CN113061050A - Multifunctional water purification ceramic material and preparation method thereof - Google Patents
Multifunctional water purification ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a multifunctional water purification ceramic material and a preparation method thereof, and relates to the technical field of new materials. Mixing pretreated phosphogypsum and hydrochloric acid at normal pressure to react to prepare calcium sulfate dihydrate crystal whiskers, then sequentially coating a silicon dioxide layer and a gamma-aminopropyl triethoxy silicon layer on the outer sides of the calcium sulfate dihydrate crystal whiskers to prepare modified calcium sulfate crystal whiskers, mixing the modified calcium sulfate crystal whiskers with a graphene oxide dispersion liquid containing aniline, adding a catalyst solution, stirring for reaction, grinding to prepare modified graphene, mixing the modified graphene with kieselguhr and purple clay, adding a sodium carboxymethyl cellulose solution, stirring for mixing, pressing for forming, and sintering to prepare the multifunctional water purifying ceramic material. The multifunctional water purification ceramic material prepared by the invention has a good filtering effect, and has bactericidal property and heat conductivity.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a multifunctional water purification ceramic material and a preparation method thereof.
Background
Along with the development of society and the improvement of living standard, people have higher and higher requirements on the quality of life, and clean and safe drinking water is the guarantee of the quality of life of people. Obtaining clean and safe drinking water has become a hot 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, the pollution of water is becoming more serious, surface water such as rivers and lakes and underground water in partial areas are polluted to different degrees, and the problem of water shortage caused by water quality is attracting wide attention.
The main pollutants in drinking water include soluble heavy metal ions, arsenic ions, trace organic pollutants, disinfection byproducts, nitrates, nitrites, pathogenic bacteria, viruses, pathogenic microorganisms and the like, and the water purification materials widely adopted at present mainly include activated carbon, molecular sieves, KDF, nanofiltration membranes and the like.
The adsorption method is one of effective methods for removing pollutants in polluted water. 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 between 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 water treatment device and recovering useful substances) and advanced treatment (improving the quality of treated water and meeting the requirement of recycled water quality), and has particularly remarkable treatment effect on extremely toxic and difficultly-degraded pollutants which are difficult to effectively treat by other methods.
At present, the ceramic material used for water purification in the market has single function, and has no other functions except for treating and filtering water-insoluble substances and adsorbing metal ions, so that the existing water purification ceramic material cannot completely meet the living needs of people.
Disclosure of Invention
The invention aims to provide a multifunctional water purification ceramic material and a preparation method thereof, which aim to solve the problems in the prior art.
The multifunctional water purifying 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 and aniline, reacting with modified calcium sulfate whiskers under the action of ammonium persulfate, and performing ball milling.
Preferably, the modified calcium sulfate whisker is prepared by treating calcium sulfate dihydrate whisker with ethyl orthosilicate and gamma-aminopropyltriethoxysilane.
Optimally, the calcium sulfate dihydrate whisker is prepared by removing impurities from phosphogypsum and then reacting the phosphogypsum with hydrochloric acid under normal pressure.
As optimization, the multifunctional water purification ceramic material is prepared from 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-purifying ceramic material mainly comprises the following preparation steps:
(1) mixing the pretreated phosphogypsum with hydrochloric acid, stirring for reaction, filtering, and drying to obtain calcium sulfate dihydrate crystal whiskers;
(2) mixing the calcium sulfate dihydrate whisker obtained in the step (1) with an ethanol solution, adding ammonia water, ethyl orthosilicate and polyvinylpyrrolidone, stirring for reaction, filtering and drying to obtain a modified calcium sulfate whisker blank, mixing the modified calcium sulfate whisker blank with a gamma-aminopropyltriethoxysilane solution, stirring for mixing, and filtering to obtain a modified calcium sulfate whisker;
(3) mixing the graphene oxide dispersion liquid with aniline, adding the modified calcium sulfate whiskers obtained in the step (2), stirring and mixing to obtain a 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 the 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, performing compression molding to obtain a blank, sintering the blank, cooling to room temperature, and discharging to obtain the multifunctional water-purifying ceramic material.
As optimization, the preparation method of the multifunctional water-purifying ceramic material mainly comprises the following preparation steps:
(1) mixing the pretreated phosphogypsum and 20% hydrochloric acid 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 ethanol aqueous solution with the mass fraction of 80% in a beaker according to the mass ratio of 1: 100-1: 250, adding ammonia water with the mass fraction of 10% which is 1-3 times of the mass of the calcium sulfate dihydrate whisker, ethyl orthosilicate with the mass fraction of 2-5 times of the mass of the calcium sulfate dihydrate whisker and polyvinylpyrrolidone with the mass fraction of 1-2 times of the mass of the calcium sulfate dihydrate whisker into the beaker, stirring and reacting for 12-13 hours at 45 ℃, filtering to obtain a filter cake, drying the filter cake for 1-3 hours at 60 ℃ to obtain a modified calcium sulfate whisker blank, mixing the modified calcium sulfate whisker blank with a gamma-aminopropyltriethoxysilane 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 modified calcium sulfate whisker;
(3) mixing the graphene oxide dispersion liquid and aniline in a mass ratio of 10: 1-10: 3 in a flask, adding 0.1-0.3 times of the modified calcium sulfate whisker obtained in the step (2) of the mass of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain a graphene oxide mixed liquid, mixing the graphene oxide mixed liquid and a catalyst solution in a volume ratio of 3: 1-8: 1, stirring and reacting for 5-8 hours at the temperature of 0-10 ℃, filtering to obtain a modified graphene blank, drying the modified graphene blank for 1-2 hours at the temperature of 80-90 ℃, 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 carboxymethylcellulose and 13 parts of modified graphene obtained in the step (3), mixing the sodium carboxymethylcellulose and water according to the mass ratio of 1: 40-1: 100 to obtain a binder, mixing the purple clay and the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture and the binder, performing compression molding to obtain a blank, sintering the blank, cooling to room temperature, and discharging to obtain the multifunctional water-purifying ceramic material.
And (3) as optimization, the preparation method of the pretreated phosphogypsum in the step (1) comprises the steps of crushing and ball-milling the phosphogypsum, sieving the crushed phosphogypsum by a 200-mesh sieve to obtain refined phosphogypsum, and washing the refined phosphogypsum by deionized water for 2-4 times to obtain the pretreated phosphogypsum.
As for 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 and hydrochloric acid with the concentration of 1mol/L according to the mass ratio of 1: 10.
And (4) optimally, the pressure condition of the compression molding in the step (4) is 35-40 MPa.
Preferably, the sintering process in the step (4) is carried out under the condition that the temperature is 195 ℃ for 2 hours in air, then the temperature is increased to 800 ℃ at the temperature increasing rate of 2-3 ℃/min in the nitrogen atmosphere, the temperature is kept for 2 hours, finally the temperature is increased to 1100-1400 ℃ at the temperature increasing rate of 2-4 ℃/min in the air atmosphere, and the temperature is kept for 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, modified graphene is used, and is prepared by mixing lamellar oxidized graphene and aniline, reacting the mixture with modified calcium sulfate whiskers under the action of ammonium persulfate, and performing 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 after modification, and gamma-aminopropyltriethoxysilane can be coated on the outer side again under the action of the silicon dioxide, and due to the action of the gamma-aminopropyltriethoxysilane, aniline can be adsorbed on the surface of the modified calcium sulfate whiskers under the action of amino groups after the modified calcium sulfate whiskers are mixed with the aniline, and meanwhile, in the preparation process of a graphene oxide mixed solution, the surface of graphene oxide also adsorbs aniline, so that when polyaniline is formed by polymerization of aniline under the catalysis of ammonium persulfate, the modified calcium sulfate whiskers can be substituted into the interlayer of the graphene oxide, so that a modified calcium sulfate whisker-polyaniline composite pillared structure is formed between the modified graphene, and the modified graphene has filtering performance, after the filter aid is added into a product, the filtering performance of the product is improved;
secondly, in the sintering process of the multifunctional water-purifying ceramic material, because the heat preservation and heating treatment is carried out in the early stage under the condition of nitrogen, polyaniline among graphene oxides can be carbonized to form a carbonaceous structure, a carbon-modified calcium sulfate whisker pillared structure is formed, the graphene oxides are reduced to form graphene, due to the existence of the graphene and the carbon, the heat conducting property of the product can be improved, so that the product has a heating function, and simultaneously, because the calcium sulfate dihydrate in the modified calcium sulfate whisker can be decomposed to generate water vapor in the later sintering process, and the decomposition temperature of the calcium sulfate whisker can be reduced under the action of carbon, so that the calcium sulphate decomposes at a relatively low temperature, producing gas and calcium oxide, and, therefore, under the decomposition effect of the modified calcium sulfate whiskers, a carbon 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 pillared structure among the graphene contains calcium oxide, so that the product can be endowed with the capability of treating acidic sewage due to the existence of the calcium oxide, and the calcium hydroxide has good bactericidal performance, so that the product has good bactericidal performance, and further can be endowed with better service performance after the modified graphene is added into the product.
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.
In order to more clearly illustrate the method provided by the invention, the method is described in detail by the following examples, and the method for testing each index of the multifunctional water-purifying ceramic material prepared in the following examples is as follows:
porosity: the porosity of the multifunctional water-purifying ceramic material obtained in each example and the porosity of the product obtained in the comparative example were measured, and the water flux was measured for 5min under the condition that the water pressure was 0.36 MPa.
Metal ion removal rate: the multifunctional water-purifying ceramic material obtained in each example and the product obtained in the comparative example were used for filtering a metal ion solution with the same concentration, and the removal rates of chromium ions, copper ions and lead ions were measured.
The sterilization rate is as follows: the multifunctional water-purifying ceramic material obtained in each example and the product obtained in the comparative example are used for filtering escherichia coli liquid with the same concentration, and the sterilization rate is measured.
Example 1
A multifunctional water purification 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-purifying ceramic material mainly comprises the following preparation steps:
(1) mixing the pretreated phosphogypsum with 20% hydrochloric acid 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% which is 2 times of the mass of the calcium sulfate dihydrate whisker, ethyl orthosilicate with the mass fraction of 3 times of the calcium sulfate dihydrate whisker and polyvinylpyrrolidone with the mass fraction of 1.5 times of the calcium sulfate dihydrate whisker into the beaker, stirring and 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-aminopropyltriethoxysilane 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 the modified calcium sulfate whisker;
(3) mixing the graphene oxide dispersion liquid and aniline in a mass ratio of 10:3 in a flask, adding the modified calcium sulfate whisker obtained in the step (2) with the mass of the graphene oxide dispersion liquid being 0.2 times of that of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain a graphene oxide mixed solution, mixing the graphene oxide mixed solution and a catalyst solution in a volume ratio of 4:1, stirring and reacting for 6 hours at the temperature of 6 ℃, filtering to obtain a modified graphene blank, drying the modified graphene blank for 1.5 hours at the temperature of 85 ℃, 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 carboxymethylcellulose and 13 parts of modified graphene obtained in the step (3), mixing the sodium carboxymethylcellulose and water according to the mass ratio of 1:50 to obtain a binder, mixing the purple clay and the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture and the binder, performing compression molding to obtain a blank, sintering the blank, cooling to room temperature, and discharging to obtain the multifunctional water-purifying ceramic material.
And (3) as optimization, the preparation method of the pretreated phosphogypsum in the step (1) comprises the steps of crushing and ball-milling the phosphogypsum, sieving the crushed phosphogypsum by a 200-mesh sieve to obtain refined phosphogypsum, and washing the refined phosphogypsum by deionized water for 2-4 times to obtain the pretreated phosphogypsum.
As for 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 ultrasonically dispersing for 20min under the condition that the frequency is 55 kHz; the catalyst solution is prepared by mixing ammonium persulfate and 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 36 MPa.
Optimally, the sintering process condition in the step (4) is that the raw materials are firstly heated in air at the temperature of 195 ℃ for 2h, then the temperature is raised to 800 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphere, the temperature is kept for 2h, finally the temperature is raised to 1150 ℃ at the heating rate of 3 ℃/min in the air atmosphere, and the temperature is kept and sintered for 35 min.
Example 2
A multifunctional water purification 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-purifying ceramic material mainly comprises the following preparation steps:
(1) mixing the pretreated phosphogypsum with 20% hydrochloric acid 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 crystal 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 2 times of the mass of the calcium sulfate dihydrate crystal whisker into the beaker, stirring and 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 crystal whisker blank, mixing the modified calcium sulfate crystal whisker blank with a gamma-aminopropyltriethoxysilane 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 the modified calcium sulfate crystal whisker;
(3) mixing the graphene oxide dispersion liquid and aniline in a mass ratio of 10:3 in a flask, adding the modified calcium sulfate whisker obtained in the step (2) with the mass of the graphene oxide dispersion liquid being 0.2 times of that of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain a graphene oxide mixed solution, mixing the graphene oxide mixed solution and a catalyst solution in a volume ratio of 4:1, stirring and reacting for 6 hours at the temperature of 6 ℃, filtering to obtain a modified graphene blank, drying the modified graphene blank for 1.5 hours at the temperature of 85 ℃, 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 carboxymethylcellulose and 13 parts of modified graphene obtained in the step (3), mixing the sodium carboxymethylcellulose and water according to the mass ratio of 1:50 to obtain a binder, mixing the purple clay and the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture and the binder, performing compression molding to obtain a blank, sintering the blank, cooling to room temperature, and discharging to obtain the multifunctional water-purifying ceramic material.
And (3) as optimization, the preparation method of the pretreated phosphogypsum in the step (1) comprises the steps of crushing and ball-milling the phosphogypsum, sieving the crushed phosphogypsum by a 200-mesh sieve to obtain refined phosphogypsum, and washing the refined phosphogypsum by deionized water for 2-4 times to obtain the pretreated phosphogypsum.
As for 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 ultrasonically dispersing for 20min under the condition that the frequency is 55 kHz; the catalyst solution is prepared by mixing ammonium persulfate and 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 36 MPa.
Optimally, the sintering process condition in the step (4) is that the raw materials are firstly heated in air at the temperature of 195 ℃ for 2h, then the temperature is raised to 800 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphere, the temperature is kept for 2h, finally the temperature is raised to 1150 ℃ at the heating rate of 3 ℃/min in the air atmosphere, and the temperature is kept and sintered for 35 min.
Example 3
A multifunctional water purification 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-purifying ceramic material mainly comprises the following preparation steps:
(1) mixing the pretreated phosphogypsum with 20% hydrochloric acid 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% which is 2 times that of the calcium sulfate dihydrate whisker, ethyl orthosilicate with the mass fraction of 3 times that of the calcium sulfate dihydrate whisker and polyvinylpyrrolidone with the mass fraction of 1.5 times that of the calcium sulfate dihydrate whisker into the beaker, stirring and reacting for 12 hours at the temperature of 45 ℃, and filtering to obtain modified calcium sulfate whisker;
(3) mixing the graphene oxide dispersion liquid and aniline in a mass ratio of 10:3 in a flask, adding the modified calcium sulfate whisker obtained in the step (2) with the mass of the graphene oxide dispersion liquid being 0.2 times of that of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain a graphene oxide mixed solution, mixing the graphene oxide mixed solution and a catalyst solution in a volume ratio of 4:1, stirring and reacting for 6 hours at the temperature of 6 ℃, filtering to obtain a modified graphene blank, drying the modified graphene blank for 1.5 hours at the temperature of 85 ℃, 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 carboxymethylcellulose and 13 parts of modified graphene obtained in the step (3), mixing the sodium carboxymethylcellulose and water according to the mass ratio of 1:50 to obtain a binder, mixing the purple clay and the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture and the binder, performing compression molding to obtain a blank, sintering the blank, cooling to room temperature, and discharging to obtain the multifunctional water-purifying ceramic material.
And (3) as optimization, the preparation method of the pretreated phosphogypsum in the step (1) comprises the steps of crushing and ball-milling the phosphogypsum, sieving the crushed phosphogypsum by a 200-mesh sieve to obtain refined phosphogypsum, and washing the refined phosphogypsum by deionized water for 2-4 times to obtain the pretreated phosphogypsum.
As for 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 ultrasonically dispersing for 20min under the condition that the frequency is 55 kHz; the catalyst solution is prepared by mixing ammonium persulfate and 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 36 MPa.
Optimally, the sintering process condition in the step (4) is that the raw materials are firstly heated in air at the temperature of 195 ℃ for 2h, then the temperature is raised to 800 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphere, the temperature is kept for 2h, finally the temperature is raised to 1150 ℃ at the heating rate of 3 ℃/min in the air atmosphere, and the temperature is kept and sintered for 35 min.
Comparative example 1
A multifunctional water purification 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-purifying ceramic material mainly comprises the following preparation steps:
(1) mixing the pretreated phosphogypsum with 20% hydrochloric acid 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 graphene oxide dispersion liquid and aniline in a mass ratio of 10:3 in a flask, adding calcium sulfate dihydrate whisker obtained in the step (2) and having the mass of 0.2 times that of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain a graphene oxide mixed liquid, mixing the graphene oxide mixed liquid and a catalyst solution in a volume ratio of 4:1, stirring and reacting for 6 hours at the temperature of 6 ℃, filtering to obtain a modified graphene blank, drying the modified graphene blank for 1.5 hours at the 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 carboxymethylcellulose and 13 parts of modified graphene obtained in the step (2), mixing the sodium carboxymethylcellulose and water according to the mass ratio of 1:50 to obtain a binder, mixing the purple clay and the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture and the binder, performing compression molding to obtain a blank, sintering the blank, cooling to room temperature, and discharging to obtain the multifunctional water-purifying ceramic material.
And (3) as optimization, the preparation method of the pretreated phosphogypsum in the step (1) comprises the steps of crushing and ball-milling the phosphogypsum, sieving the crushed phosphogypsum by a 200-mesh sieve to obtain refined phosphogypsum, and washing the refined phosphogypsum by deionized water for 2-4 times to obtain the pretreated phosphogypsum.
As for 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 ultrasonically dispersing for 20min under the condition that the frequency is 55 kHz; the catalyst solution is prepared by mixing ammonium persulfate and 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 36 MPa.
Optimally, the sintering process conditions in the step (3) are that the raw materials are firstly heated in air at the temperature of 195 ℃ for 2h, then the temperature is raised to 800 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphere, the temperature is kept for 2h, finally the temperature is raised to 1150 ℃ at the heating rate of 3 ℃/min in the air atmosphere, and the temperature is kept and sintered for 35 min.
Comparative example 2
A multifunctional water purification 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-purifying ceramic material mainly comprises the following preparation steps:
(1) mixing the pretreated phosphogypsum with 20% hydrochloric acid 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 graphene oxide dispersion liquid and aniline in a mass ratio of 10:3 in a flask, adding calcium sulfate dihydrate whisker obtained in the step (2) and having the mass of 0.2 times that of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain a graphene oxide mixed liquid, mixing the graphene oxide mixed liquid and a catalyst solution in a volume ratio of 4:1, stirring and reacting for 6 hours at the temperature of 6 ℃, filtering to obtain a modified graphene blank, drying the modified graphene blank for 1.5 hours at the 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 carboxymethylcellulose and 13 parts of modified graphene obtained in the step (2), mixing the sodium carboxymethylcellulose and water according to the mass ratio of 1:50 to obtain a binder, mixing the purple clay and the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture and the binder, performing compression molding to obtain a blank, sintering the blank, cooling to room temperature, and discharging to obtain the multifunctional water-purifying ceramic material.
And (3) as optimization, the preparation method of the pretreated phosphogypsum in the step (1) comprises the steps of crushing and ball-milling the phosphogypsum, sieving the crushed phosphogypsum by a 200-mesh sieve to obtain refined phosphogypsum, and washing the refined phosphogypsum by deionized water for 2-4 times to obtain the pretreated phosphogypsum.
As for 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 ultrasonically dispersing for 20min under the condition that the frequency is 55 kHz; the catalyst solution is prepared by mixing ammonium persulfate and 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 36 MPa.
And (4) 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 the air atmosphere, and the heat is preserved and sintered for 35 min.
Examples of effects
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
As can be seen from the comparison of the experimental data of the example 1 and the comparative example in the table 1, the addition of the modified graphene during the preparation of the multifunctional water-purifying ceramic material can effectively improve the removal rate of the product on metal ions, meanwhile, the bactericidal property and the thermal conductivity are given to the product, and the comparison of the experimental data of the example 1 and the example 2 shows that, when the modified calcium sulfate whisker in the modified graphene is not added with polyvinylpyrrolidone during preparation, the surface silicon dioxide layer of the calcium sulfate dihydrate whisker is compact, so that the product cannot have good porosity, thus, the performance of the product was reduced, as can be seen from the comparison of the experimental data of example 1 and example 3, when the modified calcium sulfate whisker is prepared, the gamma-aminopropyltriethoxysilane is not used for treating the modified calcium sulfate whisker blank, and aniline cannot be adsorbed on the surface of the modified calcium sulfate whisker, so that 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 attributes 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 (10)
1. The multifunctional water purifying 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 and aniline, reacting with modified calcium sulfate whiskers under the action of ammonium persulfate, and performing ball milling.
2. The multifunctional water purifying ceramic material of claim 1, wherein the modified calcium sulfate whisker is prepared by treating calcium sulfate dihydrate whisker with tetraethoxysilane and gamma-aminopropyltriethoxysilane.
3. The multifunctional water-purifying ceramic material of claim 2, wherein the calcium sulfate dihydrate whisker is prepared by removing impurities from phosphogypsum and reacting with hydrochloric acid under normal pressure.
4. The multifunctional water purifying ceramic material of claim 3, which is prepared from 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.
5. The preparation method of the multifunctional water-purifying ceramic material is characterized by mainly comprising the following preparation steps:
(1) mixing the pretreated phosphogypsum with hydrochloric acid, stirring for reaction, filtering, and drying to obtain calcium sulfate dihydrate crystal whiskers;
(2) mixing the calcium sulfate dihydrate whisker obtained in the step (1) with an ethanol solution, adding ammonia water, ethyl orthosilicate and polyvinylpyrrolidone, stirring for reaction, filtering and drying to obtain a modified calcium sulfate whisker blank, mixing the modified calcium sulfate whisker blank with a gamma-aminopropyltriethoxysilane solution, stirring for mixing, and filtering to obtain a modified calcium sulfate whisker;
(3) mixing the graphene oxide dispersion liquid with aniline, adding the modified calcium sulfate whiskers obtained in the step (2), stirring and mixing to obtain a 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 the 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, performing compression molding to obtain a blank, sintering the blank, cooling to room temperature, and discharging to obtain the multifunctional water-purifying ceramic material.
6. The preparation method of the multifunctional water-purifying ceramic material of claim 5, wherein the preparation method of the multifunctional water-purifying ceramic material mainly comprises the following preparation steps:
(1) mixing the pretreated phosphogypsum and 20% hydrochloric acid 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 ethanol aqueous solution with the mass fraction of 80% in a beaker according to the mass ratio of 1: 100-1: 250, adding ammonia water with the mass fraction of 10% which is 1-3 times of the mass of the calcium sulfate dihydrate whisker, ethyl orthosilicate with the mass fraction of 2-5 times of the mass of the calcium sulfate dihydrate whisker and polyvinylpyrrolidone with the mass fraction of 1-2 times of the mass of the calcium sulfate dihydrate whisker into the beaker, stirring and reacting for 12-13 hours at 45 ℃, filtering to obtain a filter cake, drying the filter cake for 1-3 hours at 60 ℃ to obtain a modified calcium sulfate whisker blank, mixing the modified calcium sulfate whisker blank with a gamma-aminopropyltriethoxysilane 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 modified calcium sulfate whisker;
(3) mixing the graphene oxide dispersion liquid and aniline in a mass ratio of 10: 1-10: 3 in a flask, adding 0.1-0.3 times of the modified calcium sulfate whisker obtained in the step (2) of the mass of the graphene oxide dispersion liquid into the flask, stirring and mixing to obtain a graphene oxide mixed liquid, mixing the graphene oxide mixed liquid and a catalyst solution in a volume ratio of 3: 1-8: 1, stirring and reacting for 5-8 hours at the temperature of 0-10 ℃, filtering to obtain a modified graphene blank, drying the modified graphene blank for 1-2 hours at the temperature of 80-90 ℃, 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 carboxymethylcellulose and 13 parts of modified graphene obtained in the step (3), mixing the sodium carboxymethylcellulose and water according to the mass ratio of 1: 40-1: 100 to obtain a binder, mixing the purple clay and the diatomite, adding the modified graphene, mixing and grinding to obtain a mixture, mixing the mixture and the binder, performing compression molding to obtain a blank, sintering the blank, cooling to room temperature, and discharging to obtain the multifunctional water-purifying ceramic material.
7. The preparation method of the multifunctional water-purifying ceramic material according to claim 6, wherein the preparation method of the pretreated phosphogypsum in the step (1) comprises the steps of crushing and ball-milling the phosphogypsum, sieving the crushed phosphogypsum 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.
8. The preparation method of the multifunctional water-purifying ceramic material according to claim 6, wherein 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 a frequency of 55 kHz; the catalyst solution is prepared by mixing ammonium persulfate and hydrochloric acid with the concentration of 1mol/L according to the mass ratio of 1: 10.
9. The method for preparing the multifunctional water-purifying ceramic material of claim 6, wherein the pressure condition of the press molding in the step (4) is 35-40 MPa.
10. The method for preparing the multifunctional water-purifying ceramic material of claim 6, wherein the sintering process in step (4) comprises heating in air at 195 ℃ for 2 hours, heating to 800 ℃ at a heating rate of 2-3 ℃/min in a nitrogen atmosphere, holding for 2 hours, heating to 1100-1400 ℃ at a heating rate of 2-4 ℃/min in an air atmosphere, and holding for sintering for 30-40 minutes.
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| CN114835477B (en) | 2023-10-31 |
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