Preparation method of water purification ceramic for improving microbial activity

Abstract

The invention provides a preparation method of water purification ceramic capable of improving microbial activity, and belongs to the technical field of ceramic. The water purification ceramic is prepared from the following raw materials in parts by mass: 25 to 45 parts of quartz powder, 5 to 25 parts of talcum powder, 10 to 35 parts of modified kaolin, 1 to 10 parts of tin oxide powder, 0.5 to 8 parts of nickel oxide powder, 5 to 20 parts of titanium dioxide powder, 1 to 15 parts of fluorapatite powder, 0.1 to 1 part of high-temperature anti-agglomeration aid, 0.5 to 5 parts of adhesive and 35 to 55 parts of solvent. Through the synergistic effect of all the components in a certain range, the prepared ceramic is used in a water environment, the metabolic rate of beneficial microorganisms can be increased, the growth and activity of the beneficial microorganisms can be promoted, and the ceramic has an obvious inhibition effect on bacteria such as staphylococcus aureus and the like and shows relatively high purification efficiency.

Description

Technical Field

[0001] The invention relates to the technical field of ceramics, and in particular to a method for preparing water-purifying ceramics capable of improving microbial activity. Background Art

[0002] Water pollutants are mainly composed of natural pollutants and artificial pollutants, including natural organic matter and bacteria produced by the decomposition of countless plants and animals, which have varying degrees of impact on human health. At present, traditional methods such as flocculation, sedimentation, filtration, adsorption and chlorine disinfection are mainly used to remove pollutants. However, due to the different types of mixtures in different water sources, the removal effect is easily affected by adsorption, season, temperature and environment.

[0003] Water purification ceramics are a kind of ceramic material with special functions. They filter suspended matter, heavy metal ions, residual chlorine and other impurities in water by physical means. They have the advantages of good chemical stability, high temperature resistance, acid and alkali resistance, etc., and are widely used in the field of water treatment. However, with the development of science and technology and the improvement of people's living standards, the existing water purification ceramics have limited filtration accuracy, are prone to clogging after long-term use, and have limited pollution resistance, which cannot meet the demand for water quality.

[0004] Terahertz (THz) waves refer to electromagnetic radiation with a frequency of 0.1 to 10 THz (1 THz = 1012 Hz) and a wavelength of 0.03 to 3 mm. It has the characteristics of low energy, penetration, transient and spectral fingerprint, and is widely used in life sciences, material sciences, astronomy, atmosphere and environmental monitoring, communications and other fields. At present, due to equipment limitations, the application of terahertz waves in the field of water treatment is still relatively small. If a ceramic material that can radiate terahertz waves can be designed based on the characteristics of terahertz waves, it will be beneficial to the development of ceramic technology. Summary of the invention

[0005] In view of the defects of the prior art, the present invention prepares a water purification ceramic that can radiate terahertz waves and increase the metabolic rate of microorganisms.

[0006] In order to achieve the above purpose, the present invention solves the technical problem by adopting the following technical solutions:

[0007] The present invention provides a water purification ceramic for improving the activity of microorganisms. The water purification ceramic comprises, by mass, 25-45 parts of quartz powder, 5-25 parts of talc powder, 10-35 parts of modified kaolin, 1-10 parts of tin oxide powder, 0.5-8 parts of nickel oxide powder, 5-20 parts of titanium dioxide powder, 1-15 parts of fluoroapatite powder, 0.1-1 parts of high-temperature anti-agglomeration aid, 0.5-5 parts of adhesive, and 35-55 parts of solvent.

[0008] In some of the embodiments, the water purification ceramic includes, by mass, 30-40 parts of quartz powder, 10-20 parts of talc powder, 15-30 parts of modified kaolin, 4-6 parts of tin oxide powder, 1-5 parts of nickel oxide powder, 10-15 parts of titanium dioxide powder, 5-10 parts of fluoroapatite powder, 0.3-0.7 parts of high temperature anti-agglomeration aid, 1-3 parts of adhesive, and 40-50 parts of solvent.

[0009] In some of the embodiments, the water purification ceramic includes, by mass, 35 parts of quartz powder, 15 parts of talc powder, 18 parts of modified kaolin, 5 parts of tin oxide powder, 3 parts of nickel oxide powder, 13 parts of titanium dioxide powder, 7 parts of fluoroapatite powder, 0.5 parts of high-temperature anti-agglomeration aid, 2 parts of adhesive, and 45 parts of solvent.

[0010] In some embodiments, the preparation of the modified kaolin includes:

[0011] First, kaolin was mixed with 0.6-1M rare earth nitrate solution and stirred at 800rpm for 20min. During the stirring period, 30mL of 0.6-1M sodium hydroxide solution was added dropwise. The mixture was stirred at 800rpm for 12-16h. After suction filtration and centrifugal washing, the solid sample was collected by filtration, dried and ground to obtain modified kaolin.

[0012] In some of the embodiments, the kaolin and the rare earth nitrate solution are mixed at a ratio of 1: (70-90).

[0013] In some of the embodiments, the rare earth nitrate solution is prepared by adding La(NO3)3·6H2O and Ce(NO3)3·6H2O into pure water in a mass ratio of 2:3.

[0014] In some of the embodiments, the particle sizes of the quartz powder, talc powder, modified kaolin, tin oxide powder, nickel oxide powder, titanium dioxide powder and fluoroapatite powder are all 50-150 μm.

[0015] In some embodiments, the high temperature anti-agglomeration aid is one or more of small molecule siloxane and small molecule silica sol.

[0016] In some embodiments, the adhesive includes one or more of polyetherimide, bismaleimide, and water glass high temperature adhesive.

[0017] In some embodiments, the preparation method of the water purification ceramic comprises the following steps:

[0018] S1. Quartz powder, talc, modified kaolin, tin oxide powder, nickel oxide powder, titanium dioxide powder, fluoroapatite powder, high temperature anti-agglomeration aid, binder, solvent were added to a ball mill and milled for 16-24h to obtain a slurry, and then pressed to obtain a ceramic blank;

[0019] S2. In an oxygen-free environment, the ceramic green body is sintered at 1100-1300° C. for 28-32 hours, and after sintering, the green body is kept warm for 2 hours and cooled to room temperature to obtain a ceramic.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The present invention modifies kaolin by doping rare earth elements, and cooperates with raw materials such as quartz powder, talcum powder, tin oxide powder, nickel oxide powder, titanium dioxide powder, and fluoroapatite powder to prepare a material that can continuously radiate terahertz waves by absorbing natural infrared and other energies. When used in a water environment, the material can make water molecules in microorganisms absorb energy, increase molecular motion, and generate heat energy, thereby improving the metabolic rate of beneficial microorganisms, promoting their growth and activity, and has a significant inhibitory effect on bacteria such as Staphylococcus aureus, showing a high purification efficiency.

[0022] In addition, the powders of the present invention are all inorganic substances, the raw materials are easily available, and can be produced on a large scale industrially. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the technical solution of the present invention, the drawings required for use in the implementation mode will be briefly introduced below. Obviously, the drawings described below are only some implementation modes of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0024] Figure 1 4 is a table showing the results of the dehydrogenase activity test of the ceramics in the embodiments of the present invention.

[0025] Figure 2 4 is a table showing the results of a catalase activity test on the ceramics in the embodiments of the present invention. DETAILED DESCRIPTION

[0026] The following is a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with specific embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the materials and reagents used are reagents and materials that can be obtained from commercial channels unless otherwise specified.

[0028] Table 1 Water purification ceramic formula (by mass)

[0029]

[0030]

[0031] Example 1

[0032] A water purification ceramic for improving microbial activity, the preparation method of which comprises the following steps:

[0033] 1. According to the formula in Table 1 above, weigh appropriate amounts of quartz powder, talcum powder, modified kaolin, tin oxide powder, nickel oxide powder, titanium dioxide powder, and fluoroapatite powder, and pass the powder through 100 mesh;

[0034] 2. Add the powders, high temperature anti-agglomeration aid (small molecule silica sol), binder (polyetherimide), and solvent (deionized water) into a ball mill and mill for 20 hours to obtain a slurry, dry it to constant weight, and then press it at 100 MPa for 3 minutes to obtain a ceramic green body;

[0035] 3. Under nitrogen atmosphere, place the ceramic green body into a sintering furnace, sinter at 1200°C for 28 hours, keep warm for 2 hours after sintering, and finally cool to room temperature to obtain ceramics.

[0036] In this embodiment, the preparation of the modified kaolin includes:

[0037] At room temperature, natural kaolin was mixed with 0.8M rare earth nitrate solution at a material-liquid ratio of 1:80 (g / mL) and stirred at 800rpm for 20min, 30mL of 0.8M sodium hydroxide solution was added dropwise during stirring, and then stirred at 800rpm for 14h. After stirring, the mixture was filtered, washed by centrifugation with pure water, and then filtered to collect the solid, dried to constant weight, and then ground through a 100μm sieve to obtain modified kaolin.

[0038] The rare earth nitrate solution is prepared by adding La(NO3)3·6H2O and Ce(NO3)3·6H2O into pure water in a mass ratio of 2:3.

[0039] Example 2

[0040] A water purification ceramic for improving microbial activity, the preparation method of which comprises the following steps:

[0041] 1. According to the formula in Table 1 above, weigh appropriate amounts of quartz powder, talcum powder, modified kaolin, tin oxide powder, nickel oxide powder, titanium dioxide powder, and fluoroapatite powder, and pass the powder through 100 mesh;

[0042] 2. Add the powders, high temperature anti-agglomeration aid (small molecule silica sol), binder (water glass high temperature glue), and solvent (deionized water) into a ball mill and mill for 16 hours to obtain a slurry, dry it to constant weight, and then press it at 100 MPa for 3 minutes to obtain a ceramic blank;

[0043] 3. Under nitrogen atmosphere, place the ceramic green body into a sintering furnace, sinter at 1100°C for 32 hours, keep warm for 2 hours after sintering, and finally cool to room temperature to obtain ceramics.

[0044] In this embodiment, the preparation of the modified kaolin includes:

[0045] At room temperature, natural kaolin was mixed with 0.6M rare earth nitrate solution at a solid-liquid ratio of 1:70 (g / mL) and stirred at 800rpm for 20min, 30mL of 0.6M sodium hydroxide solution was added dropwise during stirring, and then stirred at 800rpm for 16h. After stirring, the mixture was filtered, washed with pure water by centrifugation, and then filtered to collect the solid, dried to constant weight, and then ground through a 100μm sieve to obtain modified kaolin.

[0046] The rare earth nitrate solution is prepared by adding La(NO3)3·6H2O and Ce(NO3)3·6H2O into pure water in a mass ratio of 2:3.

[0047] Example 3

[0048] A water purification ceramic for improving microbial activity, the preparation method of which comprises the following steps:

[0049] 1. According to the formula in Table 1 above, weigh appropriate amounts of quartz powder, talcum powder, modified kaolin, tin oxide powder, nickel oxide powder, titanium dioxide powder, and fluoroapatite powder, and pass the powder through 100 mesh;

[0050] 2. Add the powders, high temperature anti-agglomeration aid (small molecule silica sol), binder (water glass high temperature glue), and solvent (deionized water) into a ball mill and mill for 24 hours to obtain a slurry, dry it to constant weight, and then press it at 100 MPa for 3 minutes to obtain a ceramic blank;

[0051] 3. Under nitrogen atmosphere, place the ceramic green body into a sintering furnace, sinter at 1300°C for 28 hours, keep warm for 2 hours after sintering, and finally cool to room temperature to obtain ceramics.

[0052] In this embodiment, the preparation of the modified kaolin includes:

[0053] At room temperature, natural kaolin was mixed with 1M rare earth nitrate solution at a material-liquid ratio of 1:90 (g / mL) and stirred at 800 rpm for 20 min. During stirring, 30 mL of 1M sodium hydroxide solution was dropped, and then stirred at 800 rpm for 12 h. After stirring, the mixture was filtered, washed by centrifugation with pure water, and then filtered to collect the solid, dried to constant weight, and then ground through a 100-mesh sieve to obtain modified kaolin.

[0054] The rare earth nitrate solution is prepared by adding La(NO3)3·6H2O and Ce(NO3)3·6H2O into pure water in a mass ratio of 2:3.

[0055] The formula of Comparative Example 1-2 is shown in Table 1 above. The preparation method of a water purification ceramic for improving microbial activity is the same as that of Example 1.

[0056] Comparative Example 3

[0057] The difference between Comparative Example 3 and Example 1 is that natural kaolin of equal mass is used instead of modified kaolin, and the other contents are the same.

[0058] Comparative Example 4

[0059] The difference between Comparative Example 4 and Example 1 is that the preparation of modified kaolin is different, and the other aspects are the same.

[0060] The preparation of the modified kaolin comprises:

[0061] At room temperature, natural kaolin was mixed with 0.8M lanthanum nitrate solution at a solid-liquid ratio of 1:80 (g / mL) and stirred at 800rpm for 20min. During stirring, 30mL of 0.8M sodium hydroxide solution was dropped, and then stirred at 800rpm for 14h. After stirring, the mixture was filtered, washed with pure water by centrifugation, and then filtered to collect the solid sample, dried to constant weight, and then ground through a 100μm sieve to obtain modified kaolin.

[0062] The lanthanum nitrate solution is prepared by adding La(NO3)3·6H2O into pure water.

[0063] Comparative Example 5

[0064] The difference between Comparative Example 5 and Example 1 is that the preparation of modified kaolin is different, and the other aspects are the same.

[0065] The preparation of the modified kaolin comprises:

[0066] At room temperature, natural kaolin was mixed with 0.8M cerium nitrate solution at a solid-liquid ratio of 1:80 (g / mL) and stirred at 800rpm for 20min, 30mL of 0.8M sodium hydroxide solution was added dropwise during stirring, and then stirred at 800rpm for 14h. After stirring, the mixture was filtered, washed with pure water by centrifugation, and then filtered to collect the solid sample, dried to constant weight, and then ground through a 100μm sieve to obtain modified kaolin.

[0067] The cerium nitrate solution is prepared by adding Ce(NO3)3·6H2O into pure water.

[0068] Comparative Example 6

[0069] The difference between Comparative Example 6 and Example 1 is that the preparation of modified kaolin is different, and the other aspects are the same.

[0070] The preparation of the modified kaolin comprises:

[0071] At room temperature, natural kaolin was mixed with 0.8M magnesium chloride solution at a solid-liquid ratio of 1:80 (g / mL) and stirred at 800rpm for 20min. During stirring, 30mL of 0.8M sodium hydroxide solution was dropped, and then stirred at 800rpm for 14h. After stirring, the mixture was filtered, washed with pure water by centrifugation, and then filtered to collect the solid sample, dried to constant weight, and then ground through a 100μm sieve to obtain modified kaolin.

[0072] Comparative Example 7

[0073] The difference between Comparative Example 7 and Example 1 is that hydroxyapatite of equal mass is used to replace fluorapatite powder, and the other contents are the same.

[0074] Comparative Example 8

[0075] The difference between Comparative Example 8 and Example 1 is that wollastonite of equal mass is used to replace the fluorapatite powder, and the other conditions are the same.

[0076] Test Example 1

[0077] The ceramics of Examples 1-3 and Comparative Examples 1-8 were tested respectively to analyze the properties of the ceramics.

[0078] Test indicators:

[0079] 1. According to GB / T 7286.1-1987 "Test method for full normal emissivity of metal and non-metal materials", test the normal total emissivity of ceramics at 20℃.

[0080] 2. According to JC / T 897-2014 "Antibacterial Performance of Antibacterial Ceramic Products", the antibacterial rate of ceramics is tested, and the test bacteria is Staphylococcus aureus. The calculation formula is as follows:

[0081]

[0082] Wherein, R is the antibacterial rate (%); B is the colony count (CFU) of the blank control group after 24 hours of culture; C is the colony count (CFU) of the ceramic after 24 hours of culture.

[0083] 3. Water purification effect

[0084] The ceramics were placed in the wastewater of a certain farm. The water quality was about 689.6 mg / L chemical oxygen demand (COD), 46.85 mg / L total nitrogen (TN), and 9.11 mg / L total phosphorus (TP). The chemical oxygen demand, total nitrogen, and total phosphorus content in the wastewater were recorded after 7 days, and the removal rates of chemical oxygen demand, total nitrogen, and total phosphorus were calculated. The calculation formula is as follows:

[0085]

[0086] Where A0 is the initial concentration (mg / L) and A is the concentration after ceramic treatment (mg / L).

[0087] 4. Microbial activity

[0088] In the water environment, microorganisms participate in the material circulation and energy flow in the water through their metabolic activities. These processes are often achieved through enzymatic reactions. Therefore, the activity of dehydrogenase and catalase is used to measure the metabolic intensity of microorganisms in water. Another group of samples that were not treated with ceramics was set up as a blank group.

[0089] Table 2 Performance test results of different ceramics

[0090]

[0091]

[0092] As can be seen from Table 2, the normal total emissivity of Examples 1-3 is higher than that of Comparative Examples 1-8, which is above 80%, indicating that the ceramics of the present invention have a good ability to emit terahertz waves; at the same time, compared with Comparative Examples 1-8, Examples 1-3 have a better antibacterial rate through the scientific ratio of each component, can effectively inhibit bacteria such as Staphylococcus aureus, and have a high removal rate for COD, TN, TP, etc. in water environments, which is beneficial to the growth and reproduction of beneficial microorganisms, enhances the competitiveness of beneficial microorganisms, and inhibits the growth of pathogenic microorganisms, thereby maintaining the balance of the microbial community.

[0093] Further by Figure 1-2 It can be seen that the dehydrogenase and catalase activities of Examples 1-3 relative to the blank group are higher than those of Comparative Examples 1-8, indicating that the ceramics of the present invention have a positive effect on the metabolic process of microorganisms in the water environment. The microorganisms decompose organic matter in the water through their metabolic activities, converting unstable organic matter into stable and harmless substances, thereby purifying the water quality.

[0094] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A water purification ceramic for improving microbial activity, characterized in that: In parts by mass, the water purification ceramic includes 25-45 parts of quartz powder, 5-25 parts of talc powder, 10-35 parts of modified kaolin, 1-10 parts of tin oxide powder, 0.5-8 parts of nickel oxide powder, 5-20 parts of titanium dioxide powder, 1-15 parts of fluoroapatite powder, 0.1-1 parts of high temperature anti-agglomeration aid, 0.5-5 parts of adhesive, and 35-55 parts of solvent.

2. The water purification ceramic according to claim 1, characterized in that: In parts by mass, the water purification ceramic includes 30-40 parts of quartz powder, 10-20 parts of talc powder, 15-30 parts of modified kaolin, 4-6 parts of tin oxide powder, 1-5 parts of nickel oxide powder, 10-15 parts of titanium dioxide powder, 5-10 parts of fluoroapatite powder, 0.3-0.7 parts of high-temperature anti-agglomeration aid, 1-3 parts of adhesive, and 40-50 parts of solvent.

3. The water purification ceramic according to claim 1, characterized in that: In parts by mass, the water purification ceramic includes 35 parts of quartz powder, 15 parts of talc powder, 18 parts of modified kaolin, 5 parts of tin oxide powder, 3 parts of nickel oxide powder, 13 parts of titanium dioxide powder, 7 parts of fluoroapatite powder, 0.5 parts of high-temperature anti-agglomeration aid, 2 parts of adhesive, and 45 parts of solvent.

4. The water purification ceramic according to claim 1, characterized in that: The preparation of the modified kaolin comprises: First, kaolin was mixed with 0.6-1M rare earth nitrate solution and stirred at 800rpm for 20min. During the stirring period, 30mL 0.6-1M sodium hydroxide solution was added dropwise. The mixture was stirred at 800rpm for 12-16h. After suction filtration and centrifugal washing, the solid sample was collected by filtration, dried and ground to obtain modified kaolin.

5. The water purification ceramic according to any one of claims 4, characterized in that: The kaolin and the rare earth nitrate solution are mixed at a ratio of 1: (70-90).

6. The water purification ceramic according to any one of claims 4, characterized in that: The rare earth nitrate solution is prepared by adding La(NO3)3·6H2O and Ce(NO3)3·6H2O into pure water in a mass ratio of 2:

3.

7. The water purification ceramic according to claim 1, characterized in that: The particle sizes of the quartz powder, talcum powder, modified kaolin, tin oxide powder, nickel oxide powder, titanium dioxide powder and fluoroapatite powder are all 50-150 μm.

8. The water purification ceramic according to claim 1, characterized in that: The high temperature anti-agglomeration aid is one or more of small molecule siloxane and small molecule silica sol.

9. The water purification ceramic according to claim 1, characterized in that: The adhesive includes one or more of polyetherimide, bismaleimide, and water glass high temperature adhesive.

10. The water purification ceramic according to claim 1, characterized in that: The preparation method of the water purification ceramic comprises the following steps: S1. Quartz powder, talc, modified kaolin, tin oxide powder, nickel oxide powder, titanium dioxide powder, fluoroapatite powder, high temperature anti-agglomeration aid, binder, solvent were added to a ball mill and milled for 16-24h to obtain a slurry, and then pressed to obtain a ceramic blank; S2. In an oxygen-free environment, the ceramic green body is sintered at 1100-1300° C. for 28-32 hours, and after sintering, the green body is kept warm for 2 hours and cooled to room temperature to obtain a ceramic.

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