CN112390539A - Salt bath purification additive material and method of use thereof - Google Patents
Salt bath purification additive material and method of use thereof Download PDFInfo
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- CN112390539A CN112390539A CN201910758511.2A CN201910758511A CN112390539A CN 112390539 A CN112390539 A CN 112390539A CN 201910758511 A CN201910758511 A CN 201910758511A CN 112390539 A CN112390539 A CN 112390539A
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- Prior art keywords
- salt bath
- additive material
- purification additive
- bath purification
- purified
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- 150000003839 salts Chemical class 0.000 title claims abstract description 230
- 238000000746 purification Methods 0.000 title claims abstract description 147
- 239000000654 additive Substances 0.000 title claims abstract description 127
- 230000000996 additive effect Effects 0.000 title claims abstract description 127
- 239000000463 material Substances 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 31
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 28
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 26
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 239000011521 glass Substances 0.000 description 48
- 238000002474 experimental method Methods 0.000 description 32
- 239000012535 impurity Substances 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 17
- 238000005728 strengthening Methods 0.000 description 17
- 239000002243 precursor Substances 0.000 description 9
- 238000003426 chemical strengthening reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 239000001488 sodium phosphate Substances 0.000 description 7
- 229910000162 sodium phosphate Inorganic materials 0.000 description 7
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910001386 lithium phosphate Inorganic materials 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000012629 purifying agent Substances 0.000 description 5
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 5
- 239000005345 chemically strengthened glass Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000006058 strengthened glass Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- -1 lithium aluminum silicon Chemical compound 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 229910001950 potassium oxide Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 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
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical group [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 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
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)
- Glass Compositions (AREA)
Abstract
A salt bath purification additive material and a using method thereof. The salt bath purification additive material contains 30-60 mol% of alkali metal oxide and 20-50 mol% of SiO in terms of mol percentage2And 8-25 mol% of other oxides. The using method comprises the following steps: step S1, providing a salt bath to be purified; step S2, adding the salt bath purification additive material to the salt bath to be purified; and step S3, taking out the salt bath purification additive material after the salt bath purification additive material reacts with the salt bath to be purified for a certain time. Step S4, the salt bath purification additive material taken out in the step S3 is put into a pure sodium salt bath; and step S5, taking out the salt bath purification additive material for the next use after the salt bath purification additive material reacts with the pure sodium salt bath for a certain time. The salt bath purification additive material has the advantages of being capable of rapidly absorbing lithium ions and sodium ions in the salt bath, being conveniently and rapidly taken out, and being capable of being repeatedly used for many times.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to the technical field of purification of salt bath for glass chemical strengthening, and specifically relates to a salt bath purification additive material and a use method thereof.
Background
In the process of placing the glass in the salt bath for chemical strengthening treatment, as the using time of the salt bath is prolonged and the number of the glass treated by the salt bath is increased, garbage ions Na in the salt bath+、Li+The content of (2) can also be increased, although only PPM level, the content of (10) can also be enough to seriously hinder the normal chemical toughening, the subsequent CS value of the glass after being strengthened is reduced, the strength is greatly reduced, and the quality of the final product is difficult to control. After the glass is chemically strengthened, the glass expands because the large ions in the salt bath replace the small ions in the glass, so that the compressive stress is formed on the surface of the glass, and the purpose of improving the strength of the glass is achieved. However, Li in the salt bath+The increase of the amount of the lithium aluminum silicon glass can seriously weaken the sodium-lithium exchange degree when the lithium aluminum silicon glass is chemically strengthened, so that the expansion degree after strengthening is reduced, the requirement of the chemically strengthened glass on the size of the glass in the cover plate of the mobile phone is within 20 microns, and Li in a salt bath is reduced+This increase in the number of steps will undoubtedly lead to an increase in the dimensional defect rate of the lithium aluminosilicate chemically strengthened glass. The above problems occurring in the field of strengthening are called "salt bath poisoning", and in order to solve the above problems, the conventional method is to replace a salt bath, but the process of replacing the salt bath is time-consuming and labor-consuming, and the cost is increased and the efficiency is reduced. At present, a method for absorbing impurity ions (lithium ions) in a salt bath is proposed in the industry, wherein powdery sodium phosphate is put into the salt bath, the sodium phosphate is dissolved in the salt bath, and the phosphate and the lithium ions form lithium phosphate to precipitate so as to reduce the content of Li in garbage ions. However, the reaction after the lithium phosphate is introduced into the salt bath requires a chemical reaction time of more than 10 hours, the salt bath is turbid due to the formation of precipitates, and the lithium phosphate can be used after long-time clarification; therefore, salt bath and glass quality can not be managed in real time on line, and at best, batch management can only be realized; after the powdery sodium phosphate is added into the salt bath, a large amount of sodium ions are brought in, so that the effective proportion of the salt bath is changed; the sodium phosphate shows strong basicity and water absorption, and a large number of OH ions are introduced when the sodium phosphate is introduced into the salt bath, so that strong corrosion is caused to glass, the network of the glass is damaged, and the sodium phosphate can not increase the strength of the glass and can also greatly reduce the strength of the glass when used for more than 30 hours; when excessive sludge is formed at the bottom of the salt bath by the precipitated lithium phosphate, the effective working area of the salt bath is reduced, the yield is reduced, and the cleaning is difficult; too much lithium phosphate precipitation over prolonged use will make it adhere stronglyTempering the surface of the glass, thereby causing defects in the glass; the residual strong alkali phosphate in the salt bath is attached to the surface of the glass, and the glass is contacted with water in the air when being taken out of the salt bath, so that the glass is strongly corroded for the second time.
In addition, in a glass processing plant, a salt bath furnace is generally 10 tons or even higher, the number of glass sheets treated in one strengthening process is as high as ten thousand, and in the ion exchange environment of the scale, if the salt bath is not subjected to environmental management and control, the strengthened glass is easily subjected to surface defects, the glass strength among batches is greatly reduced, and the salt bath is gradually failed.
Moreover, the main materials of the glass strengthening salt bath are potassium nitrate and sodium nitrate, and the potassium nitrate is a main component of a strong oxidant, inflammable and explosive; the sodium phosphate is strong base and weak acid salt, and has strong water absorption and corrosion; both of these are key materials of public safety regulations. In the glass processing process, the materials cannot be recycled, so that the use amount is large, which not only causes great damage to the environment, but also causes high production cost.
Therefore, the additive which has a large size and is convenient to take out from the salt bath and manages the salt bath on line in real time is urgently needed by people, impurity ions in the salt bath are effectively controlled, a stable ion exchange environment is provided for glass to be strengthened, and the stability and the strength of the batch production of the strengthened glass are ensured. In addition, the use amount of potassium nitrate and sodium nitrate can be greatly reduced, the pollution and damage degree to the environment can be effectively reduced, the production efficiency is improved, and the production cost is reduced. The characteristic of large size makes it have higher security and convenience in the operation process of saving, throwing in and fishing.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a salt bath purification additive material and a using method thereof, wherein the salt bath purification additive material can rapidly absorb lithium ions and sodium ions generated in a salt bath in a chemical strengthened glass process, ensure that the concentrations of the lithium ions and the sodium ions in the salt bath are at a lower level, and ensure the mass production size stability and the surface stress stability of the chemical strengthened glass. Furthermore, the salt bath purification additive material can be quickly, conveniently and quickly taken out, and the influence on the production efficiency is reduced. Furthermore, the salt bath purification additive material can be repeatedly utilized after being treated to release absorbed impurity ions, so that the use amount is greatly reduced, and the cost is reduced.
The technical scheme adopted by the invention for solving the technical problems is as follows: a salt bath purification additive material is provided, comprising, in mole percent, 30-60 mol% of an alkali metal oxide, 20-50 mol% of SiO2, and 8-25 mol% of other oxides.
As a preference for the salt bath purification additive material of the invention, the molar content of the alkali metal oxide is in relation to SiO2The ratio of the molar content of (a) is more than 0.7; the other oxide includes P2O5And/or B2O3The molar content of the alkali metal oxide and P2O5And/or B2O3The ratio of the sum of the molar contents of (A) is between 2.5 and 3.5.
As a preference for the salt bath purification additive material of the invention, the alkali metal oxide includes and includes only Na2O and/or K2O。
As a preference for the salt bath purification additive material of the invention, the other oxide comprises P2O5And also includes B2O3、Al2O3、ZrO2、SnO2、ZnO、MgO、CaO、Cr2O3、TiO2At least one of (1).
As a preference of the salt bath purification additive material of the invention, the salt bath purification additive material has a molar volume of 20-35cm3·mol-1In the meantime.
Preferably, the salt bath purification additive material of the present invention is in a granular, sheet or porous form, and an orthographic projection of the salt bath purification additive material on any one plane covers at least one square area with a length and width dimension of 0.5 × 0.5 mm.
In order to solve the technical problems, the invention also provides a use method of the salt bath purification additive material, which comprises the following steps:
step S1, providing a salt bath to be purified, wherein the salt bath to be purified contains potassium ions or/and sodium ions or/and lithium ions;
step S2 of adding the salt bath purification additive material to the salt bath to be purified;
and step S3, taking out the salt bath purification additive material after the salt bath purification additive material reacts with the salt bath to be purified for a certain time.
Preferably, the temperature of the salt bath to be purified is 350-550 ℃, the addition amount of the salt bath purification additive material is 0.3-5 wt% of the mass of the salt bath to be purified, and the reaction time of the salt bath purification additive material and the salt bath to be purified is at most 24 h.
As a preference of the use method provided by the present invention, the use method further comprises the steps of:
step S4, the salt bath purification additive material taken out in the step S3 is put into a pure sodium salt bath;
step S5, after the salt bath purification additive material and the pure sodium salt bath react for a certain time, the salt bath purification additive material is taken out for the next use, and the absorption efficiency of the salt bath purification additive material obtained in the step S5 on lithium ions or sodium ions is reduced to be 50-95% of that of the salt bath purification additive material in the step S2.
As the optimization of the using method provided by the invention, the temperature of the pure sodium salt bath is 350-550 ℃, and the reaction time of the salt bath purification additive material and the pure sodium salt bath is 1-10 h.
Compared with the prior art, the salt bath purification additive material provided by the invention can rapidly absorb lithium ions and sodium ions generated in the salt bath in the process of chemically strengthening glass, ensures that the concentrations of the lithium ions and the sodium ions in the salt bath are at a lower level, and ensures the stability of the volume production size and the stability of the surface stress of the chemically strengthened glass. Furthermore, the salt bath purification additive material can be quickly, conveniently and quickly taken out, and the influence on the production efficiency is reduced. Furthermore, the salt bath purification additive material can be repeatedly utilized after being treated to release absorbed impurity ions, so that the use amount is greatly reduced, and the cost is reduced.
Detailed Description
The invention provides a salt bath purification additive material which can absorb lithium ions or sodium ions in a glass chemical strengthening salt bath. It is known that, in the glass strengthening process, after the glass chemical strengthening salt bath is used for a period of time, impurity metal ions (lithium ions or sodium ions) exchanged from the glass are increased in the salt bath, so that the glass chemical strengthening salt bath is inactivated and the effect of strengthening the glass is weakened. The salt bath purification additive material of the invention is added into the inactivated glass chemical strengthening salt bath, and after reaction is carried out for a period of time at a certain temperature (the temperature is higher than the melting point of the molten salt compound), the salt bath purification additive material can absorb the impurity metal ions (lithium ions or sodium ions), thereby enhancing or recovering the activity of the glass chemical strengthening salt bath. More particularly, the salt bath purification additive material can release lithium ions or sodium ions after the lithium ions or the sodium ions are adsorbed, and the aim of recycling is fulfilled.
The salt bath purification additive material comprises 30-60 mol% of alkali metal oxide and 20-50 mol% of SiO in terms of mol percentage2And 8-25 mol% of other oxides. Wherein the content of the alkali metal oxide is equal to SiO2The ratio of the content of (A) is more than 0.8; the other oxide includes P2O5And B2O3The content of the alkali metal oxide and P2O5And B2O3The ratio of the content sum of (A) to (B) is between 2.5 and 3.5. The alkali metal oxide comprises Na2O and/or K2And O. The other oxide includes P2O5And also includes B2O3、Al2O3、ZrO2、SnO2、ZnO、MgO、CaO、Cr2O3、TiO2At least one of (1).
SiO2Is a backbone component of salt bath purification additive material and is a necessary component.
The other oxide and SiO2The selection of the composition and the content of the skeleton forming the covalent bond to form the salt bath purification additive network structure directly influences the adsorption performance of the salt bath purification additive network structure.
The metal element in the alkali metal oxide is intended to replace or extract the impurity metal ions in the salt bath, and it has been found through experiments that when the sum of the number of moles of the valence of at least one metal oxide in the alkali metal oxide (the alkali metal oxide participating in the reaction is not limited to the entire alkali metal oxide as long as part of the alkali metal oxide participating in the reaction can extract/replace the impurity metal ions in the salt bath to a predetermined concentration range) is equal to the sum of the number of moles of the valence of the impurity metal ions in the salt bath.
The alkali metal oxide includes a variety of cases, and may be a single monovalent metal oxide or a mixture of two or more monovalent metal oxides. Specifically, the metal element in the metal oxide is at least one of potassium and sodium; the monovalent metal oxide is selected from the group consisting of a carbonate, a fluoride, a sulfate, a nitrate, a phosphate, a hydroxide, an oxide, a chloride, or a mixture thereof. The raw materials of the monovalent metal oxide are reacted during the preparation of the salt bath purification additive according to the invention and finally present in the salt bath purification additive product in the form of the alkali metal oxide. For example, the source of potassium oxide may be potassium carbonate, potassium fluoride, potassium sulfate, potassium nitrate, potassium phosphate, potassium hydroxide, potassium oxide, potassium chloride, or mixtures thereof, and then the potassium oxide is ultimately present in the salt bath refining additive material.
Preferably, the molar volume of the salt bath purification additive material is 20-35cm3·mol-1In the meantime. At this molar volume, the salt bath purification additive material is at the appropriate stiffness, sampleEasy mechanical crushing, proper rigidity, high integrity and no powdering.
Preferably, the orthographic projection of said salt bath purifying additive material on any one plane covers at least a square area having a length and width dimension of 0.5 x 0.5 mm. Therefore, the salt bath can be smoothly taken out under the normal working condition of the salt bath.
The salt bath purification additive material provided by the invention can be prepared by the following steps: first, an alkali metal oxide and SiO are prepared2And other oxide raw materials, fully mixing, wherein the molar percentage content of each component in the salt bath purification additive material product is 30-60mol percent, and the content of the alkali metal oxide is SiO220-50 mol% and other oxides 8-25 mol%. The amount of the raw material of the alkali metal oxide is such that the content of the alkali metal oxide obtained after the reaction in the finally obtained salt bath purification additive material is 30-60 mol%. Then, the mixture is heated to 900-1500 ℃, stirred to a molten state, and a metastable salt bath purification additive precursor is formed. Optionally, after generating the metastable salt bath purification additive precursor, introducing the metastable salt bath purification additive precursor into water at a temperature of 0-90 ℃ for quenching treatment, thereby obtaining the granular salt bath purification additive material. Optionally, after generating the metastable salt bath purification additive precursor, slowly cooling the metastable salt bath purification additive precursor to 400-900 ℃, and performing drawing forming or extrusion forming treatment through mechanical external force, thereby obtaining the sheet salt bath purification additive material. Optionally, when a metastable liquid salt bath purification additive precursor is generated, a foaming agent is added to enable the interior and the surface of the precursor to be in a fine porous state, and after the precursor is cooled to room temperature, the precursor is crushed by mechanical external force to form a granular salt bath purification additive material with a porous structure in the interior.
The molar volume referred to in the present invention is calculated from the molar volume coefficient of each component and the molar volume ratio of the sample.
The invention also provides a using method of the salt bath purification additive material, and the using method comprises a purification part and an activation part.
Wherein, the purification part comprises the following steps:
step S1, providing a salt bath to be purified, wherein the salt bath to be purified contains potassium ions or/and sodium ions or/and lithium ions; wherein the salt bath to be purified is an inactivated glass chemical strengthening salt bath containing a large amount of lithium ions or sodium ions; preferably, the temperature of the salt bath to be purified is 350-550 ℃.
Step S2 of adding the salt bath purification additive material to the salt bath to be purified; preferably, the addition amount of the salt bath purification additive material is 0.5-5 wt% of the mass of the salt bath to be purified,
step S3, taking out the salt bath purification additive material after the salt bath purification additive material reacts with the salt bath to be purified for a certain time; preferably, the salt bath purification additive material and the salt bath to be purified have a reaction time of at most 24 h.
The use of the salt bath purification additive material finds that the absorption efficiency of lithium ions in the first 6h is 35PPm/h-50PPm/h per 1 wt% of the salt bath purification additive material, and the absorption efficiency of sodium ions in the first 6h is 50PPm/h-350PPm/h per 1 wt% of the salt bath purification additive material.
The following is an activation part, which specifically comprises the following steps:
step S4, the salt bath purification additive material taken out in the step S3 is put into a pure sodium salt bath;
and step S5, taking out the salt bath purification additive material for the next use after the salt bath purification additive material reacts with the pure sodium salt bath for a certain time. Through use, the absorption efficiency of lithium ions or sodium ions by the salt bath purification additive material obtained in the step S5 is reduced to be 50-95% of that of the salt bath purification additive material in the step S2. Preferably, the temperature of the pure sodium salt bath is 350-550 ℃ (if the pure sodium salt bath is recycled, the higher the temperature is better, so the lowest temperature also needs to be the IOX temperature), and the reaction time of the salt bath purification additive material and the pure sodium salt bath is 1-10 h.
The invention also provides another using method of the salt bath purification additive material, which can be placed into a brand-new salt bath without impurity ions together with the glass to be strengthened, and continuously absorbs the impurity ions generated in the ion exchange process in the salt bath in the glass strengthening process, so that the impurity ions in the salt bath are always stabilized at a lower level. The method comprises the following specific steps:
step S1, providing a salt bath to be purified, which is a brand new salt bath that does not contain impurity ions (sodium ions and lithium ions); preferably, the temperature of the salt bath to be purified is 350-550 ℃.
Step S2 of adding the salt bath purification additive material to the salt bath to be purified; preferably, the addition amount of the salt bath purification additive material is 0.3-5 wt% of the mass of the salt bath to be purified,
and step S3, the additive material to be purified by the salt bath and the glass to be strengthened enter the salt bath at the same time and are taken out along with the glass, so that the strengthening is not influenced.
It was found that, in the salt bath control using the above-described method, the concentration of lithium ions and/or sodium ions as impurities in the salt bath was controlled to 400PPm or less, preferably 200PPm or less, and more preferably 100PPm or less.
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described in detail. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Examples 1 to 6
In examples 1 to 6, 6 salt bath purification additive materials having different component morphologies were prepared from commercially available products by the above-mentioned preparation method. The composition and morphology of the salt bath purification additive materials in examples 1 to 6 are shown in table 1.
TABLE 1
In the table, β represents the content of alkali metal oxide and SiO in the salt bath purification additive material2The ratio of the contents of (A) to (B); theta is the content of alkali metal oxide and P in the salt bath purification additive material2O5And B2O3The ratio of the sum of contents of (A) to (B).
Purification experiments 1 to 6
In order to obtain real experimental data to demonstrate that the salt bath purification additive materials of examples 1 to 6 are capable of absorbing lithium ions and sodium ions in the deteriorated chemically strengthened salt bath, purification experiments were conducted in purification experiments 1 to 6 on the salt bath purification additive materials of examples 1 to 6 according to the steps of the purification part of the method of using salt bath purification additive materials mentioned hereinabove. The conditions during purification experiments 1 to 6 are shown in table 2.
TABLE 2
The above purification experiments 1 to 6 can fully prove that the salt bath purification additive material can rapidly absorb lithium ions and sodium ions generated in the salt bath in the process of chemically strengthening glass, the absorption efficiency in the first 6 hours is very high, and the minimum amount is 35.6 ppm/h.
Purification experiments 1 to 2 were repeated
In order to obtain real experimental data to demonstrate that the salt bath purification additive materials provided by the present invention can release absorbed lithium ions or sodium ions to enable recycling, repeated purification experiments were performed on the salt bath purification additive materials in examples 3 and 5 in activation experiments 1 to 2 according to the above-mentioned method of using the salt bath purification additive materials. The conditions during the repetition of the purification experiments 1 to 2 are shown in table 3.
TABLE 3
As can be seen from the above repeated purification experiments 1 to 2, the salt bath purification additive materials in examples 3 and 5 can be reused many times.
On-line purification experiments 1 to 2
On-line purification experiments 1-2 the salt bath purification additive materials of examples 3 and 5 were subjected to on-line purification experiments according to another method of use of the salt bath purification additive materials mentioned above. In addition, in order to confirm that the salt bath purification additive material can obtain an online purification effect, a blank experiment 1 and a blank experiment 2 are respectively performed, wherein the conditions of the blank experiment 1 are the same as those of the online purification experiment 1, except that the salt bath purification additive material in the embodiment 3 is not added in the blank experiment 1, and the conditions of the blank experiment 2 are the same as those of the online purification experiment 2, except that the salt bath purification additive material in the embodiment 5 is not added in the blank experiment 2. The conditions during the on-line purification experiments 1 to 2 and the blank experiments 1 to 2 are shown in table 4.
In the experimental process, a brand new salt bath without impurity ions is placed in a 12-ton-volume salt bath furnace, salt bath purification additive materials and glass to be strengthened enter the salt bath at the same time, 1.5 ten thousand pieces of glass to be strengthened are added each time, and the strengthening time is 2-7 hours each time.
TABLE 4
It can be seen from the comparison of the data of the online purification experiment 1 and the blank experiment 1 that the lithium ion concentration in the salt bath can be kept at a low level by adding the salt bath purifying agent material in each batch of strengthening process in the online purification experiment 1, the lithium ion concentration can still be controlled below 99ppm after seven times of strengthening, and the lithium ion concentration in the salt bath which is not added with the salt bath purifying agent material in the same batch in the blank experiment 1 is up to 860ppm and is at a poisoning level. It can be seen from the above online purification experiment 2 and blank experiment 2 that the sodium ion concentration in the salt bath can be kept at a low level by adding the salt bath purifying agent material in each batch of the strengthening process of the online purification experiment 2, the sodium ion concentration can still be controlled below 168ppm after seven times of strengthening, and the lithium ion concentration in the salt bath of the same batch without the salt bath purifying agent material in the blank experiment 2 is up to 1560ppm and is at a poisoning level. In conclusion, the salt bath purifying agent material and the glass to be strengthened are simultaneously put into the salt bath, and impurity ions generated in the ion exchange process in the salt bath are continuously absorbed in the glass strengthening process, so that the impurity ions in the salt bath are always stabilized at a lower level.
In summary, compared with the prior art, the salt bath purification additive material provided by the invention can rapidly absorb lithium ions and sodium ions generated in the salt bath in the process of chemically strengthening glass, ensure that the concentrations of the lithium ions and the sodium ions in the salt bath are at a lower level, and ensure the stability of mass production size and surface stress of the chemically strengthened glass. Moreover, the salt bath purification additive material can be repeatedly utilized after being treated to release absorbed impurity ions, so that the use amount can be greatly reduced, and the cost is reduced.
While embodiments of the present invention have been described, the present invention is not limited to the above-described embodiments, which are intended to be illustrative rather than limiting, and many modifications may be made by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A salt bath purification additive material is characterized in that: the salt bath purification additive material comprises 30-60 mol% of alkali metal oxide and 20-50 mol% of SiO in terms of mol percentage2And 8-25 mol% of other oxides.
2. The salt bath purification additive material of claim 1, wherein: the molar content of the alkali metal oxide and SiO2The ratio of the molar content of (a) is more than 0.7; the other oxide includes P2O5And/or B2O3The molar content of the alkali metal oxide and P2O5And/or B2O3The ratio of the sum of the molar contents of (A) is between 2.5 and 3.5.
3. The salt bath purification additive material of claim 1, wherein: the alkali metal oxide includes and includes only Na2O and/or K2O。
4. The salt bath purification additive material of claim 1, wherein: the other oxide includes P2O5And also includes B2O3、Al2O3、ZrO2、SnO2、ZnO、MgO、CaO、Cr2O3、TiO2At least one of (1).
5. The salt bath purification additive material of claim 1, wherein: the molar volume of the salt bath purification additive material is 20-35cm3·mol-1In the meantime.
6. The salt bath purification additive material of claim 1, wherein: the salt bath purification additive material is granular, flaky or porous, and the orthographic projection of the salt bath purification additive material on any one plane at least covers a square area with the length and width of 0.5 multiplied by 0.5 mm.
7. Use of a salt bath purification additive material according to any one of claims 1-6, characterized in that it comprises the following steps:
step S1, providing a salt bath to be purified, wherein the salt bath to be purified contains potassium ions or/and sodium ions or/and lithium ions;
step S2 of adding the salt bath purification additive material to the salt bath to be purified;
and step S3, taking out the salt bath purification additive material after the salt bath purification additive material reacts with the salt bath to be purified for a certain time.
8. The use method as claimed in claim 7, characterized in that the temperature of the salt bath to be purified is 350-550 ℃, the addition amount of the salt bath purification additive material is 0.3-5 wt% of the mass of the salt bath to be purified, and the reaction time of the salt bath purification additive material and the salt bath to be purified is at most 24 h.
9. Use according to claims 7-8, characterized in that it further comprises the following steps:
step S4, the salt bath purification additive material taken out in the step S3 is put into a pure sodium salt bath;
step S5, after the salt bath purification additive material and the pure sodium salt bath react for a certain time, the salt bath purification additive material is taken out for the next use, and the absorption efficiency of the salt bath purification additive material obtained in the step S5 on lithium ions or sodium ions is reduced to be 50-95% of that of the salt bath purification additive material in the step S2.
10. The use method as claimed in claim 9, wherein the temperature of the pure sodium salt bath is 350-550 ℃, and the reaction time of the salt bath purification additive material and the pure sodium salt bath is 1-10 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115304289A (en) * | 2022-08-26 | 2022-11-08 | 成都光明光电股份有限公司 | Salt bath additive suitable for silver-containing salt bath |
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