CN110981219A - Salt bath impurity ion purification method - Google Patents
Salt bath impurity ion purification method Download PDFInfo
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- CN110981219A CN110981219A CN201911267944.4A CN201911267944A CN110981219A CN 110981219 A CN110981219 A CN 110981219A CN 201911267944 A CN201911267944 A CN 201911267944A CN 110981219 A CN110981219 A CN 110981219A
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- salt bath
- lithium
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- stabilizer
- ions
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- 150000003839 salts Chemical class 0.000 title claims abstract description 119
- 239000012535 impurity Substances 0.000 title claims abstract description 37
- 238000000746 purification Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003381 stabilizer Substances 0.000 claims abstract description 41
- 230000002745 absorbent Effects 0.000 claims abstract description 34
- 239000002250 absorbent Substances 0.000 claims abstract description 34
- 150000002500 ions Chemical class 0.000 claims abstract description 29
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims abstract description 8
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 5
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 5
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 7
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 235000011008 sodium phosphates Nutrition 0.000 claims description 6
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- UTBYQPSPFXHANA-UHFFFAOYSA-N [K].[Na].[Li] Chemical compound [K].[Na].[Li] UTBYQPSPFXHANA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 30
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 description 23
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 8
- 238000005728 strengthening Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 238000003426 chemical strengthening reaction Methods 0.000 description 4
- 239000005345 chemically strengthened glass Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- -1 lithium aluminum silicon Chemical compound 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000006058 strengthened glass Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012521 purified sample Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- 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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention provides a salt bath impurity ion purification method, which comprises the steps of heating a salt bath to a reaction temperature of 350-500 ℃, wherein the salt bath is pure salt or mixed salt containing potassium nitrate and/or sodium nitrate and/or lithium nitrate; the salt bath impurity ions are formed by contacting an exchange substrate containing lithium ions with the salt bath, exchanging the lithium ions on the exchange glass substrate with sodium ions in the salt bath and diffusing the lithium ions into the salt bath; when the impurity ion lithium ion exceeds a standard value, adding an absorbent and a stabilizer; the absorbent is phosphate; the stabilizer has a siloxy group and/or has the property of a siloxy group. The invention provides a salt bath regeneration or purification and impurity removal mode, absorbs salt bath compound impurities to maintain the salt bath stable state, reduces additional damage to glass products, and finally improves the preparation process effect.
Description
Technical Field
The invention relates to the technical field of glass chemical strengthening production, in particular to a purification method of a glass reaction salt bath.
Background
At present, in the chemical strengthening process of glass, because the surface compressive stress generation process of the glass is salt bath large ion exchange salt bath small ion, small ion Na in the glass can be generated in the continuous strengthening process+、Li+Continuously enter salt bath to form impurity ions, especially Li+Although only PPM level, has severely hindered the normal chemical strengthening process, resulting in strong subsequent samplesThe CS value after conversion is lowered, and the monomer strength is lowered.
After the glass is chemically strengthened, because large ions in the salt bath replace small ions in the salt bath, the glass can generate size expansion, and the increase of impurity ions can weaken the ion exchange capacity, especially Li+The increase of the amount of the lithium aluminum silicon chemically strengthened glass leads to the severe weakening of the sodium-lithium exchange degree of the lithium aluminum silicon chemically strengthened glass, thus leading to the rapid reduction of the size expansion after strengthening, and the increase of Li + in salt bath leads to the lower limit of the volume production size of the lithium aluminum silicon chemically strengthened glass.
For the above situation, the phosphate salt is dissolved in the salt bath in the current chemically strengthened glass factory, and the phosphate salt forms lithium phosphate with lithium ions to precipitate. The method is characterized in that the salt bath is turbid, the salt bath is available after being clarified for 24-48 hours for a long time, lithium phosphate is precipitated, and partial lithium phosphate particles are suspended in the salt bath and attached to the surface of the strengthened glass, so that the glass generates defects. Excess lithium phosphate will form phosphate crystals comprising Na3PO4 with sodium on the glass substrate. As the large phosphate crystals are removed from the glass substrate after cleaning, surface defects can be seen on the glass substrate, for example, causing the glass to cause irreversible permanent damage such as a bump defect or surface haze corrosion, which reduces the mechanical strength of the glass. Therefore, the purification of salt bath impurity ions is imminent.
Disclosure of Invention
The invention relates to chemical strengthening production of glass, and mainly aims to provide a salt bath regeneration or purification impurity removal mode, absorb salt bath compound impurities to maintain a salt bath stable state, reduce additional damage of an absorbent to a glass product and finally improve the preparation process efficiency.
In order to achieve the above object, the present invention provides a method for purifying impurity ions in a salt bath, wherein the salt bath is heated to a reaction temperature of 350 to 500 ℃ and contains pure salts or mixed salts of potassium nitrate and/or sodium nitrate and/or lithium nitrate; for contacting an exchange substrate containing lithium ions with the salt bath and diffusion dissolving the lithium ions from the exchange substrate in the salt bath;
when the concentration of impurity ions and lithium ions exceeds a standard value, adding an absorbent and a stabilizer;
the absorbent is phosphate; the stabilizer has a siloxy group and/or has siloxy properties.
Preferably, the absorbent is sodium phosphate and/or sodium dihydrogen phosphate, and forms reactive precipitation and suspended particles with impurity lithium ions in the salt bath; the reactive precipitate and suspended particles include: insoluble Li3PO4, insoluble Li2NaPO4Or insoluble LiNa2PO4At least one of (1).
Preferably, the reactive precipitate and suspending particles are adsorbed on the stabilizer surface by the stabilizer.
Preferably, the stabilizer comprises at least one of silica \ silicic acid \ metasilicate \ silicate containing covalent bonds of silica. For example, the stabilizer is at least one of silica sand, silicone oil, diatomite and silica gel.
Preferably, the amount of said absorbent dosed is between 0.1 and 2 wt% of the salt bath to be purified.
Preferably, the amount of the stabilizer added is 50% or less of the mass of the absorbent.
Preferably, the amount of the stabilizer added is 20% or less of the mass of the absorbent.
Preferably, the stabilizer is dosed in sequence with or after the absorbent.
Preferably, the standard value is such as to keep the lithium ions in the salt bath below 300 PPm.
Preferably, the standard value is such as to keep the lithium ions in the salt bath below 200 PPm.
Preferably, the standard value is such as to keep the lithium ions in the salt bath below 150 PPm.
Preferably, the purification salt bath is a potassium-sodium mixed salt bath or a pure sodium salt bath, and lithium ions in the purified salt bath are lower than 300 PPm.
Preferably, the purification salt bath is a potassium-sodium-lithium mixed salt bath or a sodium-lithium salt bath, and lithium ions in the salt bath are stabilized between a specified value of plus or minus 500PPm after being fed and purified.
According to the invention, lithium phosphate generated in the using process of the impurity ion absorbent phosphate is introduced into the salt bath and is precipitated so as to be attached to glass to generate defects.
Furthermore, the scheme provided by the invention is that an absorbent and a stabilizer are added into the impurity ion salt bath, the absorbent is phosphate, and the stabilizer is a silicon-oxy group-containing stabilizer such as silicone oil, diatomite, silica gel and the like, and can actively adsorb lithium phosphate precipitate, so that the lithium phosphate precipitate cannot be precipitated at the bottom, and the lithium phosphate precipitate is prevented from being suspended in the salt bath due to excessive precipitation, so that the problems of glass defects generated when the impurities are removed by the phosphate and difficult treatment of the bottom precipitate are effectively solved. Furthermore, the salt bath impurity ion purification method can quickly exert the absorption effect, is convenient and quick to take out, and reduces the influence on the production efficiency.
For the problems of salt bath turbidity, production interruption and efficiency reduction caused by adding a phosphate absorbent, the absorbent and the stabilizer can be simultaneously added according to the optimal proportion, and the stabilizer can quickly adsorb suspended matters to clarify the salt bath and can be used within 1-2 hours in a short time. The continuous strengthening operation of the salt bath is ensured, the continuous production is convenient, and the production efficiency is improved.
Detailed Description
The embodiments described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The ions exchanged in the salt bath are sodium ions and/or lithium ions. In multi-batch strengthening, because the glass can continuously precipitate lithium ions during strengthening, the concentration of the lithium ions in the salt bath is gradually increased, and the salt bath exceeds the standard, purified substances can be added to remove impurities from the lithium ions after strengthening for a plurality of times. However, excessive purification can lead to glass quality problems that can be effectively reduced by using purified samples with stabilizers.
The invention relates to a strengthened glass salt bath process, in particular to a method for regenerating or reducing surface defects after salt bath poisoning.
The salt bath impurity ion purification method comprises the following steps:
step 1: preparing a salt bath; the salt bath contains pure salt or mixed salt of potassium nitrate and/or sodium nitrate and/or lithium nitrate;
step 2: preparing an exchange substrate containing lithium ions;
and step 3: immersing and heating the exchange substrate into a salt bath with the reaction temperature of 350-500 ℃;
and 4, step 4: contacting an exchange substrate containing lithium ions with the salt bath and diffusion dissolving the lithium ions from the exchange substrate in the salt bath;
when the concentrations of the impurity ions, namely lithium ions and sodium ions, exceed standard values, an absorbent and a stabilizer are added. The standard value can be, for example, that the purified salt bath is a potassium-sodium-lithium mixed salt bath or a sodium-lithium salt bath, lithium ions in the salt bath are stabilized between a specified value of plus or minus 500PPm after being put into the salt bath after purification, or the purified salt bath is a potassium-sodium mixed salt bath or a pure sodium salt bath, the salt bath after ion exchange contains excessive impurity lithium ions, the impurity lithium ions exceed the standard value of 500PPm, and the lithium ions in the salt bath after purification are lower than 300 PPm; optionally, the normalized value is to maintain lithium ions below 200PPm in the salt bath; preferably, the standard value is such as to keep the lithium ions in the salt bath below 150 PPm. If the mixed salt bath contains lithium nitrate, the lithium nitrate does not exceed 5 wt%, and the salt bath extract is used in such a way that the concentration of lithium ions in the salt bath is stabilized within a certain range, rather than absorbing lithium ions in the salt bath to below 300 PPm.
In the examples, the absorbent is dosed in an amount of 0.1-2 wt.% of the salt bath to be purified. The adding sequence of the stabilizing agent is that the stabilizing agent is added simultaneously with the absorbent or later than the absorbent.
The adding amount of the absorbent is less than 50% of the mass of the stabilizer; preferably, the amount of the absorbent to be added is 20% or less of the mass of the stabilizer.
Wherein the absorbent is a phosphate salt, such as sodium phosphate and/or sodium dihydrogen phosphate, and forms reactive precipitates and suspended particles with lithium ions as impurities in the salt bath; the reactive precipitate and suspended particles include: at least one of insoluble Li3PO4, insoluble Li2NaPO4, or insoluble LiNa2PO 4. These reactive precipitates and suspended particles are increasing, which also increases the level of salt bath contamination and reduces salt bath quality.
Therefore, in this example, the stabilizer is added in combination with the absorbent. The stabilizer has a siloxy group and/or has the property of a siloxy group; for example, comprising at least one of silicon dioxide, silicic acid, metasilicate, silicates containing covalent bonds of silicon oxygen. Specifically, the stabilizer may be, for example, at least one of silica sand, silicone oil, diatomaceous earth, and silica gel.
The stabilizer is adsorbed in the salt bath without decomposition and reaction with the glass, and the reactive precipitate and suspended particles are adsorbed on the surface of the stabilizer by the stabilizer.
The absorbent and the stabilizer can be powder, granules or slurry.
The experiments with absorption and impurity removal as main purposes are as follows:
the experimental process comprises the following steps: the glass base material is used as an exchange base material, the salt bath is 87 wt% of potassium nitrate, 12 wt% of sodium nitrate and 1 wt% of lithium nitrate, and the reaction temperature is 480 ℃. The weight ratio of the lithium ions in the salt bath is 1000PPm through conversion, and the preferred concentration range is between 1000 and 1500 PPm. The lithium ion concentration in the salt bath gradually exceeds this range because the glass is constantly precipitating lithium ions during strengthening, and this is preferable for maintaining the lithium ions in the salt bath. During continuous batch strengthening, a purification sample containing a stabilizing agent is continuously added, so that excess lithium ions in the salt bath can be absorbed and stabilized at 1000-1500PPm, and the defects of glass can not be caused by adding for many times.
The exchange substrate is fully immersed in the salt bath in ion exchange, and the sample at the lowermost portion of the reinforcement is raised above the bottom salt bath by 5mm or more, preferably 10 mm. And performing the feeding of the absorbent and the stabilizer according to a standard value for keeping lithium ions in the salt bath to be lower than 300 PPm; the corresponding purification agents were added in the comparative examples.
After the purification agent was added, the surface defects of the next tempered glass were observed.
5 experiments, and 2 comparative examples were performed in parallel.
Table 1: experimental parameters
TABLE 2 comparison of purification results
| Surface of the X-th purified glass Defective condition | Experiment 1 | Experiment 2 | Experiment 3 | Experiment 4 | Experiment 5 | Comparative example 1 | Comparative example 2 |
| 0 | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of |
| 1 | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of |
| 2 | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of |
| 3 | Is free of | Is free of | Is free of | Is free of | Is free of | 3-4 parts of bulges Point defect | Is free of |
| 4 | Is free of | Is free of | Is free of | Is free of | Is free of | 10 raised points Defect of | Is free of |
| 5 | Is free of | Is free of | Is free of | Is free of | Is free of | 14 raised points Defect of | Is free of |
| 6 | Is free of | Is free of | Is free of | Is free of | Is free of | Raised points at 23 Defect of | Surface fog corrosion Etching solution |
| 7 | Is free of | Is free of | Is free of | Is free of | Is free of | 24 raised points Defect of | Surface fog corrosion Etching solution |
| 8 | Is free of | Is free of | Is free of | Is free of | Is free of | Raised point at 29 Defect of | Surface fog corrosion Etching solution |
| 9 | 2-3 raised points Defect of | 2-3 raised points Defect of | 2-3 raised points Defect of | 2-3 parts of bulges Point defect | 2-3 raised points Defect of | 33 raised points Defect of | Surface fog corrosion Etching solution |
| Salt bath ion concentration after purification | 115PPm | 166PPm | 217PPm | 118PPm | 111PPm | 118PPm | 125PPm |
As can be seen from the above table, in experiments 1 to 5, the glass surface was still free of defects after the addition and purification of the absorbent and the stabilizer for 8 times. Thus showing that the salt bath can continuously strengthen the glass. In comparative examples 1 and 2, a plurality of defects or corrosion occurred after the purification agent was added 3 to 5 times.
According to the analysis of the application, when the absorbent (such as sodium phosphate) is added for too many times, most of lithium phosphate generated by the reaction can be precipitated, but a small part of lithium phosphate can be suspended in the salt bath, so that lithium phosphate and sodium phosphate suspended in the salt bath can react with lithium ions or sodium ions in the glass surface to form surface defects. The suspended portion of sodium phosphate and lithium phosphate is a minor portion of the absorbent and the stabilizer reacts with and adsorbs to the surface of the stabilizer. The amount of the lithium phosphate is less than the input amount of the absorbent, and because the precipitated lithium phosphate part does not influence the surface performance of the glass, the lithium phosphate is not required to be reacted and adsorbed by a stabilizing agent.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (8)
1. A salt bath impurity ion purification method is characterized in that the salt bath is heated to a reaction temperature of 350-500 ℃ and contains pure salt or mixed salt of potassium nitrate and/or sodium nitrate and/or lithium nitrate; the salt bath impurity ions are formed by contacting an exchange substrate containing lithium ions with the salt bath, exchanging the lithium ions on the exchange substrate with sodium ions in the salt bath and diffusing the lithium ions into the salt bath;
when the concentration of impurity ions and lithium ions exceeds a standard value, adding an absorbent and a stabilizer;
the absorbent is phosphate; the stabilizer has a siloxy group and/or has siloxy properties.
2. The salt bath impurity ion purification method of claim 1, wherein the absorbent is sodium phosphate and/or sodium dihydrogen phosphate, forming reactive precipitates and suspended particles with the impurity lithium ions in the salt bath; the reactive precipitate and suspended particles include: insoluble Li3PO4Insoluble Li2NaPO4Or insoluble LiNa2PO4At least one of (1).
3. The salt bath impurity ion purification method of claim 1 or 2, wherein said reactive precipitate and suspending particles are adsorbed on a stabilizer surface by said stabilizer.
4. The salt bath impurity ion purification method of claim 2, wherein said stabilizer comprises at least one of silica or silicic acid or metasilicate or silicate containing covalent bonds of silica.
5. The salt bath impurity ion purification method according to claim 1, wherein an amount of said absorbent to be charged is 0.1 to 2 wt% of the salt bath to be purified.
6. The salt bath impurity ion purification method according to claim 1 or 2, wherein the stabilizer is dosed in a sequence that is either simultaneously with or later than the dosing of the absorbent.
7. The salt bath impurity ion purification method of claim 1, wherein the purification salt bath is a potassium-sodium mixed salt bath or a pure sodium salt bath, and lithium ions in the salt bath after purification are less than 300 PPm.
8. The salt bath impurity ion purification method according to claim 1, wherein the purification salt bath is a potassium-sodium-lithium mixed salt bath or a sodium-lithium salt bath, and the lithium ions in the salt bath are stabilized between a prescribed value of plus or minus 500PPm after the purification.
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|---|---|---|---|
| CN201911267944.4A CN110981219B (en) | 2019-12-11 | 2019-12-11 | Salt bath impurity ion purification method |
| PCT/CN2020/135813 WO2021115441A1 (en) | 2019-12-11 | 2020-12-11 | Salt bath impurity ion purification method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911267944.4A CN110981219B (en) | 2019-12-11 | 2019-12-11 | Salt bath impurity ion purification method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608033A (en) * | 2020-09-12 | 2021-04-06 | 重庆鑫景特种玻璃有限公司 | Chemically strengthened glass ceramics and strengthening method |
| CN112645610A (en) * | 2020-09-12 | 2021-04-13 | 重庆鑫景特种玻璃有限公司 | Boron-free and phosphorus-free high-stability ionic sieve and application thereof |
| WO2021115441A1 (en) * | 2019-12-11 | 2021-06-17 | 深圳市东丽华科技有限公司 | Salt bath impurity ion purification method |
| CN113200686A (en) * | 2021-05-10 | 2021-08-03 | 南通瑞景光电科技有限公司 | High temperature heat treatment method for optical element |
| CN113955950A (en) * | 2021-11-01 | 2022-01-21 | 江苏铁锚玻璃股份有限公司 | Method for strengthening lithium-aluminum-silicon glass |
| CN115477480A (en) * | 2021-06-15 | 2022-12-16 | 常熟佳合显示科技有限公司 | Strengthening salt and strengthening method for microcrystalline glass |
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| CN107793043A (en) * | 2016-08-30 | 2018-03-13 | 深圳市力沣实业有限公司 | The method for improving chemically enhancing glass salt bath service life |
| CN109422469A (en) * | 2017-08-30 | 2019-03-05 | 康宁股份有限公司 | The method for removing the residue containing lithium phosphate compounds from surface |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021115441A1 (en) * | 2019-12-11 | 2021-06-17 | 深圳市东丽华科技有限公司 | Salt bath impurity ion purification method |
| CN112608033A (en) * | 2020-09-12 | 2021-04-06 | 重庆鑫景特种玻璃有限公司 | Chemically strengthened glass ceramics and strengthening method |
| CN112645610A (en) * | 2020-09-12 | 2021-04-13 | 重庆鑫景特种玻璃有限公司 | Boron-free and phosphorus-free high-stability ionic sieve and application thereof |
| CN116768493A (en) * | 2020-09-12 | 2023-09-19 | 重庆鑫景特种玻璃有限公司 | Boron-free and phosphorus-free ion sieve with high stability and preparation and application thereof |
| CN113200686A (en) * | 2021-05-10 | 2021-08-03 | 南通瑞景光电科技有限公司 | High temperature heat treatment method for optical element |
| CN115477480A (en) * | 2021-06-15 | 2022-12-16 | 常熟佳合显示科技有限公司 | Strengthening salt and strengthening method for microcrystalline glass |
| CN113955950A (en) * | 2021-11-01 | 2022-01-21 | 江苏铁锚玻璃股份有限公司 | Method for strengthening lithium-aluminum-silicon glass |
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| CN110981219B (en) | 2022-06-10 |
| WO2021115441A1 (en) | 2021-06-17 |
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