CN114262214A - High-weather-resistance ceramic diaphragm pipe and preparation method thereof - Google Patents
High-weather-resistance ceramic diaphragm pipe and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000011812 mixed powder Substances 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 55
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- 238000000034 method Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 13
- 239000004917 carbon fiber Substances 0.000 claims description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 13
- 239000002041 carbon nanotube Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
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- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 8
- 239000012188 paraffin wax Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 7
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 7
- 239000001639 calcium acetate Substances 0.000 claims description 7
- 229960005147 calcium acetate Drugs 0.000 claims description 7
- 235000011092 calcium acetate Nutrition 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
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- 238000001354 calcination Methods 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 5
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a high weather-resistant ceramic diaphragm tube and a preparation method thereof, belonging to the technical field of ceramic diaphragms, (Ba)0.7Ca0.3)ZrO3The powder is in a cubic phase perovskite structure and has ferroelectricity at the temperature lower than the Curie temperature; in the subsequent step, (Ba) is first0.7Ca0.3)ZrO3Mixing the powder with other raw materials to obtain mixed powder, filling the mixed powder into a mold to obtain a blank, and sintering at high temperature to obtain ceramic (Ba)0.7Ca0.3)ZrO3The crystal grains in the powder are subjected to phase change, the symmetry of the crystal structure is improved, and the powder is mixed with SiC powder and Al2O3Sintering raw materials such as powder and the like, and then reforming crystal grains; compared with common alumina ceramics, the ceramic is more compact and regular, has better corrosion resistance, and simultaneously removes raw materials (Ba)0.7Ca0.3)ZrO3The ferroelectric property of the ceramic diaphragm tube has better function of blocking electrons, and the using effect of the ceramic diaphragm tube in an electrolysis device is ensured.
Description
Technical Field
The invention belongs to the technical field of ceramic diaphragms, and particularly relates to a high-weather-resistance ceramic diaphragm tube and a preparation method thereof.
Background
In the field of fine chemical engineering, such as ammonium persulfate, sodium persulfate and other products, an electrolysis device is generally adopted for fine production, and a ceramic diaphragm tube is an important part in the electrolysis device.
The electrolyzer needs to be overhauled every six months, mainly because the ceramic membrane tubes therein are easily damaged. In the use process of the electrolysis device, the ceramic diaphragm tube is immersed in electrolyte and dilute sulfuric acid solution, and after a long time, the structure of the common ceramic diaphragm tube is disintegrated due to erosion, so that the isolation effect cannot be achieved, and the ceramic diaphragm tube needs to be overhauled and replaced regularly. The production efficiency and the economic benefit are greatly influenced because the electrolysis device needs to be shut down and stopped during maintenance, so that the ceramic diaphragm pipe needs to be improved, the service life of the ceramic diaphragm pipe is prolonged, and more influence on the production progress is avoided.
Disclosure of Invention
The invention aims to provide a high weather-resistant ceramic diaphragm pipe and a preparation method thereof, which aim to solve the problems in the background art.
The purpose of the invention can be realized by the following technical scheme: a preparation method of a high weather-resistant ceramic diaphragm pipe comprises the following steps:
the method comprises the following steps: mixing carbon fibers and carbon nanotubes according to a mass ratio of 1:2, grinding by using ball milling equipment, and sieving by using a 200-mesh sieve to obtain carbon powder; mixing 68% of nitric acid and 75% of sulfuric acid according to a volume ratio of 1:4 to prepare mixed acid; adding mixed acid and carbon powder into a flask, placing the flask in ultrasonic dispersion equipment, and setting parameters as follows: performing ultrasonic treatment for 40-60min at 40kHz and 100W, dispersing carbon powder in mixed acid, taking out the flask, heating to 90-100 ℃, stirring for 15-30min, and adding oxygen-containing functional groups on the surface of the carbon powder; standing for 24h to precipitate carbon powder to the bottom of the flask, removing the upper layer acid solution, washing the precipitate with distilled water for 2-3 times, and drying to obtain pretreated carbon powder; standby;
step two: adding glacial acetic acid into a flask, adding zirconyl nitrate and tetrabutyl zirconate, stirring for 15-30min, adding absolute ethyl alcohol into the flask, and continuously stirring for 20min to obtain a solution A;
step three: adding an acetic acid solution with the mass fraction of 30% into a flask, adding barium acetate and calcium acetate into the flask filled with the acetic acid solution, and stirring at room temperature for 15-30min to obtain a solution B;
step four: slowly adding the solution B into the solution A under the condition of continuous stirring, continuously stirring for 40-60min after the dropwise addition is finished, standing for 6h after the mixed liquid turns white, and carrying out ventilation drying at 65 ℃ to obtain a gel block; calcining the gel block at 800-900 deg.C for 5-6h, grinding to obtain perovskite compound powder (Ba)0.7Ca0.3)ZrO3Powder;
step five: will (Ba)0.7Ca0.3)ZrO3Powder, SiC powder, Al2O3The powder, ZrC powder, pretreated carbon powder and sintering aid are mixed according to the weight ratio of 2.5: 3: 5: 1: 0.6: mixing at a mass ratio of 0.45, and grinding for 30-60min by using a ball mill to obtain mixed powder;
step six: adding distilled water into a flask, adjusting the pH to 4 by using 35% hydrochloric acid by mass fraction, adding mixed powder into the flask, performing ultrasonic dispersion for 40-60min, standing, removing upper-layer clear liquid, drying lower-layer sediment at the temperature of 100-120 ℃, adding paraffin serving as a binder, stirring for 2-3h at the temperature of 90-100 ℃, preparing fluffy small particles, sieving by a sieve of 80 meshes to obtain particles with uniform particle size, filling the sieved particles into a mold, performing compression molding under the pressure of 420-450MPa, maintaining the pressure for 20-30s, and demolding to obtain a blank;
step seven: sintering the blank under the protection of argon and under the condition of 30MPa, wherein the parameters during sintering are as follows: at 1550 ℃ for 30 min; 1800 ℃ for 60 min; at 2000 deg.C for 30 min; sintering the blank and annealing to obtain the high weather-resistant ceramic diaphragm tube; the sintering aid can fill the pores among the grains and play a role in pinning;
further, the dosage ratio of the glacial acetic acid, the zirconyl nitrate, the tetrabutyl zirconate and the absolute ethyl alcohol in the solution A is 25 mL: 0.025 mol: 0.075 mol: 45 mL;
further, the dosage ratio of the acetic acid solution, the barium acetate and the calcium acetate in the solution B is 80 mL: 0.07 mol: 0.03 mol;
furthermore, in the fifth step, the sintering aid is MgO and TiO2Mixing according to the mass ratio of 3: 2.
The invention has the beneficial effects that:
1. in the production process of the high weather-resistant ceramic diaphragm tube, zirconium oxynitrate, tetrabutyl zirconate and other raw materials are used for preparing (Ba)0.7Ca0.3)ZrO3A powder having a cubic phase perovskite structure and being ferroelectric below its curie temperature; in the subsequent step, (Ba) is first0.7Ca0.3)ZrO3Mixing the powder with other raw materials to obtain mixed powder, filling the mixed powder into a mold to obtain a blank, and sintering at high temperature to obtain ceramic (Ba)0.7Ca0.3)ZrO3The crystal grains in the powder are phase-changed, the symmetry of the crystal structure is improved, and the powder is mixed with SiC powder and Al2O3Sintering raw materials such as powder and the like, and then reforming crystal grains; the sintering aid can promote the growth of crystal grains, the sintering aid is melted at high temperature to generate a liquid phase to fill pores among alumina and other particles, ceramic crystal grains in the ceramic diaphragm tube are not changed any more after annealing treatment and are uniformly distributed, and compared with common alumina ceramic, the ceramic diaphragm tube is more compact and regular, has better corrosion resistance, and simultaneously removes raw materials (Ba)0.7Ca0.3)ZrO3The ferroelectric property of the ceramic diaphragm tube has better function of blocking electrons, and the using effect of the ceramic diaphragm tube in an electrolysis device is ensured.
2. Contain the carbon dust in this high resistant ceramic diaphragm of waiting, carbon nanotube and carbon fiber in the carbon dust can further shorten under the processing of mixed acid length, and increase surperficial oxygen-containing functional group, thereby improve the dispersion ability of carbon fiber and carbon nanotube in aqueous, be favorable to with the mixing of other raw materials, the homogeneity of ceramic diaphragm pipe material everywhere has been guaranteed, add the carbon dust a small amount and can increase the intensity of ceramic diaphragm, increase the ability of anti-disintegration, the sintering auxiliary agent can compensate the influence of carbon dust to the ceramic diaphragm degree of compactness.
3. This high resistant ceramic diaphragm that waits has longer life, through the test, when guaranteeing better ionic conduction rate, life can reach more than 24 months, can increase electrolytic device's maintenance cycle to reduce the shut down and shut down the production number of times, be favorable to increasing the productivity.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Example 1
Preparation by the Sol-gel method (Ba)0.7Ca0.3)ZrO3A powder comprising the steps of:
the method comprises the following steps: adding 25mL of glacial acetic acid into a flask, then adding 0.025mol of zirconyl nitrate and 0.075mol of tetrabutyl zirconate, magnetically stirring for 15min, then adding 45mL of anhydrous ethanol into the flask, and continuously stirring for 20min to obtain a solution A;
step two: adding 80mL of 30 mass percent acetic acid solution into a flask, accurately weighing 0.07mol of barium acetate and 0.03mol of calcium acetate, adding into the flask containing the acetic acid solution, and magnetically stirring at room temperature for 15min to obtain a solution B;
step three: slowly adding the solution B into the solution A under the condition of continuous stirring, continuously stirring for 40min after the dropwise addition is finished, standing for 6h after the mixed liquid turns white, and carrying out ventilation drying at 65 ℃ to obtain a gel block; calcining the gel block at 800 deg.C for 6 hr, taking out the calcined material, and grinding to obtain (Ba)0.7Ca0.3)ZrO3And (3) powder.
Example 2
Preparation by the Sol-gel method (Ba)0.7Ca0.3)ZrO3A powder comprising the steps of:
the method comprises the following steps: adding 25mL of glacial acetic acid into a flask, then adding 0.025mol of zirconyl nitrate and 0.075mol of tetrabutyl zirconate, magnetically stirring for 20min, then adding 45mL of anhydrous ethanol into the flask, and continuously stirring for 20min to obtain a solution A;
step two: adding 80mL of 30 mass percent acetic acid solution into a flask, accurately weighing 0.07mol of barium acetate and 0.03mol of calcium acetate, adding into the flask containing the acetic acid solution, and magnetically stirring at room temperature for 20min to obtain a solution B;
step three: slowly adding the solution B into the solution A under the condition of continuous stirring, continuously stirring for 50min after the dropwise addition is finished, standing for 6h after the mixed liquid turns white, and carrying out ventilation drying at 65 ℃ to obtain a gel block; calcining the gel block at 850 deg.C for 5.5h, taking out the calcined substance, and grinding to obtain (Ba)0.7Ca0.3)ZrO3And (3) powder.
Example 3
Preparation by the Sol-gel method (Ba)0.7Ca0.3)ZrO3A powder comprising the steps of:
the method comprises the following steps: adding 25mL of glacial acetic acid into a flask, then adding 0.025mol of zirconyl nitrate and 0.075mol of tetrabutyl zirconate, magnetically stirring for 30min, then adding 45mL of anhydrous ethanol into the flask, and continuously stirring for 20min to obtain a solution A;
step two: adding 80mL of 30 mass percent acetic acid solution into a flask, accurately weighing 0.07mol of barium acetate and 0.03mol of calcium acetate, adding into the flask containing the acetic acid solution, and magnetically stirring at room temperature for 30min to obtain a solution B;
step three: slowly adding the solution B into the solution A under the condition of continuous stirring, continuously stirring for 60min after the dropwise addition is finished, standing for 6h after the mixed liquid turns white, and carrying out ventilation drying at 65 ℃ to obtain a gel block; calcining the gel block at 900 deg.C for 5 hr, taking out the calcined substance, and grinding to obtain (Ba)0.7Ca0.3)ZrO3And (3) powder.
Example 4
The preparation of the pretreated carbon powder comprises the following steps:
mixing 200g of carbon fibers and 400g of carbon nanotubes, grinding by using a small ball mill, and sieving by using a 200-mesh sieve to obtain carbon powder;
respectively measuring 300mL of nitric acid with the mass fraction of 68% and 1200mL of sulfuric acid with the mass fraction of 75% by using a measuring cylinder, placing a flask in an ice-water bath, adding the nitric acid into the flask, slowly adding the sulfuric acid, and continuously stirring to prepare mixed acid;
adding carbon powder into a flask containing mixed acid, placing the flask in ultrasonic dispersion equipment, and setting parameters as follows: dispersing carbon powder in mixed acid with the power of 100W at 40kHz for 40min by ultrasonic treatment, taking out the flask, heating to 90 ℃, stirring for 15min, further shortening the lengths of the carbon fibers and the carbon nano tubes by utilizing the strong oxidizing property of the mixed acid, and increasing oxygen-containing functional groups on the surface of the carbon powder so as to improve the dispersing capacity of the carbon fibers and the carbon nano tubes in water; and standing the flask for 24 hours to precipitate carbon powder to the bottom of the flask, removing the upper layer acid liquor, taking out the precipitate, washing the precipitate with distilled water for 2 times, and drying to obtain the pretreated carbon powder.
Example 5
The preparation of the pretreated carbon powder comprises the following steps:
mixing 200g of carbon fibers and 400g of carbon nanotubes, grinding by using a small ball mill, and sieving by using a 200-mesh sieve to obtain carbon powder;
respectively measuring 300mL of nitric acid with the mass fraction of 68% and 1200mL of sulfuric acid with the mass fraction of 75% by using a measuring cylinder, placing a flask in an ice-water bath, adding the nitric acid into the flask, slowly adding the sulfuric acid, and continuously stirring to prepare mixed acid;
adding carbon powder into a flask containing mixed acid, placing the flask in ultrasonic dispersion equipment, and setting parameters as follows: dispersing carbon powder in mixed acid with the power of 100W at 40kHz for 50min by ultrasonic treatment, taking out the flask, heating to 95 ℃, stirring for 20min, further shortening the lengths of the carbon fibers and the carbon nanotubes by utilizing the strong oxidizing property of the mixed acid, and increasing oxygen-containing functional groups on the surface of the carbon powder, thereby improving the dispersing capacity of the carbon fibers and the carbon nanotubes in water; and standing the flask for 24 hours to precipitate carbon powder to the bottom of the flask, removing the upper layer acid liquor, taking out the precipitate, washing the precipitate with distilled water for 2 times, and drying to obtain the pretreated carbon powder.
Example 6
The preparation of the pretreated carbon powder comprises the following steps:
mixing 200g of carbon fibers and 400g of carbon nanotubes, grinding by using a small ball mill, and sieving by using a 200-mesh sieve to obtain carbon powder;
respectively measuring 300mL of nitric acid with the mass fraction of 68% and 1200mL of sulfuric acid with the mass fraction of 75% by using a measuring cylinder, placing a flask in an ice-water bath, adding the nitric acid into the flask, slowly adding the sulfuric acid, and continuously stirring to prepare mixed acid;
adding carbon powder into a flask containing mixed acid, placing the flask in ultrasonic dispersion equipment, and setting parameters as follows: dispersing carbon powder in mixed acid with the power of 100W at 40kHz for 60min by ultrasonic treatment, taking out the flask, heating to 100 ℃, stirring for 30min, further shortening the lengths of the carbon fibers and the carbon nanotubes by utilizing the strong oxidizing property of the mixed acid, and increasing oxygen-containing functional groups on the surface of the carbon powder, thereby improving the dispersing capacity of the carbon fibers and the carbon nanotubes in water; and standing the flask for 24 hours to precipitate carbon powder to the bottom of the flask, removing the upper layer acid liquor, taking out the precipitate, washing the precipitate with distilled water for 3 times, and drying to obtain the pretreated carbon powder.
Example 7
The preparation method of the high weather-resistant ceramic diaphragm pipe comprises the following steps:
step S1: 30g of MgO and 20g of TiO2Mixing to prepare a sintering aid;
step S2: 250g of (Ba) prepared in example 1 were added0.7Ca0.3)ZrO3Powder, 300g SiC powder, 500g Al2O3Mixing the powder, 100g of ZrC powder, 60g of the pretreated carbon powder prepared in the example 4 and 45g of the sintering aid, and grinding the mixture for 30-60min by using a ball mill to obtain mixed powder;
step S3: adding distilled water into a flask, adjusting the pH to 4 by using 35% hydrochloric acid by mass, adding mixed powder into the flask, performing ultrasonic dispersion for 40-60min, standing, removing upper clear liquid, drying lower sediment at 100 ℃, adding paraffin serving as a binder, stirring for 2h at 90 ℃, preparing fluffy small particles, sieving by using a 80-mesh sieve to obtain particles with uniform particle size, filling the sieved particles into a mold, performing compression molding under the pressure of 420MPa, maintaining the pressure for 20s, and demolding to obtain a blank;
step S4: sintering the blank under the protection of argon and under the condition of 30MPa, wherein the parameters during sintering are as follows: at 1550 ℃ for 30 min; 1800 ℃ for 60 min; at 2000 deg.C for 30 min; fully volatilizing paraffin at the initial stage of sintering the blank, sintering the blank and annealing to obtain the high weather-resistant ceramic diaphragm tube; the sintering aid can fill the pores among the crystal grains, plays a role in pinning, and enables the sintered ceramic to be more compact.
Example 8
The preparation method of the high weather-resistant ceramic diaphragm pipe comprises the following steps:
step S1: 300g of MgO and 200g of TiO2Mixing to prepare a sintering aid;
step S2: 2.5kg of (Ba) prepared in example 20.7Ca0.3)ZrO3Powder, 3kg SiC powder, 5kg Al2O3Mixing the powder, 1kg of ZrC powder, 600g of the pretreated carbon powder prepared in example 5 and 450g of the sintering aid, and grinding the mixture for 40min by using a ball mill to obtain mixed powder;
step S3: adding distilled water into a flask, adjusting the pH to 4 by using 35% hydrochloric acid by mass, adding mixed powder into the flask, performing ultrasonic dispersion for 50min, standing, removing upper clear liquid, drying lower sediment at 110 ℃, adding paraffin serving as a binder, stirring for 2.5h at 95 ℃, preparing fluffy small particles, sieving by a 80-mesh sieve to obtain particles with uniform particle size, filling the sieved particles into a mold, performing compression molding under the pressure of 430MPa, maintaining the pressure for 25s, and demolding to obtain a blank;
step S4: sintering the blank under the protection of argon and under the condition of 30MPa, wherein the parameters during sintering are as follows: at 1550 ℃ for 30 min; 1800 ℃ for 60 min; at 2000 deg.C for 30 min; fully volatilizing paraffin at the initial stage of sintering the blank, sintering the blank and annealing to obtain the high weather-resistant ceramic diaphragm tube; the sintering aid can fill the pores among the crystal grains, plays a role in pinning, and enables the sintered ceramic to be more compact.
Example 9
The preparation method of the high weather-resistant ceramic diaphragm pipe comprises the following steps:
step S1: 300g of MgO and 200g of TiO2Mixing to prepare a sintering aid;
step S2: 2.5kg of (Ba) prepared in example 30.7Ca0.3)ZrO3Powder, 3kg SiC powder, 5kg Al2O3Mixing the powder, 1kg of ZrC powder, 600g of the pretreated carbon powder prepared in the example 6 and 450g of the sintering aid, and grinding the mixture for 60min by using a ball mill to obtain mixed powder;
step S3: adding distilled water into a flask, adjusting the pH to 4 by using 35% hydrochloric acid by mass, adding mixed powder into the flask, performing ultrasonic dispersion for 60min, standing, removing upper clear liquid, drying lower sediment at 120 ℃, adding paraffin serving as a binder, stirring for 3h at 100 ℃, preparing fluffy small particles, sieving by a 80-mesh sieve to obtain particles with uniform particle size, filling the sieved particles into a mold, performing compression molding under the pressure of 450MPa, maintaining the pressure for 30s, and demolding to obtain a blank;
step S4: sintering the blank under the protection of argon and under the condition of 30MPa, wherein the parameters during sintering are as follows: at 1550 ℃ for 30 min; 1800 ℃ for 60 min; at 2000 deg.C for 30 min; in the initial sintering stage, paraffin is fully volatilized, and the high-weather-resistance ceramic diaphragm tube is obtained after the blank is sintered and annealed; the sintering aid can fill the pores among the crystal grains, plays a role in pinning, and enables the sintered ceramic to be more compact.
Comparative example 1: on the basis of example 9, a ceramic diaphragm tube was prepared without adding pretreatment carbon powder and with the remaining steps unchanged.
Comparative example 2: in addition to example 9, no (Ba) was added0.7Ca0.3)ZrO3And (4) powder, and the rest steps are kept unchanged, so that the ceramic diaphragm tube is prepared.
Comparative example 3: on the basis of example 9, no pretreatment carbon powder and (Ba) were added0.7Ca0.3)ZrO3And (4) powder, and the rest steps are kept unchanged, so that the ceramic diaphragm tube is prepared.
The ceramic membrane tubes prepared in examples 7-9 and comparative examples 1-3 were taken, tested for performance according to standard JC/T2344-2015 and the test data recorded, with the results shown in Table 1:
TABLE 1
| Item | Example 7 | Example 8 | Example 9 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Flexural strength/MPa | 46 | 46 | 46 | 38 | 44 | 37 |
| Acid resistance/% | 99.4 | 99.4 | 99.4 | 99.4 | 98.1 | 98 |
| Alkali resistance/%) | 97.2 | 97.2 | 97.2 | 98.0 | 95.9 | 95.9 |
| Permeability/% | 0.4 | 0.4 | 0.4 | 0.6 | 1.2 | 1.3 |
| Maximum pore diameter/. mu.m | 2 | 2 | 2 | 2 | 4 | 4 |
As can be seen from Table 1, the ceramic diaphragm tubes fired in examples 7 to 9 had better flexural strength and were also more excellent in acid resistance and alkali resistance.
It should be noted that, in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The preparation method of the high weather-resistant ceramic diaphragm pipe is characterized by comprising the following steps of:
the method comprises the following steps: adding glacial acetic acid, zirconyl nitrate and tetrabutyl zirconate into a flask, stirring for 15-30min, adding absolute ethyl alcohol, and stirring for 20min to obtain a solution A; dissolving barium acetate and calcium acetate in an acetic acid solution to obtain a solution B;
step two: adding the solution B into the solution A, stirring for 40-60min, standing for 6h, drying, calcining, and grinding to obtain perovskite type compound powder;
step three: mixing perovskite type compound powder, SiC powder, Al2O3The powder, ZrC powder, pretreated carbon powder and sintering aid are mixed according to the weight ratio of 2.5: 3: 5: 1: 0.6: 0.45, and grinding to obtain mixed powder;
step four: post-treating the mixed powder, filling the mixed powder into a mold, performing compression molding under the pressure of 420-450MPa, maintaining the pressure for 20-30s, and demolding to obtain a blank;
step five: and sintering and annealing the blank according to set parameters under the conditions of 30MPa and inert gas protection to obtain the high weather-resistant ceramic diaphragm tube.
2. The method for preparing a high weather-resistant ceramic diaphragm tube according to claim 1, wherein the pretreated carbon powder in step three is prepared by the following method:
mixing carbon fibers and carbon nanotubes according to a mass ratio of 1:2, grinding, and sieving with a 200-mesh sieve to obtain carbon powder; preparing mixed acid by using nitric acid and sulfuric acid, adding the mixed acid and carbon powder into a flask for ultrasonic treatment for 40-60min, stirring for 15-30min at the temperature of 90-100 ℃, standing for 24h, taking precipitate, washing the precipitate with distilled water, and drying to obtain pretreated carbon powder.
3. The method for preparing the high weather-resistant ceramic diaphragm tube according to claim 1, wherein the post-treatment in the fourth step is as follows: adding distilled water into a flask, adjusting pH to 4 with hydrochloric acid, adding the mixed powder, performing ultrasonic dispersion for 40-60min, standing, drying, adding paraffin, stirring at 90-100 deg.C for 2-3h, and sieving with 80 mesh sieve to obtain granules.
4. The method for preparing a high weather-resistant ceramic membrane tube as claimed in claim 1, wherein the sintering aid is MgO and TiO2Mixing according to the mass ratio of 3: 2.
5. The method for preparing a high weather-resistant ceramic diaphragm tube according to claim 1, wherein the parameters during sintering are as follows: at 1550 ℃ for 30 min; 1800 ℃ for 60 min; 2000 deg.C, 30 min.
6. The method for preparing a high weather-resistant ceramic diaphragm tube according to claim 1, wherein the dosage ratio of the glacial acetic acid, the zirconyl nitrate, the tetrabutyl zirconate and the absolute ethyl alcohol in the solution A is 25 mL: 0.025 mol: 0.075 mol: 45 mL.
7. The method for preparing a high weather-resistant ceramic diaphragm tube according to claim 1, wherein the dosage ratio of the acetic acid solution, the barium acetate and the calcium acetate in the solution B is 80 mL: 0.07 mol: 0.03 mol.
8. A highly weather-resistant ceramic diaphragm tube produced by the production method according to any one of claims 1 to 7.
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