CN114835477B - Multifunctional water purification ceramic material - Google Patents
Multifunctional water purification ceramic material Download PDFInfo
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- CN114835477B CN114835477B CN202210398759.4A CN202210398759A CN114835477B CN 114835477 B CN114835477 B CN 114835477B CN 202210398759 A CN202210398759 A CN 202210398759A CN 114835477 B CN114835477 B CN 114835477B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 40
- 238000000746 purification Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000002156 mixing Methods 0.000 claims abstract description 100
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001914 filtration Methods 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004927 clay Substances 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 238000000227 grinding Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 24
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 24
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000000748 compression moulding Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 abstract 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 abstract 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical class [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 80
- 238000005457 optimization Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 229920000767 polyaniline Polymers 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- -1 arsenic ions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/466—Conversion of one form of calcium sulfate to another
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- C04B35/71—Ceramic products containing macroscopic reinforcing agents
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Abstract
The invention discloses a multifunctional water purification ceramic material, and relates to the technical field of new materials. The preparation method comprises the steps of firstly mixing pretreated phosphogypsum and hydrochloric acid to react under normal pressure to obtain calcium sulfate dihydrate whisker, then coating a silicon dioxide layer and a gamma-aminopropyl triethoxy silicon layer on the outer side of the calcium sulfate dihydrate whisker in sequence to obtain modified calcium sulfate whisker, mixing the modified calcium sulfate whisker with graphene oxide dispersion liquid containing aniline, adding a catalyst solution, stirring to react, grinding to obtain modified graphene, mixing the modified graphene with diatomite and purple clay, adding a carboxymethyl cellulose sodium solution, stirring, mixing, pressing, forming and sintering to obtain the multifunctional water purification ceramic material. The multifunctional water purification ceramic material prepared by the invention has good filtering effect, bactericidal property and thermal conductivity.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a multifunctional water purification ceramic material.
Background
Along with the development of society and the improvement of living standard, the requirements of people on living quality are higher and higher, and clean and safe drinking water is the guarantee of living quality of people. Obtaining clean and safe drinking water has become a popular issue worldwide. Water is the main carrier for the transmission of various germs, and 80% of diseases suffered by human beings are related to water pollution. At present, water pollution is serious day by day, surface water such as rivers and lakes and groundwater in partial areas are polluted to different degrees, and water shortage problem of water quality has attracted wide attention.
The main pollutants in the drinking water comprise soluble heavy metal ions, arsenic ions, trace organic pollutants, disinfection byproducts, nitrate, nitrite, pathogenic bacteria, viruses, pathogenic microorganisms and the like, and the water purifying materials widely adopted at present mainly comprise active carbon, molecular sieves, KDF, nanofiltration membranes and the like.
Adsorption is one of the effective methods for removing contaminants from a contaminated water body. Adsorption is a physicochemical phenomenon in which an adsorbate is adsorbed onto an adsorbent by the action of intermolecular van der Waals forces, electrostatic forces, hydrogen bonds, chemical bonds, and the like of the adsorbate and the adsorbent. In the field of environmental protection, the adsorption method is mainly applied to pretreatment (reducing the load of a main device for water treatment and recycling useful substances) and advanced treatment (improving the quality of treated water and meeting the water quality requirement of recycled water), and has particularly obvious treatment effect on extremely toxic and hardly degradable pollutants which are difficult to effectively treat by other methods.
At present, ceramic materials used for purifying water in the market have single functions, and are used for treating and filtering substances insoluble in water and adsorbing metal ions, and have no other functions, so that the conventional water-purifying ceramic materials cannot be completely suitable for living needs of people.
Disclosure of Invention
The invention aims to provide a multifunctional water purification ceramic material and a preparation method thereof, which are used for solving the problems in the prior art.
The multifunctional water purification ceramic material is characterized by mainly comprising the following raw material components in parts by weight: 60-85 parts of diatomite, 10-15 parts of purple clay, 2-4 parts of sodium carboxymethylcellulose and 8-16 parts of modified graphene;
the modified graphene is prepared by mixing lamellar graphene oxide with aniline, reacting with modified calcium sulfate whisker under the action of ammonium persulfate, and ball milling.
As optimization, the modified calcium sulfate whisker is prepared by treating calcium sulfate dihydrate whisker with tetraethoxysilane and gamma-aminopropyl triethoxysilane.
As optimization, the calcium sulfate dihydrate whisker is prepared by removing impurities from phosphogypsum and then reacting with hydrochloric acid under normal pressure.
As optimization, the multifunctional water purification ceramic material is composed of the following raw materials in parts by weight: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethylcellulose and 13 parts of modified graphene.
As optimization, the preparation method of the multifunctional water purification ceramic material mainly comprises the following preparation steps:
(1) Mixing pretreated phosphogypsum with hydrochloric acid, stirring for reaction, filtering, and drying to obtain calcium sulfate dihydrate whisker;
(2) Mixing the calcium sulfate dihydrate whisker obtained in the step (1) with an ethanol solution, adding ammonia water, tetraethoxysilane and polyvinylpyrrolidone, stirring for reaction, filtering, drying to obtain a modified calcium sulfate whisker blank, mixing the modified calcium sulfate whisker blank with a gamma-aminopropyl triethoxysilane solution, stirring and mixing, and filtering to obtain the modified calcium sulfate whisker;
(3) Mixing graphene oxide dispersion liquid with aniline, adding the modified calcium sulfate whisker obtained in the step (2), stirring and mixing to obtain graphene oxide mixed liquid, mixing the graphene oxide mixed liquid with a catalyst solution, stirring and reacting, filtering, drying and grinding to obtain modified graphene;
(4) Weighing the following components in parts by weight: 60-85 parts of diatomite, 10-15 parts of purple clay, 2-4 parts of sodium carboxymethyl cellulose and 8-16 parts of modified graphene obtained in the step (3), mixing sodium carboxymethyl cellulose with water to obtain a binder, mixing the purple clay with the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture with the binder, press-molding to obtain a green body, sintering the green body, cooling to room temperature, and discharging to obtain the multifunctional water purification ceramic material.
As optimization, the preparation method of the multifunctional water purification ceramic material mainly comprises the following preparation steps:
(1) Mixing pretreated phosphogypsum and hydrochloric acid with the mass fraction of 20% according to the mass ratio of 1:3-1:6, stirring and reacting for 8-12 min at the temperature of 80 ℃, filtering to obtain a calcium sulfate dihydrate whisker blank, and drying the calcium sulfate dihydrate whisker blank for 1-3 h at the temperature of 85 ℃ to obtain the calcium sulfate dihydrate whisker;
(2) Mixing the calcium sulfate dihydrate whisker obtained in the step (1) with an aqueous ethanol solution with the mass fraction of 80% according to the mass ratio of 1:100-1:250 in a beaker, adding ammonia water with the mass fraction of 10% and the mass ratio of 1-3 times of the calcium sulfate dihydrate whisker into the beaker, stirring and reacting for 12-13 hours at the temperature of 45 ℃ the ethyl orthosilicate with the mass fraction of 2-5 times of the calcium sulfate dihydrate whisker and polyvinylpyrrolidone with the mass fraction of 1-2 times of the calcium sulfate dihydrate whisker, filtering to obtain a filter cake, drying the filter cake for 1-3 hours at the temperature of 60 ℃ to obtain a modified calcium sulfate whisker blank, mixing the modified calcium sulfate whisker blank with a gamma-aminopropyl triethoxysilane ethanol solution with the mass fraction of 15% according to the mass ratio of 1:20-1:25, stirring and mixing for 5-10 hours, and filtering to obtain the modified calcium sulfate whisker;
(3) Mixing graphene oxide dispersion liquid and aniline in a weight ratio of 10:1-10:3 in a flask, adding modified calcium sulfate whiskers obtained in the step (2) with the mass of 0.1-0.3 times of that of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain graphene oxide mixed liquid, mixing the graphene oxide mixed liquid and catalyst solution in a volume ratio of 3:1-8:1, stirring and reacting for 5-8 hours at a temperature of 0-10 ℃, filtering to obtain modified graphene blank, drying the modified graphene blank at a temperature of 80-90 ℃ for 1-2 hours, and grinding for 30-40 minutes to obtain modified graphene;
(4) Weighing the following components in parts by weight: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethyl cellulose and 13 parts of modified graphene obtained in the step (3), mixing sodium carboxymethyl cellulose with water according to a mass ratio of 1:40-1:100 to obtain a binder, mixing the purple clay with the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture with the binder, compacting to obtain a green body, sintering the green body, cooling to room temperature, and discharging to obtain the multifunctional water purification ceramic material.
As optimization, the preparation method of the pretreated phosphogypsum in the step (1) comprises the steps of crushing and ball milling phosphogypsum, sieving with a 200-mesh sieve to obtain refined phosphogypsum, and washing the refined phosphogypsum with deionized water for 2-4 times to obtain the pretreated phosphogypsum.
As optimization, the graphene oxide dispersion liquid in the step (3) is obtained by mixing graphene oxide and water according to a mass ratio of 1:100-1:150, and performing ultrasonic dispersion for 10-30 min under the condition of a frequency of 55 kHz; the catalyst solution is prepared by mixing ammonium persulfate with hydrochloric acid with the concentration of 1mol/L according to the mass ratio of 1:10.
And (3) as optimization, the pressure condition of the compression molding in the step (4) is 35-40 MPa.
And (3) as optimization, heating the sintering process conditions in the step (4) in the air for 2 hours at the temperature of 195 ℃, then heating to 800 ℃ at the heating rate of 2-3 ℃/min in the nitrogen atmosphere, preserving heat for 2 hours, heating to 1100-1400 ℃ at the heating rate of 2-4 ℃/min in the air atmosphere, and preserving heat and sintering for 30-40 minutes.
Compared with the prior art, the invention has the beneficial effects that:
when the multifunctional water purification ceramic material is prepared, the modified graphene is prepared by mixing lamellar graphene oxide and aniline, reacting the mixture with modified calcium sulfate whisker under the action of ammonium persulfate, and ball milling.
Firstly, modified calcium sulfate whiskers are used in modified graphene, the surface of the modified calcium sulfate whiskers is coated with silicon dioxide, gamma-aminopropyl triethoxysilane can be coated outside under the action of the silicon dioxide, and due to the action of the gamma-aminopropyl triethoxysilane, after the modified calcium sulfate whiskers are mixed with aniline, aniline can be adsorbed on the surface of the modified calcium sulfate whiskers under the action of amino, and meanwhile, in the preparation process of graphene oxide mixed solution, the surface of the graphene oxide is also adsorbed with aniline, so that when aniline is polymerized to form polyaniline under the catalysis of ammonium persulfate, the modified calcium sulfate whiskers can be substituted into the interlaminar of the graphene oxide, so that a modified calcium sulfate whisker-polyaniline composite pillared structure is formed among the modified graphene, the modified graphene has filtering performance, and the filtering performance of the product is improved after the modified graphene is added into the product;
secondly, in the sintering process of the multifunctional water purification ceramic material, polyaniline among graphene oxide can be carbonized to form a carbonaceous structure under the condition of nitrogen in the early stage, a carbon-modified calcium sulfate whisker pillared structure is formed, and the graphene oxide is reduced to form graphene, and due to the existence of graphene and carbon, the heat conducting property of a product can be improved, so that the product has a heating function, meanwhile, in the later sintering process, calcium sulfate dihydrate in the modified calcium sulfate whisker can be decomposed to generate steam, and the decomposition temperature of the calcium sulfate whisker can be reduced under the action of the carbon, so that the calcium sulfate is decomposed at a relatively low temperature to generate gas and calcium oxide, and therefore, under the decomposition action of the modified calcium sulfate whisker, a carbonaceous layer formed by polyaniline can form a porous structure, so that the filtering effect of the product on metal ions is further improved;
in addition, the carbon-modified calcium sulfate whisker column support structure among the graphenes contains calcium oxide, and the calcium oxide can endow the product with the capability of treating acidic sewage, and the calcium hydroxide has good bactericidal property, so that the product has good bactericidal property, and further, after the modified grapheme is added into the product, the product can be endowed with better service performance.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. 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.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the method for testing each index of the multifunctional water purification ceramic material manufactured in the following examples is as follows:
porosity: the porosities of the multifunctional water purifying ceramic materials obtained in each example and the products obtained in the comparative example were measured, and the water flux was measured for 5 minutes under the condition of a water pressure of 0.36 MPa.
Metal ion removal rate: the multifunctional water purification ceramic material obtained in each example and the product obtained in the comparative example are used for filtering metal ion solution with the same concentration, and the removal rate of chromium ions, copper ions and lead ions is measured.
Sterilization rate: the multifunctional water purification ceramic material obtained in each example and the product obtained in the comparative example are used for filtering coliform bacteria liquid with the same concentration, and the sterilization rate is measured.
Example 1
The multifunctional water purifying ceramic material mainly comprises the following components in parts by weight: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethylcellulose and 13 parts of modified graphene.
The preparation method of the multifunctional water purification ceramic material mainly comprises the following preparation steps:
(1) Mixing pretreated phosphogypsum and hydrochloric acid with the mass fraction of 20% according to the mass ratio of 1:5, stirring and reacting for 10min at the temperature of 80 ℃, filtering to obtain a calcium sulfate dihydrate whisker blank, and drying the calcium sulfate dihydrate whisker blank for 2h at the temperature of 85 ℃ to obtain the calcium sulfate dihydrate whisker;
(2) Mixing the calcium sulfate dihydrate whisker obtained in the step (1) with an aqueous ethanol solution with the mass fraction of 80% according to the mass ratio of 1:150 in a beaker, adding ammonia water with the mass fraction of 10% and the mass ratio of 2 times of the calcium sulfate dihydrate whisker into the beaker, stirring ethyl orthosilicate with the mass ratio of 3 times of the calcium sulfate dihydrate whisker and polyvinylpyrrolidone with the mass ratio of 1.5 times of the calcium sulfate dihydrate whisker, reacting for 12 hours at the temperature of 45 ℃, filtering to obtain a filter cake, drying the filter cake for 2 hours at the temperature of 60 ℃ to obtain a modified calcium sulfate whisker blank, mixing the modified calcium sulfate whisker blank with a gamma-aminopropyl triethoxysilane ethanol solution with the mass fraction of 15% according to the mass ratio of 1:22, stirring and mixing for 6 hours, and filtering to obtain modified calcium sulfate whisker;
(3) Mixing graphene oxide dispersion liquid and aniline in a flask according to a mass ratio of 10:3, adding modified calcium sulfate whiskers obtained in the step (2) with the mass of 0.2 times of that of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain graphene oxide mixed liquid, mixing the graphene oxide mixed liquid and catalyst solution according to a volume ratio of 4:1, stirring and reacting for 6 hours at a temperature of 6 ℃, filtering to obtain a modified graphene blank, drying the modified graphene blank at a temperature of 85 ℃ for 1.5 hours, and grinding for 35 minutes to obtain modified graphene;
(4) Weighing the following components in parts by weight: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethyl cellulose and 13 parts of modified graphene obtained in the step (3), mixing sodium carboxymethyl cellulose with water according to a mass ratio of 1:50 to obtain a binder, mixing the purple clay with the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture with the binder, pressing and forming to obtain a green body, sintering the green body, cooling to room temperature, and discharging to obtain the multifunctional water purification ceramic material.
As optimization, the preparation method of the pretreated phosphogypsum in the step (1) comprises the steps of crushing and ball milling phosphogypsum, sieving with a 200-mesh sieve to obtain refined phosphogypsum, and washing the refined phosphogypsum with deionized water for 2-4 times to obtain the pretreated phosphogypsum.
As optimization, the graphene oxide dispersion liquid in the step (3) is obtained by mixing graphene oxide and water according to a mass ratio of 1:120, and performing ultrasonic dispersion for 20min under the condition that the frequency is 55 kHz; the catalyst solution is prepared by mixing ammonium persulfate with hydrochloric acid with the concentration of 1mol/L according to the mass ratio of 1:10.
Preferably, the pressure condition of the compression molding in the step (4) is 36MPa.
As optimization, the sintering process condition in the step (4) is that after heating in air for 2 hours at the temperature of 195 ℃, the temperature is raised to 800 ℃ at the temperature raising rate of 3 ℃/min in nitrogen atmosphere, the temperature is kept for 2 hours, and finally the temperature is raised to 1150 ℃ at the temperature raising rate of 3 ℃/min in air atmosphere, and the temperature is kept for 35 minutes for sintering.
Example 2
The multifunctional water purifying ceramic material mainly comprises the following components in parts by weight: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethylcellulose and 13 parts of modified graphene.
The preparation method of the multifunctional water purification ceramic material mainly comprises the following preparation steps:
(1) Mixing pretreated phosphogypsum and hydrochloric acid with the mass fraction of 20% according to the mass ratio of 1:5, stirring and reacting for 10min at the temperature of 80 ℃, filtering to obtain a calcium sulfate dihydrate whisker blank, and drying the calcium sulfate dihydrate whisker blank for 2h at the temperature of 85 ℃ to obtain the calcium sulfate dihydrate whisker;
(2) Mixing the calcium sulfate dihydrate whisker obtained in the step (1) with an 80% ethanol aqueous solution according to a mass ratio of 1:150 in a beaker, adding ammonia water with a mass fraction of 10% and 2 times that of the calcium sulfate dihydrate whisker into the beaker, stirring ethyl orthosilicate with a mass fraction of 3 times that of the calcium sulfate dihydrate whisker, reacting for 12 hours at a temperature of 45 ℃, filtering to obtain a filter cake, drying the filter cake at a temperature of 60 ℃ for 2 hours to obtain a modified calcium sulfate whisker blank, mixing the modified calcium sulfate whisker blank with a 15% gamma-aminopropyl triethoxysilane ethanol solution according to a mass ratio of 1:22, stirring and mixing for 6 hours, and filtering to obtain the modified calcium sulfate whisker;
(3) Mixing graphene oxide dispersion liquid and aniline in a flask according to a mass ratio of 10:3, adding modified calcium sulfate whiskers obtained in the step (2) with the mass of 0.2 times of that of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain graphene oxide mixed liquid, mixing the graphene oxide mixed liquid and catalyst solution according to a volume ratio of 4:1, stirring and reacting for 6 hours at a temperature of 6 ℃, filtering to obtain a modified graphene blank, drying the modified graphene blank at a temperature of 85 ℃ for 1.5 hours, and grinding for 35 minutes to obtain modified graphene;
(4) Weighing the following components in parts by weight: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethyl cellulose and 13 parts of modified graphene obtained in the step (3), mixing sodium carboxymethyl cellulose with water according to a mass ratio of 1:50 to obtain a binder, mixing the purple clay with the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture with the binder, pressing and forming to obtain a green body, sintering the green body, cooling to room temperature, and discharging to obtain the multifunctional water purification ceramic material.
As optimization, the preparation method of the pretreated phosphogypsum in the step (1) comprises the steps of crushing and ball milling phosphogypsum, sieving with a 200-mesh sieve to obtain refined phosphogypsum, and washing the refined phosphogypsum with deionized water for 2-4 times to obtain the pretreated phosphogypsum.
As optimization, the graphene oxide dispersion liquid in the step (3) is obtained by mixing graphene oxide and water according to a mass ratio of 1:120, and performing ultrasonic dispersion for 20min under the condition that the frequency is 55 kHz; the catalyst solution is prepared by mixing ammonium persulfate with hydrochloric acid with the concentration of 1mol/L according to the mass ratio of 1:10.
Preferably, the pressure condition of the compression molding in the step (4) is 36MPa.
As optimization, the sintering process condition in the step (4) is that after heating in air for 2 hours at the temperature of 195 ℃, the temperature is raised to 800 ℃ at the temperature raising rate of 3 ℃/min in nitrogen atmosphere, the temperature is kept for 2 hours, and finally the temperature is raised to 1150 ℃ at the temperature raising rate of 3 ℃/min in air atmosphere, and the temperature is kept for 35 minutes for sintering.
Example 3
The multifunctional water purifying ceramic material mainly comprises the following components in parts by weight: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethylcellulose and 13 parts of modified graphene.
The preparation method of the multifunctional water purification ceramic material mainly comprises the following preparation steps:
(1) Mixing pretreated phosphogypsum and hydrochloric acid with the mass fraction of 20% according to the mass ratio of 1:5, stirring and reacting for 10min at the temperature of 80 ℃, filtering to obtain a calcium sulfate dihydrate whisker blank, and drying the calcium sulfate dihydrate whisker blank for 2h at the temperature of 85 ℃ to obtain the calcium sulfate dihydrate whisker;
(2) Mixing the calcium sulfate dihydrate whisker obtained in the step (1) with an ethanol aqueous solution with the mass fraction of 80% in a beaker according to the mass ratio of 1:150, adding ammonia water with the mass fraction of 10% and the mass fraction of 2 times of the calcium sulfate dihydrate whisker into the beaker, stirring ethyl orthosilicate with the mass of 3 times of the calcium sulfate dihydrate whisker and polyvinylpyrrolidone with the mass of 1.5 times of the calcium sulfate dihydrate whisker, reacting for 12 hours at the temperature of 45 ℃, and filtering to obtain modified calcium sulfate whisker;
(3) Mixing graphene oxide dispersion liquid and aniline in a flask according to a mass ratio of 10:3, adding modified calcium sulfate whiskers obtained in the step (2) with the mass of 0.2 times of that of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain graphene oxide mixed liquid, mixing the graphene oxide mixed liquid and catalyst solution according to a volume ratio of 4:1, stirring and reacting for 6 hours at a temperature of 6 ℃, filtering to obtain a modified graphene blank, drying the modified graphene blank at a temperature of 85 ℃ for 1.5 hours, and grinding for 35 minutes to obtain modified graphene;
(4) Weighing the following components in parts by weight: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethyl cellulose and 13 parts of modified graphene obtained in the step (3), mixing sodium carboxymethyl cellulose with water according to a mass ratio of 1:50 to obtain a binder, mixing the purple clay with the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture with the binder, pressing and forming to obtain a green body, sintering the green body, cooling to room temperature, and discharging to obtain the multifunctional water purification ceramic material.
As optimization, the preparation method of the pretreated phosphogypsum in the step (1) comprises the steps of crushing and ball milling phosphogypsum, sieving with a 200-mesh sieve to obtain refined phosphogypsum, and washing the refined phosphogypsum with deionized water for 2-4 times to obtain the pretreated phosphogypsum.
As optimization, the graphene oxide dispersion liquid in the step (3) is obtained by mixing graphene oxide and water according to a mass ratio of 1:120, and performing ultrasonic dispersion for 20min under the condition that the frequency is 55 kHz; the catalyst solution is prepared by mixing ammonium persulfate with hydrochloric acid with the concentration of 1mol/L according to the mass ratio of 1:10.
Preferably, the pressure condition of the compression molding in the step (4) is 36MPa.
As optimization, the sintering process condition in the step (4) is that after heating in air for 2 hours at the temperature of 195 ℃, the temperature is raised to 800 ℃ at the temperature raising rate of 3 ℃/min in nitrogen atmosphere, the temperature is kept for 2 hours, and finally the temperature is raised to 1150 ℃ at the temperature raising rate of 3 ℃/min in air atmosphere, and the temperature is kept for 35 minutes for sintering.
Comparative example 1
The multifunctional water purifying ceramic material mainly comprises the following components in parts by weight: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethylcellulose and 13 parts of modified graphene.
The preparation method of the multifunctional water purification ceramic material mainly comprises the following preparation steps:
(1) Mixing pretreated phosphogypsum and hydrochloric acid with the mass fraction of 20% according to the mass ratio of 1:5, stirring and reacting for 10min at the temperature of 80 ℃, filtering to obtain a calcium sulfate dihydrate whisker blank, and drying the calcium sulfate dihydrate whisker blank for 2h at the temperature of 85 ℃ to obtain the calcium sulfate dihydrate whisker;
(2) Mixing graphene oxide dispersion liquid and aniline in a flask according to a mass ratio of 10:3, adding calcium sulfate dihydrate whisker obtained in the step (2) with the mass of 0.2 times of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain graphene oxide mixed liquid, mixing the graphene oxide mixed liquid and catalyst solution according to a volume ratio of 4:1, stirring and reacting for 6 hours at a temperature of 6 ℃, filtering to obtain a modified graphene blank, drying the modified graphene blank for 1.5 hours at a temperature of 85 ℃, and grinding for 35 minutes to obtain modified graphene;
(3) Weighing the following components in parts by weight: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethyl cellulose and 13 parts of modified graphene obtained in the step (2), mixing sodium carboxymethyl cellulose with water according to a mass ratio of 1:50 to obtain a binder, mixing the purple clay with the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture with the binder, pressing and forming to obtain a green body, sintering the green body, cooling to room temperature, and discharging to obtain the multifunctional water purification ceramic material.
As optimization, the preparation method of the pretreated phosphogypsum in the step (1) comprises the steps of crushing and ball milling phosphogypsum, sieving with a 200-mesh sieve to obtain refined phosphogypsum, and washing the refined phosphogypsum with deionized water for 2-4 times to obtain the pretreated phosphogypsum.
As optimization, the graphene oxide dispersion liquid in the step (2) is obtained by mixing graphene oxide and water according to a mass ratio of 1:120, and performing ultrasonic dispersion for 20min under the condition that the frequency is 55 kHz; the catalyst solution is prepared by mixing ammonium persulfate with hydrochloric acid with the concentration of 1mol/L according to the mass ratio of 1:10.
Preferably, the pressure condition of the compression molding in the step (3) is 36MPa.
As optimization, the sintering process condition in the step (3) is that after heating in air for 2 hours at the temperature of 195 ℃, the temperature is raised to 800 ℃ at the temperature raising rate of 3 ℃/min in nitrogen atmosphere, the temperature is kept for 2 hours, and finally the temperature is raised to 1150 ℃ at the temperature raising rate of 3 ℃/min in air atmosphere, and the temperature is kept for 35 minutes for sintering.
Comparative example 2
The multifunctional water purifying ceramic material mainly comprises the following components in parts by weight: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethylcellulose and 13 parts of modified graphene.
The preparation method of the multifunctional water purification ceramic material mainly comprises the following preparation steps:
(1) Mixing pretreated phosphogypsum and hydrochloric acid with the mass fraction of 20% according to the mass ratio of 1:5, stirring and reacting for 10min at the temperature of 80 ℃, filtering to obtain a calcium sulfate dihydrate whisker blank, and drying the calcium sulfate dihydrate whisker blank for 2h at the temperature of 85 ℃ to obtain the calcium sulfate dihydrate whisker;
(2) Mixing graphene oxide dispersion liquid and aniline in a flask according to a mass ratio of 10:3, adding calcium sulfate dihydrate whisker obtained in the step (2) with the mass of 0.2 times of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain graphene oxide mixed liquid, mixing the graphene oxide mixed liquid and catalyst solution according to a volume ratio of 4:1, stirring and reacting for 6 hours at a temperature of 6 ℃, filtering to obtain a modified graphene blank, drying the modified graphene blank for 1.5 hours at a temperature of 85 ℃, and grinding for 35 minutes to obtain modified graphene;
(3) Weighing the following components in parts by weight: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethyl cellulose and 13 parts of modified graphene obtained in the step (2), mixing sodium carboxymethyl cellulose with water according to a mass ratio of 1:50 to obtain a binder, mixing the purple clay with the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture with the binder, pressing and forming to obtain a green body, sintering the green body, cooling to room temperature, and discharging to obtain the multifunctional water purification ceramic material.
As optimization, the preparation method of the pretreated phosphogypsum in the step (1) comprises the steps of crushing and ball milling phosphogypsum, sieving with a 200-mesh sieve to obtain refined phosphogypsum, and washing the refined phosphogypsum with deionized water for 2-4 times to obtain the pretreated phosphogypsum.
As optimization, the graphene oxide dispersion liquid in the step (2) is obtained by mixing graphene oxide and water according to a mass ratio of 1:120, and performing ultrasonic dispersion for 20min under the condition that the frequency is 55 kHz; the catalyst solution is prepared by mixing ammonium persulfate with hydrochloric acid with the concentration of 1mol/L according to the mass ratio of 1:10.
Preferably, the pressure condition of the compression molding in the step (3) is 36MPa.
As optimization, the sintering process condition in the step (3) is that the temperature is increased to 1150 ℃ at the heating rate of 3 ℃/min in an air atmosphere, and the sintering is carried out for 35min.
Effect example
The following table 1 shows the results of performance analysis of the multifunctional water purifying ceramic materials using examples 1 to 3 of the present invention and comparative examples.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Porosity (%) | 65.7 | 64.2 | 52.5 | 50.6 | 63.2 |
| Water flux (mL) | 664 | 623 | 526 | 507 | 628 |
| Chromium ion removal Rate (%) | 99 | 91 | 81 | 76 | 78 |
| Copper ion removal Rate (%) | 99 | 88 | 82 | 72 | 73 |
| Lead ion removal Rate (%) | 99 | 90 | 80 | 70 | 75 |
| Sterilization rate (%) | 96 | 78 | 62 | 50 | 42 |
| Thermal conductivity (W/mK) | 156 | 105 | 88 | 66 | 63 |
From comparison of experimental data of example 1 and comparative example in table 1, it can be found that the addition of modified graphene can effectively improve the removal rate of metal ions of the product while imparting bactericidal property and thermal conductivity to the product, and from comparison of experimental data of example 1 and example 2, it can be found that when polyvinylpyrrolidone is not added to modified calcium sulfate whisker in modified graphene during preparation, the silicon dioxide layer on the surface of calcium sulfate dihydrate whisker is compact, and thus the product has good porosity, and thus the performance of the product is reduced, and from comparison of experimental data of example 1 and example 3, it can be found that gamma-aminopropyl triethoxysilane is not used to treat the modified calcium sulfate whisker blank when preparing modified calcium sulfate whisker, and the surface of modified calcium sulfate whisker cannot adsorb aniline, thus the performance of the product is reduced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (1)
1. A multifunctional water purification ceramic material is characterized in that: the weight portions of the components are as follows: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethylcellulose and 13 parts of modified graphene;
the preparation method of the multifunctional water purification ceramic material mainly comprises the following preparation steps:
(1) Mixing pretreated phosphogypsum and hydrochloric acid with the mass fraction of 20% according to the mass ratio of 1:5, stirring and reacting for 10min at the temperature of 80 ℃, filtering to obtain a calcium sulfate dihydrate whisker blank, and drying the calcium sulfate dihydrate whisker blank for 2h at the temperature of 85 ℃ to obtain the calcium sulfate dihydrate whisker;
(2) Mixing the calcium sulfate dihydrate whisker obtained in the step (1) with an aqueous ethanol solution with the mass fraction of 80% according to the mass ratio of 1:150 in a beaker, adding ammonia water with the mass fraction of 10% and the mass ratio of 2 times of the calcium sulfate dihydrate whisker into the beaker, stirring ethyl orthosilicate with the mass ratio of 3 times of the calcium sulfate dihydrate whisker and polyvinylpyrrolidone with the mass ratio of 1.5 times of the calcium sulfate dihydrate whisker, reacting for 12 hours at the temperature of 45 ℃, filtering to obtain a filter cake, drying the filter cake for 2 hours at the temperature of 60 ℃ to obtain a modified calcium sulfate whisker blank, mixing the modified calcium sulfate whisker blank with a gamma-aminopropyl triethoxysilane ethanol solution with the mass fraction of 15% according to the mass ratio of 1:22, stirring and mixing for 6 hours, and filtering to obtain modified calcium sulfate whisker;
(3) Mixing graphene oxide dispersion liquid and aniline in a flask according to a mass ratio of 10:3, adding modified calcium sulfate whiskers obtained in the step (2) with the mass of 0.2 times of that of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain graphene oxide mixed liquid, mixing the graphene oxide mixed liquid and catalyst solution according to a volume ratio of 4:1, stirring and reacting for 6 hours at a temperature of 6 ℃, filtering to obtain a modified graphene blank, drying the modified graphene blank at a temperature of 85 ℃ for 1.5 hours, and grinding for 35 minutes to obtain modified graphene;
(4) Weighing the following components in parts by weight: 75 parts of diatomite, 10 parts of purple clay, 2 parts of sodium carboxymethyl cellulose and 13 parts of modified graphene obtained in the step (3), mixing sodium carboxymethyl cellulose with water according to a mass ratio of 1:50 to obtain a binder, mixing the purple clay with the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture with the binder, pressing and forming to obtain a green body, sintering the green body, cooling to room temperature, and discharging to obtain the multifunctional water purification ceramic material;
the preparation method of the pretreated phosphogypsum comprises the steps of crushing and ball milling phosphogypsum, sieving with a 200-mesh sieve to obtain refined phosphogypsum, and washing the refined phosphogypsum with deionized water for 2-4 times to obtain the pretreated phosphogypsum;
the graphene oxide dispersion liquid in the step (3) is obtained by mixing graphene oxide with water according to a mass ratio of 1:120, and performing ultrasonic dispersion for 20min under the condition that the frequency is 55 kHz; the catalyst solution is prepared by mixing ammonium persulfate with hydrochloric acid with the concentration of 1mol/L according to the mass ratio of 1:10;
the pressure condition of the compression molding in the step (4) is 36MPa;
and (3) heating the sintering process condition in the step (4) in the air for 2 hours at the temperature of 195 ℃ before heating the material to 800 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphere, preserving the heat for 2 hours, heating the material to 1150 ℃ at the heating rate of 3 ℃/min in the air atmosphere, and preserving the heat and sintering the material for 35 minutes.
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| CN202210398759.4A CN114835477B (en) | 2021-02-25 | 2021-02-25 | Multifunctional water purification ceramic material |
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