CN113398910A - Antibacterial wastewater treatment agent and preparation method thereof - Google Patents
Antibacterial wastewater treatment agent and preparation method thereof Download PDFInfo
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- CN113398910A CN113398910A CN202110558822.1A CN202110558822A CN113398910A CN 113398910 A CN113398910 A CN 113398910A CN 202110558822 A CN202110558822 A CN 202110558822A CN 113398910 A CN113398910 A CN 113398910A
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- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 49
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 48
- 238000005245 sintering Methods 0.000 claims abstract description 42
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 33
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 238000005286 illumination Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- XWFVFZQEDMDSET-UHFFFAOYSA-N gadolinium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XWFVFZQEDMDSET-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 29
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 29
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002351 wastewater Substances 0.000 abstract description 12
- 239000001045 blue dye Substances 0.000 abstract description 11
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 230000009471 action Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B01J35/39—
-
- B01J35/50—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses an antibacterial wastewater treatment agent and a preparation method thereof, wherein titanium dioxide nanoparticles are prepared by a sol-gel method, gadolinium is doped in the titanium dioxide nanoparticles to prepare gadolinium-doped nano titanium dioxide, the gadolinium-doped nano titanium dioxide is dried and then immersed in ammonia water for a period of time, and then alkali sintering is carried out to prepare gadolinium-doped nano titanium dioxide particles; electrifying the solution when the solution is immersed in ammonia water, being more beneficial to growth along the surface direction with high surface energy during sintering, changing the concentration of the ammonia water after the electrification is stopped, reducing the pH value of the solution and enhancing the treatment capacity of the methylene blue dye wastewater; during sintering, the short-time pretreatment is carried out under normal pressure and illumination, alkali steam is introduced after a period of time, and then sintering is carried out in a step-type pressurization mode to prepare gadolinium-doped nano titanium dioxide particles, so that the photocatalytic activity is improved, and the treatment of methylene blue dye wastewater is accelerated.
Description
Technical Field
The invention relates to the field of new materials, in particular to an antibacterial wastewater treatment agent and a preparation method thereof.
Background
The human demand for water resources is expanding at an alarming rate, while the increasing water pollution has contributed to the consumption of large quantities of water resources. According to the survey data in recent years, more than 1/3 rivers in China are polluted, nearly 50% of the water-bearing areas of important cities do not meet the drinking water standard, and more than 90% of the urban water areas are seriously polluted. Industrial waste water is a major source of environmental pollution. The pollution of the waste water containing heavy ions is particularly serious. Heavy metals are important pollutants with potential hazards, and cause great harm to human health and the living environment. The development of the heavy metal wastewater treatment technology is not only beneficial to environmental protection, but also can promote industrial development and human social progress.
Dye wastewater is one of important and difficult-to-treat harmful industrial wastewater, so that the chromaticity of a water body is increased rapidly, sunlight is absorbed, the photosynthesis of aquatic plants is influenced, the oxygen content in water is reduced, the normal respiration of aquatic organisms is influenced, and the ecological balance of the water body is damaged. Therefore, it is necessary to research and prepare an antibacterial wastewater treatment agent with strong wastewater treatment capacity and high speed aiming at methylene blue dye wastewater.
Disclosure of Invention
The present invention is to provide an antibacterial wastewater treatment agent to solve the problems of the background art.
In order to solve the above technical problem, a first aspect of the present invention provides the following technical solutions: the preparation method of the antibacterial wastewater treatment agent is characterized in that the process flow for preparing the antibacterial wastewater treatment agent is as follows:
preparing a solution A, preparing a solution B, preparing titanium dioxide sol, preparing titanium dioxide gel, soaking ammonia water, and sintering by using alkali to prepare the wastewater treatment agent.
Preferably, the method comprises the following specific steps:
(1) adding tetrabutyl titanate into absolute ethyl alcohol, magnetically stirring for 0.5-3 h, and fully dissolving to obtain a solution A;
(2) adding concentrated nitric acid, deionized water and gadolinium nitrate hexahydrate into absolute ethyl alcohol, magnetically stirring for 0.5-1 h, and fully dissolving to obtain a solution B;
(3) mixing the solution B with the solution A, and magnetically stirring for 6-12 hours to prepare titanium dioxide sol;
(4) standing and aging the titanium dioxide sol at room temperature for 2 days to prepare titanium dioxide gel;
(5) drying titanium dioxide gel in a forced air drying oven at 80 ℃ for 10-15 h, soaking the dried product in ammonia water, performing power-on reaction for 5-10 h, stopping power-on, adding deionized water for dilution, and magnetically stirring for 6-12 h to prepare a titanium dioxide wet material;
(6) placing the wet material into a ball mill for ball milling for 2-3 h;
(7) placing the ball-milled titanium dioxide in a sintering furnace for pretreatment;
(8) and (3) after pretreatment, keeping the temperature unchanged, introducing alkali steam, sintering for 10-15 min, performing step pressurization, sintering for 5-10 h after pressurization is completed, and naturally cooling to room temperature to obtain a finished product.
Preferably, in the step (1) above: the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1: 2 to 2.2.
Preferably, in the step (2) above: the volume ratio of the concentrated nitric acid to the deionized water to the absolute ethyl alcohol is 5; 11: 110; the molar ratio of gadolinium nitrate hexahydrate to titanium is 1: 10.
preferably, in the step (5) above: the concentration of ammonia water is 25%; 220V direct current is supplied. The volume ratio of ammonia water to deionized water is 1: 0.5 to 1.5.
Preferably, in the step (5) above: the volume ratio of ammonia water to deionized water is 1: 0.5 to 1.5.
Preferably, in the step (7) above: the pressure is normal pressure during pretreatment, the temperature is increased to 1300-1500 ℃ during illumination, and the time is 15-30 min.
Preferably, in the step (8) above: the volume of the introduced alkali steam is 10-15 times of the solid volume.
Preferably, in the step (8) above: during pressurizing, the pressure is increased to 1-5 MPa for the first time, the second pressure is performed after sintering for 1-2 h, the pressure is increased to 10-20 MPa for the second time, and the third pressure is performed after sintering for 1-2 h, and the pressure is increased to 30-40 MPa
In a second aspect of the present invention, a method for producing an antibacterial wastewater treatment agent is characterized in that the treatment agent produced by the method for producing an antibacterial wastewater treatment agent comprises the following raw materials in parts by weight: 20-40 parts of tetrabutyl titanate, 80-160 parts of absolute ethyl alcohol, 1-2 parts of concentrated nitric acid, 8-16 parts of deionized water and 2-4 parts of gadolinium nitrate hexahydrate.
Compared with the prior art, the invention has the following beneficial effects:
preparing titanium dioxide nano particles by using a sol-gel method, doping gadolinium element into the titanium dioxide nano particles to prepare gadolinium-doped titanium dioxide, drying the titanium dioxide nano particles, soaking the titanium dioxide nano particles into ammonia water for a period of time, and then performing alkali sintering to prepare gadolinium-doped titanium dioxide nano particles; the dried gadolinium-doped nano titanium dioxide is rod-shaped and ten-surface-shaped, and is electrified when being immersed in ammonia water, so that a large amount of directional negative ions exist in the solution, the charge property of each mirror surface of the amorphous gadolinium-doped nano titanium dioxide is changed, the growth along the surface direction with high surface energy is facilitated during sintering, and the oxidation activity of the gadolinium-doped nano titanium dioxide is enhanced; after the electrification is stopped, the concentration of ammonia water is changed, the pH value of the solution is reduced, the proportion of crystal form anatase and rutile of the nano titanium dioxide is increased, the activity of the nano titanium dioxide is maximized, and the treatment capacity of the methylene blue dye wastewater is enhanced.
During sintering, carrying out short-time pretreatment under normal pressure and illumination, introducing alkali steam after a period of time, and sintering in a step-type pressurization mode to prepare gadolinium-doped nano titanium dioxide particles; the lattice distortion of the gadolinium-doped nano titanium dioxide generates strain energy, and the gadolinium-doped nano titanium dioxide is pretreated under normal pressure and illumination, so that holes are not easily generated by compounding, the particle surface area is increased, and the photocatalytic activity is improved; simultaneously, the terminal hydroxyl and the bridge hydroxyl on the surface are exposed after pretreatment, and the terminal hydroxyl connected to an acid position is reduced after alkali steam is introduced, so that the balance between the terminal hydroxyl and the bridge hydroxyl is broken; and then, through step-type pressurization, crystal grains grow along the surface direction with high surface energy, and simultaneously, more bridge hydroxyl groups are generated on the surface, so that the isoelectric point can be reduced when more bridge hydroxyl groups are treated in the nano titanium dioxide dye wastewater, and the surface carries a large amount of negative charges, thereby being more beneficial to the transfer of photon-generated carriers, promoting the generation of free radicals and further accelerating the treatment of the methylene blue dye wastewater.
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.
The first aspect of the invention provides the following technical scheme: the preparation method of the antibacterial wastewater treatment agent is characterized in that the process flow for preparing the antibacterial wastewater treatment agent is as follows:
preparing a solution A, preparing a solution B, preparing titanium dioxide sol, preparing titanium dioxide gel, soaking ammonia water, and sintering by using alkali to prepare the wastewater treatment agent.
Preferably, the method comprises the following specific steps:
(1) adding tetrabutyl titanate into absolute ethyl alcohol, magnetically stirring for 0.5-3 h, and fully dissolving to obtain a solution A;
(2) adding concentrated nitric acid, deionized water and gadolinium nitrate hexahydrate into absolute ethyl alcohol, magnetically stirring for 0.5-1 h, and fully dissolving to obtain a solution B;
(3) mixing the solution B with the solution A, and magnetically stirring for 6-12 hours to prepare titanium dioxide sol;
(4) standing and aging the titanium dioxide sol at room temperature for 2 days to prepare titanium dioxide gel;
(5) drying titanium dioxide gel in a forced air drying oven at 80 ℃ for 10-15 h, soaking the dried product in ammonia water, performing power-on reaction for 5-10 h, stopping power-on, adding deionized water for dilution, and magnetically stirring for 6-12 h to prepare a titanium dioxide wet material;
(6) placing the wet material into a ball mill for ball milling for 2-3 h;
(7) placing the ball-milled titanium dioxide in a sintering furnace for pretreatment;
(8) and (3) after pretreatment, keeping the temperature unchanged, introducing alkali steam, sintering for 10-15 min, performing step pressurization, sintering for 5-10 h after pressurization is completed, and naturally cooling to room temperature to obtain a finished product.
Preferably, in the step (1) above: the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1: 2 to 2.2.
Preferably, in the step (2) above: the volume ratio of the concentrated nitric acid to the deionized water to the absolute ethyl alcohol is 5; 11: 110; the molar ratio of gadolinium nitrate hexahydrate to titanium is 1: 10.
preferably, in the step (5) above: the concentration of ammonia water is 25%; 220V direct current is supplied. The volume ratio of ammonia water to deionized water is 1: 0.5 to 1.5.
Preferably, in the step (5) above: the volume ratio of ammonia water to deionized water is 1: 0.5 to 1.5.
Preferably, in the step (7) above: the pressure is normal pressure during pretreatment, the temperature is increased to 1300-1500 ℃ during illumination, and the time is 15-30 min.
Preferably, in the step (8) above: the volume of the introduced alkali steam is 10-15 times of the solid volume.
Preferably, in the step (8) above: during pressurizing, the pressure is increased to 1-5 MPa for the first time, the second pressure is performed after sintering for 1-2 h, the pressure is increased to 10-20 MPa for the second time, and the third pressure is performed after sintering for 1-2 h, and the pressure is increased to 30-40 MPa
In a second aspect of the present invention, a method for producing an antibacterial wastewater treatment agent is characterized in that the treatment agent produced by the method for producing an antibacterial wastewater treatment agent comprises the following raw materials in parts by weight: 20-40 parts of tetrabutyl titanate, 80-160 parts of absolute ethyl alcohol, 1-2 parts of concentrated nitric acid, 8-16 parts of deionized water and 2-4 parts of gadolinium nitrate hexahydrate.
Example 1: the antibacterial wastewater treatment agent I:
an antibacterial wastewater treatment agent comprises the following components in parts by weight:
the weight fraction of tetrabutyl titanate is 20 parts, the weight fraction of absolute ethyl alcohol is 80 parts, the weight fraction of concentrated nitric acid is 1 part, the weight fraction of deionized water is 8 parts, and the weight fraction of gadolinium nitrate hexahydrate is 2 parts.
The preparation method of the treating agent comprises the following steps:
(1) tetrabutyl titanate and absolute ethyl alcohol are mixed according to the volume ratio of 1: 2, mixing, magnetically stirring for 0.5h, and fully dissolving to obtain a solution A;
(2) adding concentrated nitric acid, deionized water and gadolinium nitrate hexahydrate into absolute ethyl alcohol, wherein the volume ratio of the concentrated nitric acid to the deionized water is 5; 11; the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 10, the molar ratio of gadolinium nitrate hexahydrate to titanium is 1: 10, stirring for 0.5h by magnetic force, and fully dissolving to obtain a solution B;
(3) mixing the solution B with the solution A, and magnetically stirring for 6 hours to prepare titanium dioxide sol;
(4) standing and aging the titanium dioxide sol at room temperature for 2 days to prepare titanium dioxide gel;
(5) drying titanium dioxide gel in a forced air drying oven at 80 ℃ for 10h, soaking a product in ammonia water after drying, wherein the concentration of the ammonia water is 25%, introducing 220V direct current to react for 5h, stopping energization, and adding deionized water to dilute, wherein the volume ratio of the ammonia water to the added deionized water is 1: 0.5, magnetically stirring for 6 hours to prepare a titanium dioxide wet material;
(6) placing the wet material in a ball mill for ball milling for 2 hours;
(7) placing the ball-milled titanium dioxide in a sintering furnace for pretreatment, wherein the pressure is normal pressure, the temperature is raised to 1300 ℃ while illumination is carried out, and the time is 15 min;
(8) keeping the temperature unchanged after pretreatment, introducing alkali steam, wherein the volume of the alkali steam is 10 times of the solid volume, sintering for 10min, performing step pressurization, pressurizing to 1MPa for the first time, pressurizing to 10MPa for the second time after sintering for 1h, pressurizing to 30MPa for the third time after sintering for 1h, sintering for 5h after pressurization, and naturally cooling to room temperature to obtain the finished product.
Example 2: and (2) antibacterial wastewater treatment agent II:
an antibacterial wastewater treatment agent comprises the following components in parts by weight:
the weight fraction of tetrabutyl titanate is 40 parts, the weight fraction of absolute ethyl alcohol is 160 parts, the weight fraction of concentrated nitric acid is 2 parts, the weight fraction of deionized water is 16 parts, and the weight fraction of gadolinium nitrate hexahydrate is 4 parts.
The preparation method of the treating agent comprises the following steps:
(1) tetrabutyl titanate and absolute ethyl alcohol are mixed according to the volume ratio of 1: 2, mixing, magnetically stirring for 3 hours, and fully dissolving to obtain a solution A;
(2) adding concentrated nitric acid, deionized water and gadolinium nitrate hexahydrate into absolute ethyl alcohol, wherein the volume ratio of the concentrated nitric acid to the deionized water is 5; 11; the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 10, the molar ratio of gadolinium nitrate hexahydrate to titanium is 1: 10, stirring for 1 hour by magnetic force, and fully dissolving to obtain a solution B;
(3) mixing the solution B with the solution A, and magnetically stirring for 12 hours to prepare titanium dioxide sol;
(4) standing and aging the titanium dioxide sol at room temperature for 2 days to prepare titanium dioxide gel;
(5) drying titanium dioxide gel in a forced air drying oven at 80 ℃ for 15h, soaking a product in ammonia water after drying, wherein the concentration of the ammonia water is 25%, introducing 220V direct current to react for 10h, stopping energization, and adding deionized water to dilute, wherein the volume ratio of the ammonia water to the added deionized water is 1: 0.5, magnetically stirring for 12 hours to prepare a titanium dioxide wet material;
(6) placing the wet material in a ball mill for ball milling for 2 hours;
(7) placing the ball-milled titanium dioxide in a sintering furnace for pretreatment, wherein the pressure is normal pressure, the temperature is raised to 1500 ℃ while illumination is carried out, and the time is 30 min;
(8) keeping the temperature unchanged after pretreatment, introducing alkali steam, wherein the volume of the alkali steam is 15 times of the solid volume, sintering for 10min, performing step pressurization, pressurizing to 5MPa for the first time, pressurizing to 20MPa for the second time after sintering for 2h, pressurizing to 40MPa for the third time after sintering for 2h, sintering for 5h after pressurization, and naturally cooling to room temperature to obtain the finished product.
Comparative example 1
The formulation of comparative example 1 was the same as example 1. The preparation method of the antibacterial wastewater treatment agent is different from the preparation method of the antibacterial wastewater treatment agent in the step (5), and the step (4) is modified as follows: drying titanium dioxide gel in a forced air drying oven at 80 ℃ for 10h, soaking a product in ammonia water after drying, wherein the concentration of the ammonia water is 25%, standing for 5h for reaction, and adding deionized water for dilution, wherein the volume ratio of the ammonia water to the added deionized water is 1: and (3) performing magnetic stirring for 6 hours to obtain the titanium dioxide wet material. The rest of the preparation steps are the same as example 1.
Comparative example 2
Comparative example 2 was formulated as in example 1. The preparation method of the antibacterial wastewater treatment agent is different from the preparation method of the antibacterial wastewater treatment agent in the embodiment 1 only in the difference of the step (5), and the step (5) is modified as follows: drying the titanium dioxide gel in a forced air drying oven at 80 ℃ for 10h, soaking the dried product in ammonia water with the concentration of 25%, introducing 220V direct current to react for 5h, and stopping energization to obtain the titanium dioxide wet material. The rest of the preparation steps are the same as example 1.
Comparative example 3
The formulation of comparative example 3 was the same as example 1. The method for producing the antibacterial wastewater treatment agent differs from example 1 only in that the step (7) is not performed, and the step (8) is performed by alkali sintering while keeping the temperature constant. The rest of the preparation steps are the same as example 1.
Comparative example 4
Comparative example 4 was formulated as in example 1. The preparation method of the antibacterial wastewater treatment agent is different from the preparation method of the antibacterial wastewater treatment agent in the embodiment 1 only in the difference of the step (8), and the step (8) is modified as follows: and (3) after pretreatment, keeping the temperature unchanged, carrying out step pressure sintering, carrying out first pressure to 1MPa, carrying out second pressure to 10MPa after sintering for 1h, carrying out third pressure to 30MPa after sintering for 1h, and naturally cooling to room temperature after sintering for 5h to obtain the finished product. The rest of the preparation steps are the same as example 1.
Test example 1
1. Test method
Example 1 and comparative examples 1 and 2 are control tests, 1 g of example 1 and comparative examples 1 and 2 are weighed and applied to methylene blue dye wastewater treatment, the concentration of the methylene blue is 10mg/L, the volume of the methylene blue is 200mL, the methylene blue is catalytically degraded for 3h under the action of visible light and stirring at normal temperature and normal pressure, and the degradation rate of the methylene blue is measured after stabilization for comparison.
2. Test results
The methylene blue degradation rate of example 1 is compared with that of comparative examples 1 and 2.
TABLE 1 degradation rate of methylene blue
| Methylene blue degradation rate (%) | |
| Example 1 | 99.2 |
| Comparative example 1 | 97.3 |
| Comparative example 2 | 96.4 |
By comparing the degradation rate of methylene blue of example 1 with that of comparative examples 1 and 2, the antibacterial wastewater treatment agent prepared in example 1 can be obviously found to have stronger ability of degrading methylene blue, which indicates that the treatment ability of the treatment agent on methylene blue dye wastewater can be enhanced to different degrees by diluting ammonia water after the treatment agent is immersed in the ammonia water and electrified and stopped, indicating that the antibacterial wastewater treatment agent prepared in the invention has stronger treatment ability on methylene blue dye wastewater.
Test example 2
1. Test method
Example 1 and comparative examples 3 and 4 are comparison tests, 1 g of example 1 and comparative examples 1 and 2 are weighed and applied to methylene blue dye wastewater treatment, the concentration of the methylene blue is 10mg/L, the volume of the methylene blue is 200mL, the methylene blue is catalytically degraded under the action of visible light and stirring at normal temperature and normal pressure for 1min, and the degradation rate of the methylene blue is measured and compared.
2. Test results
Example 1 comparison of the degradation rates of methylene blue in the same time as comparative example 3
TABLE 2 degradation Rate of methylene blue
| Methylene blue degradation rate (%/min) | |
| Example 1 | 94.3 |
| Comparative example 3 | 84.5 |
| Comparative example 4 | 89.3 |
By comparing the methylene blue degradation rate in the same time of the example 1 with that of the comparative examples 3 and 4, the antibacterial wastewater treatment agent prepared in the example 1 can be obviously found to have a significantly higher methylene blue degradation rate, which indicates that the methylene blue dye wastewater can be obviously accelerated to be treated by the special alkali sintering mode, and indicates that the antibacterial wastewater treatment agent prepared in the invention not only has a stronger treatment capacity of the methylene blue dye wastewater, but also has a faster treatment rate.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the antibacterial wastewater treatment agent is characterized in that the process flow for preparing the antibacterial wastewater treatment agent is as follows: preparing a solution A, preparing a solution B, preparing titanium dioxide sol, preparing titanium dioxide gel, soaking ammonia water, and sintering by using alkali to prepare the wastewater treatment agent.
2. The method for preparing an antibacterial wastewater treatment agent according to claim 1, comprising the following specific steps:
(1) adding tetrabutyl titanate into absolute ethyl alcohol, magnetically stirring for 0.5-3 h, and fully dissolving to obtain a solution A;
(2) adding concentrated nitric acid, deionized water and gadolinium nitrate hexahydrate into absolute ethyl alcohol, magnetically stirring for 0.5-1 h, and fully dissolving to obtain a solution B;
(3) mixing the solution B with the solution A, and magnetically stirring for 6-12 hours to prepare titanium dioxide sol;
(4) standing and aging the titanium dioxide sol at room temperature for 2 days to prepare titanium dioxide gel;
(5) drying titanium dioxide gel in a forced air drying oven at 80 ℃ for 10-15 h, soaking the dried product in ammonia water, performing power-on reaction for 5-10 h, stopping power-on, adding deionized water for dilution, and magnetically stirring for 6-12 h to prepare a titanium dioxide wet material;
(6) placing the wet material into a ball mill for ball milling for 2-3 h;
(7) placing the ball-milled titanium dioxide in a sintering furnace for pretreatment;
(8) and (3) after pretreatment, keeping the temperature unchanged, introducing alkali steam, sintering for 10-15 min, performing step pressurization, sintering for 5-10 h after pressurization is completed, and naturally cooling to room temperature to obtain a finished product.
3. The method for producing an antibacterial wastewater treatment agent according to claim 2, wherein in the step (1): the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1: 2 to 2.2.
4. The method for producing an antibacterial wastewater treatment agent according to claim 2, wherein in the step (2): the volume ratio of the concentrated nitric acid to the deionized water to the absolute ethyl alcohol is 5: 11: 110; the molar ratio of gadolinium nitrate hexahydrate to tetrabutyl titanate is 1: 10.
5. the method for producing an antibacterial wastewater treatment agent according to claim 2, wherein in the step (5): the concentration of ammonia water is 25%; 220V direct current is supplied. The volume ratio of ammonia water to deionized water is 1: 0.5 to 1.5.
6. The method for producing an antibacterial wastewater treatment agent according to claim 2, wherein in the step (5): the volume ratio of ammonia water to deionized water is 1: 0.5 to 1.5.
7. The method for producing an antibacterial wastewater treatment agent according to claim 2, wherein in the step (7): the pressure is normal pressure during pretreatment, the temperature is increased to 1300-1500 ℃ during illumination, and the time is 15-30 min.
8. The method for producing an antibacterial wastewater treatment agent according to claim 2, wherein in the step (8): the volume of the introduced alkali steam is 10-15 times of the solid volume.
9. The method for producing an antibacterial wastewater treatment agent according to claim 2, wherein in the step (8): and during pressurization, the first pressurization is carried out to 1-5 MPa, the second pressurization is carried out after sintering for 1-2 h, the pressurization is carried out to 10-20 MPa, and the third pressurization is carried out after sintering for 1-2 h, and the pressurization is carried out to 30-40 MPa.
10. The method for preparing an antibacterial wastewater treatment agent according to claim 1, wherein the wastewater treatment agent prepared by the method for preparing an antibacterial wastewater treatment agent comprises the following raw materials in parts by weight: 20-40 parts of tetrabutyl titanate, 80-160 parts of absolute ethyl alcohol, 1-2 parts of concentrated nitric acid, 8-16 parts of deionized water and 2-4 parts of gadolinium nitrate hexahydrate.
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