CN113800938B - Preparation method of titanium oxide ceramic ultrafiltration membrane - Google Patents
Preparation method of titanium oxide ceramic ultrafiltration membrane Download PDFInfo
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- CN113800938B CN113800938B CN202010539827.5A CN202010539827A CN113800938B CN 113800938 B CN113800938 B CN 113800938B CN 202010539827 A CN202010539827 A CN 202010539827A CN 113800938 B CN113800938 B CN 113800938B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000012528 membrane Substances 0.000 title claims abstract description 41
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 23
- 239000011224 oxide ceramic Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims description 17
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 7
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000004530 micro-emulsion Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 229920002307 Dextran Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 150000003608 titanium Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a titanium oxide ceramic ultrafiltration membrane. The invention combines a sol-gel method with a microemulsion medium hydrothermal method to prepare titanium oxide nano sol, an additive is added into the titanium oxide sol to prepare a coating solution, the coating solution is dipped and coated on a porous alumina ceramic membrane, and the titanium oxide ultrafiltration membrane layer is obtained through drying and calcining. The invention prepares the titanium oxide nano sol by adding a specific emulsifier into the titanium oxide sol and carrying out hydrothermal reaction in a shorter time and at a lower temperature, and prepares the titanium oxide ultrafiltration membrane by preparing a membrane coating solution, drying and calcining.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a preparation method of a titanium oxide ceramic ultrafiltration membrane.
Background
The membrane separation is mainly divided into microfiltration, ultrafiltration, nanofiltration and reverse osmosis. The application field of membrane separation technology has been deep into various aspects of people's life and production, such as chemical industry, environmental protection, electronics, textiles, medicine, food, etc. The organic membrane is not high temperature resistant, has poor chemical corrosion resistance, is easy to pollute, swells and contracts in a solvent and the like, so that the organic membrane is limited in the separation process needing special conditions. The inorganic film has the characteristics of good chemical stability, high mechanical strength, high temperature resistance, microbial corrosion resistance, long service life and the like, and can be applied to the fields with harsh conditions.
In the prior art, the preparation method of the nano particles mainly comprises a chemical precipitation method, a sol-gel method, a hydrothermal method, a micro-emulsion method and the like. Wherein the sol-gel method is the most important method for preparing the titanium dioxide ceramic ultrafiltration membrane by the liquid phase method. However, when the ceramic ultrafiltration membrane is prepared from the titanium dioxide nano solution obtained by the sol-gel method, because the titanium dioxide nano solution shrinks seriously in the calcining process, multiple coating is needed, the stability of the prepared sol has a great influence on the coating effect, and the expansion production of the sol-gel method is limited to a certain extent. The hydrothermal method for preparing titanium dioxide can avoid the problem of hard agglomeration possibly generated by high-temperature treatment in wet chemistry, the prepared titanium dioxide has a good crystal structure and a high specific surface area, but the hydrothermal method has high requirements on equipment and can be prepared only under the conditions of high temperature and high pressure.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a titanium oxide ceramic ultrafiltration membrane.
The technical scheme of the invention is as follows:
a preparation method of a titanium oxide ceramic ultrafiltration membrane comprises the following steps:
(1) Preparing titanium oxide sol from raw materials including organic titanium salt and a first dispersing agent by a sol-gel method;
(2) Adding an emulsifier into the titanium oxide sol, and carrying out hydrothermal reaction for 1-3h at 100-150 ℃, wherein the emulsifier consists of cyclohexane, n-hexanol and OP-10 (a condensation product of alkylphenol and ethylene oxide);
(3) Shearing or ultrasonically treating the material obtained in the step (2) to obtain a transparent titanium oxide nano solution;
(4) Adding a second dispersing agent, a plasticizer, a binder and a defoaming agent into the titanium oxide nano solution, and fully stirring to obtain a coating solution;
(5) And coating the coating liquid on a support, and sequentially drying, calcining and naturally cooling to obtain the titanium oxide ceramic ultrafiltration membrane.
In a preferred embodiment of the present invention, the molar ratio of cyclohexane, n-hexanol and OP-10 is 7-9: 2: 1.
Further preferably, the emulsifier is added in an amount of 1 to 5wt% of the titania sol.
In a preferred embodiment of the present invention, the organic titanium salt is n-butyl titanate or isopropyl titanate, and the molar ratio of the organic titanium salt to water is preferably 1: 10-50.
In a preferred embodiment of the present invention, the first dispersant is sodium citrate or sodium polyacrylate, the second dispersant is polyethylene glycol, the amount of the first dispersant added is preferably 0.1 to 1wt% of the titanium oxide sol, and the amount of the second dispersant added is preferably 0.1 to 1wt% of the titanium oxide nano solution.
In a preferred embodiment of the present invention, the plasticizer is polyvinyl alcohol, and the addition amount thereof is preferably 1 to 5wt% of the titanium oxide nano solution.
In a preferred embodiment of the present invention, the binder is hydroxyethyl cellulose, and the addition amount thereof is preferably 0.1 to 5wt% of the titanium oxide nano solution.
In a preferred embodiment of the present invention, the defoaming agent is a silicone defoaming agent, and the addition amount thereof is preferably 0.01 to 0.1wt% of the titanium oxide nano solution.
In a preferred embodiment of the invention, the drying is carried out at a temperature of from 80 to 120 ℃ for a period of from 2 to 5 hours.
In a preferred embodiment of the invention, the calcination is carried out at a temperature of from 350 to 500 ℃ for a time of from 2 to 5 hours.
The invention has the beneficial effects that:
1. the invention combines a sol-gel method with a microemulsion medium hydrothermal method to prepare titanium oxide nano sol, adds an additive into the titanium oxide sol to prepare a coating liquid, and the coating liquid is dipped on a porous alumina ceramic membrane, dried and calcined to obtain a titanium oxide ultrafiltration membrane layer.
2. The method comprises the steps of adding a specific emulsifier into titanium oxide sol, preparing titanium oxide nano sol under the hydrothermal reaction of shorter time and lower temperature, preparing coating liquid, drying and calcining, and preparing the defect-free high-quality titanium oxide ultrafiltration membrane without coating for many times.
Drawings
FIG. 1 is a scanning electron micrograph of a comparative film obtained in comparative example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of a comparative film obtained according to comparative example 2 of the present invention.
FIG. 3 is a scanning electron micrograph of a titania ceramic ultrafiltration membrane prepared in examples 1 to 3 of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Comparative example 1
(1) Mixing tetrabutyl titanate and water in a molar ratio of 1:10 to perform sol-gel reaction, adding acid to perform dispergation, wherein the pH of the dispergated material is 3, then adding 1wt% of sodium citrate, and uniformly mixing to obtain well-dispersed titanium oxide sol;
(2) Adding 0.5wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 8:2: 1) into the titanium oxide sol, and carrying out hydrothermal reaction for 3h at 100 ℃;
(3) Naturally cooling the material obtained in the step (2), and then shearing or ultrasonically treating to obtain a semitransparent titanium oxide nano solution;
(4) Adding 1wt% of polyethylene glycol, 3wt% of polyvinyl alcohol and 0.3wt% of hydroxyethyl cellulose into the titanium oxide nano solution, fully and uniformly mixing, adding 0.01wt% of organic silicon defoamer, and fully stirring to obtain a coating solution;
(5) Coating the film coating liquid on a porous ceramic film support with the average pore diameter of 0.1um in an immersion manner, and sequentially drying, calcining and naturally cooling to obtain a contrast film; wherein, the first and the second end of the pipe are connected with each other,
the drying comprises the following steps: heating to 120 ℃ at the speed of 3 ℃/min, and keeping the temperature and drying for 5 hours;
the calcination is as follows: heating to 350 ℃ at the speed of 3 ℃/min, and carrying out heat preservation and calcination for 3h.
The comparative membrane prepared in this comparative example is shown in FIG. 1, and the membrane layer is split, and the rejection rate of 2g/L glucan (molecular weight: 2 ten thousand) is 0%.
Comparative example 2
(1) Mixing n-butyl titanate and water in a molar ratio of 1:10 to perform sol-gel reaction, adding acid to perform dispergation, wherein the pH of the dispergated material is 3, then adding 1wt% of sodium polyacrylate, and uniformly mixing to obtain well-dispersed titanium oxide sol;
(2) Adding 7wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 8:2: 1) into the titanium oxide sol, and carrying out hydrothermal reaction for 3h at 100 ℃;
(3) Naturally cooling the material obtained in the step (2), and then shearing or ultrasonically treating to obtain a semitransparent titanium oxide nano solution;
(4) Adding 1wt% of polyethylene glycol, 3wt% of polyvinyl alcohol and 0.3wt% of hydroxyethyl cellulose into the titanium oxide nano solution, fully and uniformly mixing, adding 0.01wt% of organic silicon defoamer, and fully stirring to obtain a coating solution;
(5) Coating the film coating liquid on a porous ceramic film support with the average pore diameter of 0.1um in an immersion manner, and sequentially drying, calcining and naturally cooling to obtain a contrast film; wherein, the first and the second end of the pipe are connected with each other,
the drying comprises the following steps: heating to 120 ℃ at the speed of 3 ℃/min, and keeping the temperature and drying for 5 hours;
the calcination is as follows: heating to 350 ℃ at the speed of 3 ℃/min, and carrying out heat preservation and calcination for 3h.
The comparative membrane prepared in this comparative example is shown in FIG. 2, and the membrane layer is split, and the rejection rate of 2g/L dextran (molecular weight: 2 ten thousand) is 15%.
Example 1
(1) Mixing n-butyl titanate and water in a molar ratio of 1:10 to perform sol-gel reaction, adding acid to perform dispergation, wherein the pH of the dispergated material is 3, then adding 1wt% of sodium citrate, and uniformly mixing to obtain well-dispersed titanium oxide sol;
(2) Adding 1wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 8:2: 1) into the titanium oxide sol, and carrying out hydrothermal reaction for 3h at 100 ℃;
(3) Naturally cooling the material obtained in the step (2), and then shearing or ultrasonically treating to obtain a semitransparent titanium oxide nano solution;
(4) Adding 1wt% of polyethylene glycol, 3wt% of polyvinyl alcohol and 0.3wt% of hydroxyethyl cellulose into the titanium oxide nano solution, fully and uniformly mixing, adding 0.01wt% of organic silicon defoamer, and fully stirring to obtain a coating solution;
(5) Dipping the coating liquid on a porous ceramic membrane support with the average pore diameter of 0.1um, and sequentially drying, calcining and naturally cooling to obtain a titanium oxide ceramic ultrafiltration membrane; wherein, the first and the second end of the pipe are connected with each other,
the drying comprises the following steps: heating to 120 ℃ at the speed of 3 ℃/min, and keeping the temperature and drying for 5 hours;
the calcination is as follows: heating to 350 ℃ at the speed of 3 ℃/min, and keeping the temperature for 3h.
As shown in FIG. 3, the ultrafiltration membrane of the titania ceramic membrane prepared in this example has a complete membrane layer and a rejection rate of 94% for 2g/L dextran (molecular weight: 2 ten thousand).
Example 2
(1) Mixing n-butyl titanate and water in a molar ratio of 1:10 to perform sol-gel reaction, adding acid to perform dispergation, wherein the pH of the dispergated material is 3, then adding 1wt% of sodium citrate, and uniformly mixing to obtain well-dispersed titanium oxide sol;
(2) Adding 3wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 8:2: 1) into the titanium oxide sol, and carrying out hydrothermal reaction for 3h at 100 ℃;
(3) Naturally cooling the material obtained in the step (2), and then shearing or ultrasonically treating to obtain a semitransparent titanium oxide nano solution;
(4) Adding 1wt% of polyethylene glycol, 3wt% of polyvinyl alcohol and 0.3wt% of hydroxyethyl cellulose into the titanium oxide nano solution, fully and uniformly mixing, adding 0.01wt% of organic silicon defoamer, and fully stirring to obtain a coating solution;
(5) Dipping the coating liquid on a porous ceramic membrane support with the average pore diameter of 0.1um, and sequentially drying, calcining and naturally cooling to obtain a titanium oxide ceramic ultrafiltration membrane; wherein, the first and the second end of the pipe are connected with each other,
the drying comprises the following steps: heating to 120 ℃ at the speed of 3 ℃/min, and keeping the temperature and drying for 5 hours;
the calcination is as follows: heating to 350 ℃ at the speed of 3 ℃/min, and carrying out heat preservation and calcination for 3h.
As shown in FIG. 3, the titanium oxide ceramic ultrafiltration membrane prepared in this example has a complete membrane layer and a retention rate of 95% for 2g/L dextran (molecular weight: 2 ten thousand).
Example 3
(1) Mixing n-butyl titanate and water in a molar ratio of 1: 50 to perform sol-gel reaction, adding acid to perform dispergation, wherein the pH of the dispergated material is 3, then adding 1wt% of sodium polyacrylate, and uniformly mixing to obtain well-dispersed titanium oxide sol;
(2) Adding 3wt% of emulsifier (the molar ratio of cyclohexane, n-hexanol and OP-10 is 8:2: 1) into the titanium oxide sol, and carrying out hydrothermal reaction for 1h at 150 ℃;
(3) Naturally cooling the material obtained in the step (2), and then shearing or ultrasonically treating to obtain a semitransparent titanium oxide nano solution;
(4) Adding 1wt% of polyethylene glycol, 5wt% of polyvinyl alcohol and 1wt% of hydroxyethyl cellulose into the titanium oxide nano solution, fully and uniformly mixing, adding 0.1wt% of organic silicon defoamer, and fully stirring to obtain a coating solution;
(5) Dipping the coating liquid on a porous ceramic membrane support with the average pore diameter of 0.1um, and sequentially drying, calcining and naturally cooling to obtain a titanium oxide ceramic ultrafiltration membrane; wherein the content of the first and second substances,
the drying is as follows: heating to 120 ℃ at the speed of 1 ℃/min, and keeping the temperature and drying for 5 hours;
the calcination is as follows: heating to 450 ℃ at the speed of 5 ℃/min, and keeping the temperature for 5h.
As shown in FIG. 3, the titanium oxide ceramic ultrafiltration membrane prepared in this example has a complete membrane layer and a retention rate of 90% for 2g/L dextran (molecular weight: 2 ten thousand).
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (1)
1. A preparation method of a titanium oxide ceramic ultrafiltration membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) Mixing n-butyl titanate and water according to a molar ratio of 1-50 to perform sol-gel reaction, adding acid to perform dispergation, wherein the pH of the dispergated material is 3, then adding 1wt% of sodium citrate or sodium polyacrylate, and uniformly mixing to obtain well-dispersed titanium oxide sol;
(2) Adding an emulsifier into the titanium oxide sol, and carrying out hydrothermal reaction for 1-3h at 100-150 ℃, wherein the emulsifier is composed of cyclohexane, n-hexanol and OP-10 according to a molar ratio of 8;
(3) Shearing or ultrasonically treating the material obtained in the step (2) to obtain a transparent titanium oxide nano solution;
(4) Adding polyethylene glycol, polyvinyl alcohol, hydroxyethyl cellulose and an organic silicon defoamer into the titanium oxide nano solution, and fully stirring to obtain a coating solution;
(5) Coating the coating liquid on a support, and sequentially drying, calcining and naturally cooling to obtain a titanium oxide ceramic ultrafiltration membrane; drying at 80-120 deg.C for 2-5 hr; the calcining temperature is 350-500 deg.C, and the calcining time is 2-5h.
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