CN116354619B - Silicon-free salt bath purification additive material and application method thereof - Google Patents
Silicon-free salt bath purification additive material and application method thereof Download PDFInfo
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- CN116354619B CN116354619B CN202310434707.2A CN202310434707A CN116354619B CN 116354619 B CN116354619 B CN 116354619B CN 202310434707 A CN202310434707 A CN 202310434707A CN 116354619 B CN116354619 B CN 116354619B
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- 150000003839 salts Chemical class 0.000 title claims abstract description 250
- 238000000746 purification Methods 0.000 title claims abstract description 158
- 239000000654 additive Substances 0.000 title claims abstract description 146
- 230000000996 additive effect Effects 0.000 title claims abstract description 146
- 239000000463 material Substances 0.000 title claims abstract description 143
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000011521 glass Substances 0.000 claims abstract description 64
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 41
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000002500 ions Chemical class 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 28
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 23
- 238000005728 strengthening Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 238000010521 absorption reaction Methods 0.000 claims description 19
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000005345 chemically strengthened glass Substances 0.000 abstract description 4
- 150000004760 silicates Chemical class 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 238000003723 Smelting Methods 0.000 description 9
- 238000003426 chemical strengthening reaction Methods 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 229910001386 lithium phosphate Inorganic materials 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 6
- -1 lithium aluminum silicon Chemical compound 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 150000003376 silicon Chemical class 0.000 description 5
- 239000001488 sodium phosphate Substances 0.000 description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- 229910001950 potassium oxide Inorganic materials 0.000 description 3
- 239000006058 strengthened glass Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000010452 phosphate 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
- 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
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 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
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 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
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 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
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 239000002699 waste material Substances 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)
- Silicon Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A non-silicate salt bath purified additive material and a use method thereof. The additive material for purification in a silicate-free bath contains 30-60mol% of alkali metal oxide and 30-65mol% of B 2 O 3 8-25mol% of other oxides, and the silicate-free bath purification additive material is free of silica; the sum of the mole percentages of the oxides is 100%; the Al is 2 O 3 The content of (B) 2 O 3 10% and above. The silicon-free salt bath purification additive material provided by the invention can rapidly absorb lithium ions and sodium ions generated in salt bath in the process of chemically strengthening glass, ensures that the concentration of the lithium ions and the sodium ions in the salt bath is at a lower level, and ensures the stability of the mass production size and the stability of the surface stress of the chemically strengthened glass; the additive material for purification of the non-silicon salt bath can be quickly, conveniently and quickly taken out, so that the influence on the production efficiency is reduced; the additive material for purification of the non-silicon salt bath can be repeatedly utilized after being treated to release absorbed impurity ions, so that the use amount is greatly reduced, and the cost is lowered.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a silicon-free salt bath purification additive material and a use method thereof. The patent application of the invention is a divisional application of the invention patent application of which the application date is 2019, 10, 16, application number is 201910984155.6 and the invention name is 'a silicon-free salt bath purification additive material and a using method thereof'.
Background
In the process of placing glass in salt bath for chemical strengthening treatment, as the service time of the salt bath is prolonged and the quantity of glass treated by the salt bath is increased, garbage ions Na in the salt bath + 、Li + Although the content of (2) is just PPM level, the content is also increased, but the normal chemical tempering is also seriously hindered, so that the CS value of the subsequent strengthened glass 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 large ions in the salt bath replace the small ions in the glass, so that the glass expands, compressive stress is formed on the surface of the glass, and the purpose of improving the strength of the glass is achieved. However, saltsLi in bath + The increase of (2) seriously weakens the sodium-lithium exchange degree when the lithium aluminum silicon glass is subjected to chemical strengthening, thereby leading to the reduction of the expansion degree after strengthening, and the application of the chemical strengthening glass in a mobile phone cover plate has the requirement that the glass size is deviated within 20 micrometers, so that the Li in a salt bath is formed + The increase in (3) clearly leads to an increase in the defective size of the lithium aluminum silicon alloy reinforced glass. For the above problems occurring in the strengthening field, called "salt bath poisoning", in order to solve the above problems, conventionally, the solution is to replace the salt bath, but the process of replacing the salt bath is time consuming and laborious, which results in increased cost and reduced efficiency.
At present, a method for absorbing impurity ions (lithium ions) in a salt bath has been proposed, in which powdered sodium phosphate is put into the salt bath, the sodium phosphate is dissolved in the salt bath, and phosphate groups and lithium ions form lithium phosphate to precipitate, thereby reducing the content of Li in the waste ions. However, the reaction requires more than 10 hours of chemical reaction time after lithium phosphate is introduced into the salt bath, the salt bath is turbid due to the formation of precipitates, and the lithium phosphate can be used after long-time clarification; therefore, the on-line real-time management of salt bath and glass quality cannot be realized, and at best, only batch management can be realized; after the powdery sodium phosphate is added into the salt bath, a large amount of sodium ions are carried in, so that the effective proportion of the salt bath is changed; sodium phosphate is strong in alkalinity and water absorbability, a large amount of OH ions are introduced when salt bath is introduced, so that strong corrosion is caused to glass, phosphate radicals invade silica bonds in a glass network structure, and the phosphate radicals and the silica bonds structure change the network structure on the surface of the glass, so that the network of the glass is further destroyed, the strength of the glass cannot be increased after the glass is used for more than 30 hours, and the strength of the glass is greatly reduced; when the precipitated lithium phosphate is too much in the 'sludge' formed at the bottom of the salt bath, the effective working area of the salt bath is reduced, the yield is reduced, and the cleaning is difficult; too much precipitation of lithium phosphate after use can cause the lithium phosphate to adhere to the surface of the reinforced glass, thereby causing defects to the glass; the residual phosphoric acid strong alkali salt in the salt bath adheres to the surface of the glass, and when the glass is taken out of the salt bath, the residual phosphoric acid strong alkali salt contacts with water in the air to form second strong corrosion on the glass.
In addition, another method for absorbing impurity ions (lithium ions) in a salt bath has been proposed in the art, in which a silicon-containing ion sieve is put into the salt bath, and lithium ions are complexed and absorbed in the salt bath by using the silicon-containing ion sieve. However, the silicon-containing ion sieve is formed based on silicon-oxygen as a main backbone basis, and has smaller backbone, so that the absorption efficiency and the absorption rate are lower; the silicon has larger atomic number and larger atomic mass, so that the active ingredients in the ion sieve are lower, the service efficiency is lower, and if certain absorption efficiency is achieved, the consumption of the silicon-containing ion sieve is larger, and the cost is higher. And the silicon-containing ion sieve is pulverized under the action of high temperature in the long-term use process, and the pulverized silicon-containing ion sieve contains a large amount of silicon component substances, and is bonded and crosslinked with silicon dioxide components in the surface of glass at the height Wen Zhongyi of the salt bath, so that the surface of the reinforced glass finished product has particle defects, and the quality of the finished product is affected.
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 tens of thousands, and in such a large-scale ion exchange environment, if the salt bath is not subjected to environment control, the surface defects of the strengthened glass are easily caused, the glass strength between batches is greatly reduced, and the salt bath is gradually failed.
Furthermore, the main materials of the glass reinforced salt bath are potassium nitrate and sodium nitrate, and the potassium nitrate is a main component of strong oxidant, inflammable, explosive and explosive; sodium phosphate is a strong alkali weak acid salt, and has strong water absorption and corrosiveness; both of which are important substances of public safety regulations. In the glass processing process, the materials cannot be recycled and have huge usage, which not only causes great damage to the environment, but also causes high production cost.
Therefore, an additive which is large in size and convenient to take out from a salt bath and manages the salt bath on line in real time is urgently needed, so that impurity ions in the salt bath are effectively managed and controlled, a stable ion exchange environment is provided for glass to be strengthened, and the stability and strength of mass production of the strengthened glass are ensured. In addition, the method can greatly reduce the use amount of potassium nitrate and sodium nitrate, effectively reduce the pollution and damage degree to the environment, improve the production efficiency and reduce the production cost. The large size ensures that the device has higher safety and convenience in the operation processes of storage, throwing and fishing.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a silicon-free salt bath purification additive material and a use method thereof, wherein the silicon-free salt bath purification additive material can quickly absorb lithium ions and sodium ions generated in salt bath in the process of chemically strengthening glass, ensure the concentration of the lithium ions and the sodium ions in the salt bath to be at a lower level, and ensure the stability of the mass production size and the stability of the surface stress of the chemically strengthened glass. Furthermore, the additive material for purification of the non-silicon salt bath can be quickly, conveniently and quickly taken out, so that the influence on the production efficiency is reduced. Furthermore, the additive material for purification of the non-silicon salt bath 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. It is further noted that the silicon-free salt bath purification additive material is free of silica and employs B 2 O 3 As a main framework, al 2 O 3 As a secondary network architecture, it has a lower synthesis temperature than the silica-containing, non-siliceous salt bath purification additive material, its smelting temperature can be below 1000 ℃, so its smelting equipment constraints will be relaxed and its smelting costs will be greatly reduced. Still further, even if the additive material for purification of the silicon-free salt bath is pulverized under the action of high temperature in the long-term use process, the additive material mainly contains boron component substances instead of silicon components, so that bonding and crosslinking are not easy to form between the additive material and silicon dioxide components in the surface of glass at the high temperature of the salt bath, the defect that a finished glass product has granular shape after strengthening is avoided, and the good quality of the product is ensured.
The technical scheme adopted for solving the technical problems is as follows: providing the silicon-free salt bath purification additive material, wherein the silicon-free salt bath purification additive material comprises 30-60mol% of alkali metal oxide and 30-65mol% of B in terms of mole percent 2 O 3 And 8-25mol% of other oxides, andthe silicon-free salt bath purification additive material is free of silicon dioxide; the sum of the mole percentages of the oxides is 100%; the other oxide includes Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The Al is 2 O 3 The content of (B) 2 O 3 10% and above.
As a preference for the purification of additive materials in the silicon-free salt bath according to the invention, the molar content of alkali metal oxide is as follows 2 O 3 The ratio of the molar content of (2) is 0.55 or more, preferably 0.6 or more.
As a preferred feature of the silicon-free salt bath purification additive material of the present invention, the alkali metal oxide comprises Na 2 O and/or K 2 O。
As a preferable example of the silicon-free salt bath purification additive material of the present invention, the silicon-free salt bath purification additive material further comprises, in mole percent, P 2 O 5 、ZrO 2 、SnO 2 、ZnO、Cr 2 O 3 、TiO 2 At least one of them.
As a preferable example of the silicon-free salt bath purification additive material of the present invention, the absorption efficiency of lithium ions per 1% by weight of the silicon-free salt bath purification additive material in the preceding 6 hours is 35ppm/h to 50ppm/h, and the absorption efficiency of sodium ions per 1% by weight of the silicon-free salt bath purification additive material in the preceding 6 hours is 50ppm/h to 350ppm/h.
In order to solve the technical problems, the invention also provides a use method of the silicon-free salt bath purification additive material, which is characterized in that the silicon-free salt bath purification additive material and glass to be strengthened are simultaneously placed in a brand new salt bath without impurity ions, and the impurity ions generated in the ion exchange process in the salt bath are continuously absorbed in the glass strengthening process, so that the salt bath is managed in real time and on line.
As a preferred use method provided by the invention, the temperature of the salt bath is 350-550 ℃; the addition amount of the silicon-free salt bath purification additive material is 0.3-5wt% of the mass of the salt bath.
In the method of use provided by the present invention, the salt bath is preferably controlled so that the concentration of lithium ions and/or sodium ions as impurities in the salt bath is 400ppm or less, preferably 200ppm or less, and more preferably 100ppm or less.
In order to solve the technical problems, the invention also provides a use method of the silicon-free 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, adding the silicon-free salt bath purification additive material into the salt bath to be purified;
and S3, taking out the silicon-free salt bath purification additive material after the silicon-free salt bath purification additive material reacts with the salt bath to be purified for a certain time.
As a preference of the use method provided by the invention, the temperature of the salt bath to be purified is 350-550 ℃, the adding amount of the silicon-free salt bath purification additive material is 0.3-5wt% of the mass of the salt bath to be purified, and the reaction time of the silicon-free salt bath purification additive material and the salt bath to be purified is at most 24 hours.
As a preferred use method provided by the invention, the use method further comprises the following steps:
s4, placing the silicon-free salt bath purification additive material extracted in the step S3 into a pure sodium salt bath;
and S5, taking out the silicon-free salt bath purification additive material for next use after the silicon-free salt bath purification additive material reacts with the pure sodium salt bath for a certain time, wherein the absorption efficiency of the silicon-free salt bath purification additive material obtained by the step S5 on lithium ions or sodium ions is reduced to be 50-95% of that of the silicon-free salt bath purification additive material in the step S2.
As a preferred use method provided by the invention, the absorption efficiency of lithium ions per 1wt% of the silicon-free salt bath purification additive material in the first 6 hours is 35ppm/h to 50ppm/h, and the absorption efficiency of sodium ions per 1wt% of the silicon-free salt bath purification additive material in the first 6 hours is 50ppm/h to 350ppm/h.
Compared with the prior art, the silicon-free salt bath purification additive material provided by the invention can quickly absorb lithium ions and sodium ions generated in salt bath in the process of chemically strengthening glass, ensures that the concentration of the lithium ions and the sodium ions in the salt bath is at a lower level, and ensures the stability of the mass production size and the surface stress of the chemically strengthened glass. Furthermore, the additive material for purification of the non-silicon salt bath can be quickly, conveniently and quickly taken out, so that the influence on the production efficiency is reduced. Furthermore, the additive material for purification of the non-silicon salt bath 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. It is further noted that the silicon-free salt bath purification additive material is free of silica and employs B 2 O 3 As a main framework, al 2 O 3 As a secondary network architecture, it has a lower synthesis temperature than the silica-containing, non-siliceous salt bath purification additive material, its smelting temperature can be below 1000 ℃, so its smelting equipment constraints will be relaxed and its smelting costs will be greatly reduced. The silicon-free salt bath purification additive material is pulverized under the action of high temperature in the long-term use process, and mainly contains boron component substances instead of silicon components, so that bonding and crosslinking are not easy to form between the silicon dioxide components in the surface of glass in the high temperature of the salt bath, the defect that a finished glass product has granular shape after strengthening is avoided, and good product quality is ensured.
Detailed Description
The invention provides a silicon-free salt bath purification additive material which can absorb lithium ions or sodium ions in a glass chemical strengthening salt bath. It is known that, during glass strengthening, after a 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 deactivated and the effect of strengthening the glass is weakened. The silicon-free salt bath purification additive material of the invention is added into the deactivated glass chemical strengthening salt bath, and after a certain period of reaction is carried out at a certain temperature (the temperature higher than the melting point of the molten salt compound), the silicon-free salt bath purification additive material can absorb metal ions (lithium ions or sodium ions) of the impurities, so that the activity of the glass chemical strengthening salt bath is enhanced or restored. More particularly, the silicon-free salt bath purification additive material can release lithium ions or sodium ions after absorbing the lithium ions or the sodium ions through activating treatment, so that the aim of recycling is fulfilled.
The silicon-free salt bath purifying additive material comprises 30-60mol% of alkali metal oxide and 30-65mol% of B by mol percent 2 O 3 And 8-25mol% of other oxides, and the silicate-free bath purification additive material is free of silica. Wherein the molar content of the alkali metal oxide is equal to B 2 O 3 The molar content ratio of (2) is more than 0.6; the other oxide includes Al 2 O 3 ，Al 2 O 3 The content of (B) 2 O 3 More than 10 percent of the total weight of the composition; the other oxide also includes P 2 O 5 、ZrO 2 、SnO 2 、ZnO、Cr 2 O 3 、TiO 2 At least one of them. The alkali metal oxide includes Na 2 O and/or K 2 O。
B 2 O 3 Is used as the backbone component of the additive material for purifying the non-silicate bath and is a necessary component.
Said other oxides and B 2 O 3 The selection of the composition and content of the skeleton forming the covalent bond to form the network structure of the salt bath purification additive directly influences the adsorption performance of the network structure of the salt bath purification additive.
The metal element in the alkali metal oxide is intended to displace or extract the impurity metal ion in the salt bath, and it has been found through experiments that when at least one metal oxide of the alkali metal oxides (the alkali metal oxide involved in the reaction is not limited to the entire alkali metal oxide, as long as a part of the alkali metal oxide involved in the reaction can extract/displace the impurity metal ion in the salt bath to a predetermined concentration range) the sum of the molar numbers of the valence of the metal atom is equal to the sum of the molar numbers of the valence of the impurity metal ion in the salt bath.
The alkali metal oxide 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 raw material is selected from carbonates, fluorides, sulfates, nitrates, phosphates, hydroxides, oxides, chlorides or mixtures thereof. The raw materials of the monovalent metal oxide are those which are reacted during the preparation of the salt bath purification additive according to the invention and which are finally present in the form of the alkali metal oxide in the salt bath purification additive product. For example, the starting material for potassium oxide may be potassium carbonate, potassium fluoride, potassium sulfate, potassium nitrate, potassium phosphate, potassium hydroxide, potassium oxide, potassium chloride, or mixtures thereof, then potassium oxide is ultimately present in the silicate-free bath purification additive material.
Preferably, the orthographic projection of the non-silicate bath purification additive material on any one plane covers at least one square area with the length and width dimensions of 0.5 multiplied by 0.5 mm. Thus, the salt bath can be taken out smoothly under the normal working condition of the salt bath.
The silicon-free salt bath purification additive material provided by the invention can be prepared by the following steps: first, an alkali metal oxide, B, is prepared 2 O 3 Fully mixing raw materials of other oxides, wherein the mol percent of each component in the obtained silicon-free salt bath purification additive material product is 30-60mol percent of alkali metal oxide and B 2 O 3 30-65mol% and 8-25mol% of other oxides. The amount of the raw material of the alkali metal oxide is such that the alkali metal oxide obtained after the reaction is contained in the finally obtained silicon-free salt bath purification additive material in an amount of 30 to 60mol%. And then heating the mixture to 900-1000 ℃, and stirring to a molten state to form a metastable salt bath purification additive precursor. Optionally, after the metastable salt bath purification additive precursor is generated, the metastable salt bath purification additive precursor is introduced into water with the temperature of 0-90 ℃ for quenching treatment, so that the granular silicon-free salt bath purification additive material is obtained. Optionally, when generatingAfter the metastable salt bath purification additive precursor is cooled slowly to 400-900 ℃, the metastable salt bath purification additive precursor is subjected to drawing forming or extrusion forming treatment by mechanical external force, and thus the sheet-shaped silicon-free salt bath purification additive material is obtained. Optionally, when generating a metastable liquid salt bath purification additive precursor, adding a foaming agent to make the inside and the surface of the precursor be fine and porous, and after the precursor is cooled to room temperature, crushing the precursor by mechanical external force to form a granular salt bath purification additive material with a porous structure inside.
The invention also provides a use method of the silicon-free salt bath purification additive material, which 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 deactivated 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, adding the silicon-free salt bath purification additive material into the salt bath to be purified; preferably, the addition amount of the silicon-free salt bath purification additive material is 0.5-5wt% of the mass of the salt bath to be purified,
s3, taking out the silicon-free salt bath purification additive material after the silicon-free salt bath purification additive material reacts with the salt bath to be purified for a certain time; preferably, the reaction time of the silicon-free salt bath purification additive material with the salt bath to be purified is at most 24 hours.
Using it was found that the absorption efficiency of lithium ions per 1wt% of the silicon-free salt bath purification additive material in the first 6 hours was 35PPm/h to 50PPm/h, and the absorption efficiency of sodium ions per 1wt% of the silicon-free salt bath purification additive material in the first 6 hours was 50PPm/h to 350PPm/h.
The following is an activating part, which specifically comprises the following steps:
s4, placing the silicon-free salt bath purification additive material extracted in the step S3 into a pure sodium salt bath;
and S5, taking out the silicon-free salt bath purification additive material for the next use after the silicon-free salt bath purification additive material reacts with the pure sodium salt bath for a certain time. It was found through use that the absorption efficiency of lithium ions or sodium ions by the silicon-free salt bath purification additive material obtained through the step S5 was reduced to between 50 and 95% of the silicon-free salt bath purification additive material in the step S2. Preferably, the temperature of the pure sodium salt bath is 350-550 ℃ (the higher the temperature is, the better if recycled, and therefore the lowest temperature must also be the IOX temperature), and the reaction time of the silicon-free salt bath purification additive material with the pure sodium salt bath is 1-10 hours.
The invention also provides another application method of the silicon-free salt bath purification additive material, which can be placed in a brand new salt bath without impurity ions together with 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, wherein the salt bath to be purified is a brand new salt bath which 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, adding the silicon-free salt bath purification additive material into the salt bath to be purified; preferably, the addition amount of the silicon-free salt bath purification additive material is 0.3-5wt% of the mass of the salt bath to be purified,
and S3, enabling the additive material to be purified in the silicon-free salt bath and the glass to be strengthened to enter a salt bath at the same time, and taking out along with the glass, so that strengthening is not affected.
It was found that 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, more preferably 100PPm or less.
Specific embodiments of the present invention will now be described in detail for a clearer understanding of the technical features, objects and effects of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples 1 to 6
In examples 1-6, 6 silicon-free salt bath purification additive materials having different component morphologies were prepared using the preparation methods mentioned above from commercially available products. The composition and morphology of the silicon-free salt bath purified additive materials in examples 1 to 6 are shown in table 1.
In the table, beta refers to the content of alkali metal oxide and B in the additive material for purification in a silicate-free bath 2 O 3 Ratio of the contents of (3); theta refers to Al in the additive material purified by a silicate bath 2 O 3 Content of (B) and B 2 O 3 The ratio of the sum of the contents of (3).
Purification experiments 1 to 6
In order to obtain actual experimental data to demonstrate that the silicon-free 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 performed on the silicon-free salt bath purification additive materials of examples 1 to 6 in accordance with the steps of the purification section of the method of using the silicon-free salt bath purification additive materials mentioned hereinabove in purification experiments 1 to 6. The conditions during purification experiments 1 to 6 are shown in table 2.
TABLE 2
The purification experiments 1 to 6 can fully prove that the silicon-free salt bath purification additive material can quickly absorb lithium ions and sodium ions generated in a salt bath in the process of chemically strengthening glass, the absorption efficiency in the first 6 hours is very high, and the minimum absorption efficiency is 31.0 ppm/h.
Purification experiments 1 to 2 were repeated
In order to obtain actual experimental data to demonstrate that the silicon-free salt bath purification additive material provided by the present invention can release absorbed lithium ions or sodium ions to be reused, repeated purification experiments were performed on the silicon-free salt bath purification additive materials of examples 3 and 5 in accordance with the methods of use of the silicon-free salt bath purification additive materials mentioned hereinabove in activation experiments 1 to 2. The conditions during the repeated purification experiments 1 to 2 are shown in Table 3.
TABLE 3 Table 3
As can be seen from the above repeated purification experiments 1 to 2, the silicon-free salt bath purification additive materials in examples 3 and 5 can be reused a plurality of times.
On-line purification experiments 1 to 2
In-line purification experiments 1 to 2 the silicon-free salt bath purification additive materials of examples 3 and 5 were subjected to in-line purification experiments according to another method of use of the silicon-free salt bath purification additive materials mentioned hereinabove. In addition, in order to confirm that the silicon-free salt bath purification additive material can achieve the on-line purification effect, blank experiment 1 and blank experiment 2 were also performed, respectively, and each condition of blank experiment 1 was the same as that of on-line purification experiment 1 in that the silicon-free salt bath purification additive material of example 3 was not added in blank experiment 1, and each condition of blank experiment 2 was the same as that of on-line purification experiment 2 in that the silicon-free salt bath purification additive material of example 5 was not added in 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, the brand new salt bath without impurity ions is placed in a 12-ton-volume salt bath furnace, the salt bath is fed with the silicon-free salt bath purification additive material and the glass to be strengthened simultaneously, 1.5 ten thousand pieces of glass to be strengthened are put into each time, and each strengthening time is 2-7 hours.
TABLE 4 Table 4
As can be seen from the comparison of the above data in the on-line purification experiment 1 and the blank experiment 1, the addition of the salt bath purifier material in each batch strengthening process in the on-line purification experiment 1 can keep the lithium ion concentration in the salt bath at a low level, and after seven times of strengthening, the lithium ion concentration can still be controlled below 113.79ppm, while the lithium ion concentration in the salt bath without the salt bath purifier material in the same batch in the blank experiment 1 is already up to 860ppm, which is at a poisoning level. As can be seen from the above online purification experiment 2 and blank experiment 2, the addition of the salt bath purifier material in each batch strengthening process of the online purification experiment 2 can keep the sodium ion concentration in the salt bath at a low level, and after seven times of strengthening, the sodium ion concentration can still be controlled below 193.10ppm, while the lithium ion concentration in the salt bath of the same batch without the salt bath purifier material in blank experiment 2 is already up to 1560ppm, which is at a poisoning level. In summary, the salt bath purifier material and the glass to be strengthened are simultaneously put into the salt bath, and the salt bath purifier material continuously absorbs 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.
In summary, compared with the prior art, the silicon-free salt bath purification additive material provided by the invention can quickly absorb lithium ions and sodium ions generated in salt bath in the process of chemically strengthening glass, ensure the concentration of the lithium ions and the sodium ions in the salt bath to be at a lower level, and ensure the stability of the mass production size and the surface stress of the chemically strengthened glass. In addition, the additive material for purification of the non-silicon salt bath 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.
In addition, since the silicon-free salt bath purification additive material does not contain silicon dioxide, it is prepared by using B 2 O 3 As a main framework, al 2 O 3 As a secondary network architecture, it has a lower synthesis temperature than the silica-containing, non-siliceous salt bath purification additive material, its smelting temperature can be below 1000 ℃, so its smelting equipment constraints will be relaxed and its smelting costs will be greatly reduced.
Furthermore, even if the additive material for purification of the silicon-free salt bath is pulverized under the action of high temperature in the long-term use process, the additive material mainly comprises boron component substances instead of silicon components, so that bonding and crosslinking are not easy to form between the additive material and silicon dioxide components in the surface of glass at the high temperature of the salt bath, the defect that a finished glass product has granular shape after strengthening is avoided, and the good quality of the product is ensured.
While the present invention has been described with reference to the above-described embodiments, it is to be understood that the same is not limited to the above-described embodiments, but rather that the same is intended to be illustrative only, and that many modifications may be made by one of ordinary skill in the art without departing from the spirit of the invention and scope of the appended claims.
Claims (15)
1. A silicon-free salt bath purification additive material, characterized in that the silicon-free salt bath purification additive material comprises, in mole percent, 30-60mol% of an alkali metal oxide, 30-65mol% of B 2 O 3 8-25mol% of other oxides, and the silicate-free bath purification additive material is free of silica; the sum of the mole percentages of the oxides is 100%; the other oxide includes Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The Al is 2 O 3 The content of (B) 2 O 3 10% and above.
2. The silicon-free salt bath purification addition of claim 1An additive material characterized in that the molar content of the alkali metal oxide is equal to B 2 O 3 The ratio of the molar content of (2) is 0.55 or more.
3. The silicate-free salt bath purification additive material of claim 2 wherein the molar content of alkali metal oxide is as follows 2 O 3 The ratio of the molar content of (2) is 0.6 or more.
4. A silicon-free salt bath purification additive material according to any one of claims 1 to 3, wherein the alkali metal oxide comprises Na 2 O and/or K 2 O。
5. A silicon-free salt bath purification additive material according to any one of claims 1 to 3, further comprising, in mole percent, P 2 O 5 、ZrO 2 、SnO 2 、ZnO、Cr 2 O 3 、TiO 2 At least one of them.
6. The silicon-free salt bath purification additive material of claim 1, wherein the absorption efficiency of lithium ions per 1wt% of the silicon-free salt bath purification additive material in the preceding 6 hours is 35ppm/h to 50ppm/h, and the absorption efficiency of sodium ions per 1wt% of the silicon-free salt bath purification additive material in the preceding 6 hours is 50ppm/h to 350ppm/h.
7. A method of using the silicon-free salt bath purification additive material of any one of claims 1-6, wherein the silicon-free salt bath purification additive material and glass to be strengthened are simultaneously placed in a completely new salt bath free of impurity ions, and the salt bath is managed in real time and on line by continuously absorbing the impurity ions generated in the ion exchange process in the salt bath during the glass strengthening process.
8. The method of use according to claim 7, wherein the temperature of the salt bath is 350-550 ℃; the addition amount of the silicon-free salt bath purification additive material is 0.3-5wt% of the mass of the salt bath.
9. Use according to claim 7 or 8, characterized in that the salt bath is controlled in such a way that the impurity lithium ion and/or sodium ion concentration in the salt bath is controlled below 400 ppm.
10. Use according to claim 9, characterized in that the salt bath is controlled in such a way that the impurity lithium ion and/or sodium ion concentration in the salt bath is controlled below 200 ppm.
11. Use according to claim 9, characterized in that the salt bath is controlled in such a way that the impurity lithium ion and/or sodium ion concentration in the salt bath is controlled below 100 ppm.
12. A method of using the silicon-free salt bath purification additive material of any one of claims 1-6, comprising the steps of:
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, adding the silicon-free salt bath purification additive material into the salt bath to be purified;
and S3, taking out the silicon-free salt bath purification additive material after the silicon-free salt bath purification additive material reacts with the salt bath to be purified for a certain time.
13. Use according to claim 12, characterized in that the temperature of the salt bath to be purified is 350-550 ℃, the addition amount of the silicon-free salt bath purification additive material is 0.3-5wt% of the mass of the salt bath to be purified, and the reaction time of the silicon-free salt bath purification additive material and the salt bath to be purified is at most 24h.
14. The method of use according to claim 12 or 13, further comprising the step of:
s4, placing the silicon-free salt bath purification additive material extracted in the step S3 into a pure sodium salt bath;
and S5, taking out the silicon-free salt bath purification additive material for next use after the silicon-free salt bath purification additive material reacts with the pure sodium salt bath for a certain time, wherein the absorption efficiency of the silicon-free salt bath purification additive material obtained by the step S5 on lithium ions or sodium ions is reduced to be 50-95% of that of the silicon-free salt bath purification additive material in the step S2.
15. The use according to claim 12 or 13, characterized in that the absorption efficiency of lithium ions per 1wt% of the silicon-free salt bath purification additive material in the first 6 hours is 35ppm/h to 50ppm/h, and the absorption efficiency of sodium ions per 1wt% of the silicon-free salt bath purification additive material in the first 6 hours is 50ppm/h to 350ppm/h.
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