 1.02~1.04 and is reacted, reaction temperature is controlled 70~80
DEG C, after reaction 5-10 minutes, reactant precipitating obtains peacock green copper carbonate；In entire reaction process, pH value should be maintained at
7.5~8；
3.3) reactant of step 3.2) is entered into plate and frame filter press, the sulphur in copper carbonate is washed with 80~90 DEG C of deionized water
Acid ion, until sulfate ion content is 20-40ppm；
Step 4, synthesis biphosphate copper:
4.1) the high purity reagent grade phosphoric acid that concentration is 85% is added in enamel reaction still, then plus suitable deionized water dilution
It is evenly stirred until that concentration is 45-50%, 80~85 DEG C are warming up to, the copper carbonate that step 3.3) has been washed slowly is added portionwise, adds
After complete material, continuing heat preservation reacts it completely in 30-45 minutes, and synthetic end point pH value is 2~3；Entire reaction process keeps temperature
It is 80~85 DEG C；
4.2) the resulting reaction solution of step 4.1) is warming up to 105~120 DEG C to be concentrated, concentration crystalline film occurs or specific gravity is
When 1.46-1.48, blowing enters cooling container, is cooled to temperature at 55~60 DEG C, can stir once every 30min, until cooling
To room temperature, the crystallization of biphosphate copper is obtained；
4.3) it pulls the crystallization of biphosphate copper out, enters centrifuge separation solid-liquor separation；
4.4) the biphosphate copper being centrifuged out is crystallized, it is 1.5~3 hours dry in 150~160 DEG C of baking oven；
Step 5, synthesis metaphosphoric acid copper:
5.1) the biphosphate copper crystallization after step 4.4) drying is packed into calcining, calcination temperature 1400~1500 in silica crucible
DEG C, so that the crystallization of biphosphate copper is gradually aggregated into the metaphosphoric acid copper material of glass liquid, pours into and fill
In the container of cooling deionized water, the metaphosphoric acid copper of disintegrating slag shape is formed；
5.2) the metaphosphoric acid copper of disintegrating slag shape and cooling deionized mixture are put into centrifuge, after solid-liquor separation, take out inclined phosphorus
Sour copper enters drying oven and is dried, and drying temperature is 120~125 DEG C, dries 4-6 hours to get metaphosphoric acid copper finished product.
2. the preparation method of high-purity optical glass additive metaphosphoric acid copper according to claim 1, it is characterised in that: step
It is rapid 1.4) in, during solid-liquor separation, collect mother liquor, then use step 1.1-1.3) method, sulfuric acid is extracted from mother liquor
Copper crystallization, is used as the raw material of industry.
3. the preparation method of high-purity optical glass additive metaphosphoric acid copper according to claim 2, it is characterised in that: step
It is rapid 4.3) in, during solid-liquor separation, collect mother liquor, then use step 4.1-4.2) method, mentioned from the mother liquor of collection
Dihydrogen sulfate copper is taken to crystallize.
4. the preparation method of high-purity optical glass additive metaphosphoric acid copper according to claim 1,2 or 3, feature exist
In: add deionized water in step 1.1) into technical grade sulfuric acid copper raw material, 80-90 DEG C of dissolution copper sulphate is heated to, until copper sulphate
Gravity is 1.12.
5. the preparation method of high-purity optical glass additive metaphosphoric acid copper according to claim 4, it is characterised in that: step
The volume ratio of rapid 1.1) the middle hydrogen peroxide being added and copper-bath is 1-3:1000-1500.
6. the preparation method of high-purity optical glass additive metaphosphoric acid copper according to claim 5, it is characterised in that: step
It is rapid 1.2) in, high purity reagent sulfuric acid is added, adjustment pH value is to 2.7.
7. the preparation method of high-purity optical glass additive metaphosphoric acid copper according to claim 6, it is characterised in that: step
The volume ratio of rapid 2.2) the middle hydrogen peroxide being added and sodium carbonate liquor is 1-1.5:1000-1500.
8. the preparation method of high-purity optical glass additive metaphosphoric acid copper according to claim 7, it is characterised in that: step
It is rapid 2.3) described in sodium sulfide solution concentration be 2%.
9. the preparation method of high-purity optical glass additive metaphosphoric acid copper according to claim 8, it is characterised in that: step
It is rapid 4.2) in, reaction solution is warming up to 108 DEG C and is concentrated, crystalline film or specific gravity occurs in concentration when being 1.47, and blowing enters cooling
Container.
10. the preparation method of high-purity optical glass additive metaphosphoric acid copper according to claim 9, it is characterised in that:
Calcination temperature is 1430 DEG C in step 5.1).
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| CN111579714A (en) * | 2020-06-28 | 2020-08-25 | 成都光明光电股份有限公司 | Method for measuring content of copper oxide in copper metaphosphate |
| CN114275752A (en) * | 2022-01-21 | 2022-04-05 | 上海太洋科技有限公司 | Preparation method of high-purity copper pyrophosphate |
| CN114275753A (en) * | 2022-01-21 | 2022-04-05 | 上海太洋科技有限公司 | Preparation method of high-purity copper metaphosphate |
| CN115924871A (en) * | 2022-12-02 | 2023-04-07 | 上海太洋科技有限公司 | Preparation method of optical-grade copper metaphosphate |
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| JPH06207161A (en) * | 1993-01-12 | 1994-07-26 | Asahi Glass Co Ltd | Improved near infrared light absorbing material and ink using the same |
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| CN111579714A (en) * | 2020-06-28 | 2020-08-25 | 成都光明光电股份有限公司 | Method for measuring content of copper oxide in copper metaphosphate |
| CN114275752A (en) * | 2022-01-21 | 2022-04-05 | 上海太洋科技有限公司 | Preparation method of high-purity copper pyrophosphate |
| CN114275753A (en) * | 2022-01-21 | 2022-04-05 | 上海太洋科技有限公司 | Preparation method of high-purity copper metaphosphate |
| CN115924871A (en) * | 2022-12-02 | 2023-04-07 | 上海太洋科技有限公司 | Preparation method of optical-grade copper metaphosphate |
| CN115924871B (en) * | 2022-12-02 | 2023-09-15 | 上海太洋科技有限公司 | Preparation method of optical-grade copper metaphosphate |
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