CN112093844A - Nitrogen-removing water purifying agent and preparation method thereof - Google Patents
Nitrogen-removing water purifying agent and preparation method thereof Download PDFInfo
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- C02F2101/163—Nitrates
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- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses a preparation method of a nitrogen removal water purifying agent, which comprises the following steps: preparing titanium-containing wet gel; mixing the prepared titanium-containing wet gel, plant straw powder, fly ash, clay, zeolite powder and deionized water, granulating, and sintering to obtain mesoporous composite ceramsite; grafting 3-aminopropyl triethoxysilane on the surface of the mesoporous composite ceramsite to prepare modified mesoporous composite ceramsite; preparing a graphene oxide dispersion liquid and a mesoporous composite ceramsite dispersion liquid, dropwise adding the mesoporous composite ceramsite dispersion liquid into the graphene oxide dispersion liquid, stirring after dropwise adding, dropwise adding an ammonia water solution and hydrazine hydrate, stirring, transferring into a high-pressure kettle for reaction, cooling to room temperature after the reaction is finished, and aging to obtain the nitrogen-removing water purifying agent. The nitrogen-removing water purifying agent prepared by the invention has large specific surface area, extremely strong adsorption force, certain photocatalytic activity and certain ion exchange capacity, can effectively remove ammonia nitrogen and nitrate nitrogen in wastewater, and has no secondary pollution to water.
Description
The technical field is as follows:
the invention relates to the field of wastewater treatment, and particularly relates to a nitrogen removal water purifying agent and a preparation method thereof.
Background art:
the eutrophication of water body refers to the phenomenon that under the influence of natural and human activities, the concentration of nitrogen, phosphorus and other nutrient elements in surface water bodies such as lakes, rivers and the like is greatly increased, so that a large amount of algae and other plankton are increased and propagated, the DO concentration of the water body is reduced, the water quality is seriously deteriorated, a large amount of aquatic plants and animals die, and the balance of an aquatic ecosystem is damaged. The increase of nutrient substances such as nitrogen and phosphorus is the root cause of water eutrophication, the nitrogen concentration in the water is at a relatively low level in a natural state, and nitrogen is a main restriction factor for the growth and propagation of aquatic plants. The eutrophication of water body caused by the increase of nitrogen is caused by a plurality of factors, which can be divided into natural factors and human factors on the whole. The natural factors mainly comprise precipitation, atmospheric sedimentation, soil erosion and eluviation, change of climatic conditions, self circulation of an aquatic ecosystem and the like; the artificial factors are the main factors causing eutrophication of water bodies, and the artificial factors refer to the increase of water body nitrogen caused by human activities, and mainly comprise discharge of industrial and domestic sewage, agricultural non-point source pollution and the like. Therefore, how to remove ammonia nitrogen and nitrate nitrogen in water is an urgent problem to be solved.
At present, the denitrification methods mainly comprise physicochemical denitrification methods and biological denitrification methods. The biological denitrification method mainly comprises a nitrification-denitrification process, namely firstly oxidizing nitrogen compounds into nitrates by using nitrifying bacteria in the wastewater under an aerobic condition, then reducing the nitrates into gaseous nitrogen and other final gaseous products by using denitrifying bacteria in the wastewater under an anoxic condition, and releasing the gaseous nitrogen and other final gaseous products into the atmosphere. The physicochemical methods include a selective ion exchange method, a breakpoint oxidation method, and the like. Biological denitrification is a very complex biochemical process and is not easy to control; while the physical and chemical denitrification is relatively simple. Chinese patent 200510024373.3 discloses a nitrogen-containing sewage treatment method, specifically a biological denitrification treatment method for coking wastewater. The nitrification and denitrification reactions are carried out in the SBR reactor, the zeolite powder with the aperture of 0.4nm is added into the reactor, and the denitrification effect of the SBR reactor is enhanced by adopting the restrictive aeration, so that the ammonia nitrogen in the effluent reaches the national first-level sewage discharge standard. The method is mainly used for biologically removing ammonia nitrogen contained in the coking wastewater. Chinese patent 201210451145.4 provides a process for deep denitrification of wastewater, which comprises the following steps: (1) performing microwave irradiation coagulative precipitation, adding a certain amount of NaOH into high-concentration ammonia nitrogen wastewater, adjusting the pH value to 11-13, performing coagulative precipitation on a flocculating agent and a coagulant under an alkaline condition, and obtaining a supernatant after precipitation; (2) introducing the supernatant obtained in the step (1) into a stripping tower; the top of the stripping tower is provided with a sprayer, the middle part in the tower body is provided with a plurality of packing layers, and the wastewater forms a fine liquid flow through the packing layers through the sprayer; simultaneously, air is sent into an aeration port at the bottom of the tower through a blower, so that gas-liquid contact is carried out on the surface of the filler; then leading the blow-off tail gas to enter an absorption tank filled with waste hydrochloric acid or waste sulfuric acid absorption liquid to absorb part of ammonia nitrogen; (3) continuously and circularly precipitating ammonia from a Magnesium Ammonium Phosphate (MAP) pyrolysis product; then the MAP precipitation effluent enters a biological denitrification process for treatment; (4) 3 an 3 A 3- 3 A 3- 3 O 3 biological 3 denitrification 3 process 3, 3 wherein 3 the 3 effluent 3 water 3 of 3 the 3 step 3 ( 3 3 3) 3 is 3 introduced 3 into 3 an 3 anaerobic 3 ( 3 A 3) 3- 3 anoxic 3 ( 3 A 3) 3- 3 aerobic 3 ( 3 O 3) 3 biological 3 denitrification 3 process 3; 3 (5) The rest nitrogen is denitrified by a denitrification biological filter and a membrane filter. Finally, the ammonia nitrogen and the total nitrogen of the treated effluent can reach the first-class A standard of pollutant discharge Standard of urban Sewage treatment plant (GB 18918-2002). Chinese patent 201510767294.5 discloses a denitrifier, which comprises the following components in parts by weight: the composition comprises 50-70 parts of a main component, 20-40 parts of a promoting component and 1-10 parts of an auxiliary component, wherein the main component is formed by mixing chlorite, hypochlorite and trichloroisocyanuric acid according to a mass ratio of 1: 1.5-2.5: 1-5, the promoting component is formed by mixing manganese dioxide and ferric trichloride according to a mass ratio of 1: 2-8, and the auxiliary component is soluble carbonate. The denitrifying agent can effectively remove residual ammonia nitrogen in low-concentration ammonia nitrogen wastewater, and has the advantages of high removal efficiency, small using amount, economic and easily-obtained denitrifying agent raw materials, simple processing and preparation and low cost. According to the prior art, the chemical method is mainly used for removing the ammonia nitrogen and the nitrate nitrogen in the wastewater at present, and high-performance filler is added into the wastewater to further carry out advanced treatment on the wastewater. The key point is how to develop a water purifying agent which has small addition amount and can deeply remove ammonia nitrogen and nitrate nitrogen in wastewater.
The invention content is as follows:
the invention aims to solve the technical problem that the defects of the prior art are overcome, and the invention provides the denitrogenation water purifying agent and the preparation method thereof; then mixing and drying the rest plant straw powder, fly ash, clay, zeolite powder and deionized water, and sintering to prepare mesoporous composite ceramsite, wherein the mesoporous composite ceramsite has the advantages of large specific surface area, strong adsorption force, certain photocatalytic activity and certain ion exchange capacity, can effectively remove ammonia nitrogen and nitrate nitrogen in wastewater, and has no secondary pollution to water; after the mesoporous composite ceramsite is compounded with graphene, the mesoporous composite ceramsite is uniformly dispersed on a graphene sheet layer to form more adsorption active sites, so that the wastewater treatment effect is further improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a nitrogen-removing water purifying agent comprises the following steps:
(1) mixing cetyl trimethyl ammonium bromide and deionized water, stirring at 50-60 deg.C until solid is dissolved, then dropwise adding ammonia water solution, stirring for 10-15min, adding tetrabutyl titanate, stirring for hydrolysis, cooling to room temperature, aging for 20-24 hr, and filtering to obtain white wet gel;
(2) mixing and stirring the prepared white wet gel, plant straw powder, fly ash, clay, zeolite powder and deionized water uniformly, granulating, drying, and placing in a muffle furnace for sintering treatment to prepare mesoporous composite ceramsite;
(3) dispersing the mesoporous composite ceramsite in a toluene solvent, stirring and dispersing for 1-2h at 50-60 ℃, adding 3-aminopropyltriethoxysilane, continuing stirring for 2-3h, filtering, washing precipitates with absolute ethyl alcohol and deionized water in sequence, and drying to obtain modified mesoporous composite ceramsite;
(4) preparing a graphene oxide dispersion liquid by adopting a Hummer method; dispersing the prepared modified mesoporous composite ceramsite in deionized water to prepare mesoporous composite ceramsite dispersion, dropwise adding the mesoporous composite ceramsite dispersion into graphene oxide dispersion while stirring, continuously stirring for 30min after dropwise adding, then heating to 50-60 ℃, stirring for 1-2h, continuously dropwise adding an ammonia water solution and hydrazine hydrate, stirring for 30-50min, transferring the prepared mixed solution into a high-pressure kettle, reacting for 10-15h at 120-150 ℃, cooling to room temperature after the reaction is finished, aging for 10-15h, filtering, precipitating, washing, and freeze-drying to obtain the nitrogen-removing water purifying agent.
Preferably, in the step (1), the mass concentration of the aqueous ammonia solution is 20 to 25%.
Preferably, in the step (1), the dosage ratio of the cetyl trimethyl ammonium bromide, the deionized water, the ammonia water solution and the tetrabutyl titanate is (1-3) g: 50 ml: (8-10) ml: 10 ml.
Preferably, in the step (2), the mass ratio of the white wet gel to the plant straw powder to the fly ash to the clay to the zeolite powder to the deionized water is (10-15): 10: (20-30): 30: (5-10): 10.
as a preferable aspect of the above, in the step (2), the conditions of the sintering treatment are: firstly, the heat preservation treatment is carried out for 30min at 500 ℃, and then the heat preservation treatment is carried out for 1h at 900 ℃.
Preferably, in the step (3), the usage ratio of the mesoporous composite ceramsite to the 3-aminopropyltriethoxysilane is (1-3) g: 5 ml.
Preferably, in the step (4), the concentration of the graphene oxide dispersion liquid is 5 g/L; the concentration of the mesoporous composite ceramsite dispersion liquid is 0.4 g/ml.
Preferably, in the step (4), the volume ratio of the graphene oxide dispersion liquid to the mesoporous composite ceramsite dispersion liquid to the ammonia water solution to the hydrazine hydrate is 1: (2-3): 0.1:0.1.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the nitrogen-removing water purifying agent is prepared by mixing, granulating and sintering mesoporous titanium oxide, plant straw powder, fly ash, clay and zeolite powder to prepare mesoporous composite ceramsite compound graphene; the mesoporous composite ceramsite is uniformly dispersed among the graphene sheets. The mesoporous composite ceramsite prepared by the method has a plurality of pore structures, and the internal net structures are criss-cross, so that the mesoporous composite ceramsite has a strong adsorption effect; the mesoporous composite ceramsite has certain ion exchange capacity, ammonium ions in wastewater can migrate to the surface of the mesoporous composite ceramsite among graphene sheets and enter pores of the mesoporous composite ceramsite in wastewater treatment, an effective exchange position is achieved for exchange reaction, and the exchanged ions enter the wastewater through the pores of the mesoporous composite ceramsite; the mesoporous composite ceramsite has more adsorption active points and exchange points, and can effectively remove nitrogen elements in wastewater. The nitrogen-removing water purifying agent prepared by the invention also has certain photocatalytic activity and can effectively degrade nitrogen-containing pollutants in wastewater.
In the process of preparing the nitrogen-removing water purifying agent, firstly, cetyl trimethyl ammonium bromide is taken as a template, then sol gel is adopted to prepare titanium-containing wet gel, the titanium-containing wet gel is directly mixed with plant straw powder, fly ash, clay, zeolite powder and deionized water without being dried, granulated, primarily dried and sintered to prepare the composite ceramsite with the multistage pore structure, and the composite ceramsite has the advantages of large specific surface area, strong adsorption capacity, certain photocatalytic activity and ion exchange capacity; then, the surface of the composite ceramic particle is aminated and compounded with graphene, and the composite ceramic particle is uniformly dispersed on a graphene sheet layer. When the nitrogen removal water purifier prepared by the invention is used for wastewater treatment, the nitrogen removal rate is high, and no secondary pollution is caused to water.
The specific implementation mode is as follows:
the present invention is further illustrated by the following examples, which are provided for the purpose of illustration only and are not intended to be limiting.
Example 1
(1) Mixing 1g of hexadecyl trimethyl ammonium bromide and 50ml of deionized water, stirring at 50 ℃ until the solid is dissolved, then dropwise adding 8ml of ammonia water solution with the mass concentration of 20%, continuously stirring for 10 inches, adding 10ml of tetrabutyl titanate, stirring, hydrolyzing, cooling to room temperature, aging for 20 hours, and filtering to obtain white wet gel;
(2) mixing and stirring 10g of the prepared white wet gel, 10g of plant straw powder, 20g of fly ash, 30g of clay, 5g of zeolite powder and 10g of deionized water uniformly, granulating, drying, placing in a muffle furnace, firstly carrying out heat preservation treatment at 500 ℃ for 30min, and then carrying out heat preservation treatment at 900 ℃ for 1h to prepare mesoporous composite ceramsite;
(3) dispersing 2g of the mesoporous composite ceramsite in 80ml of toluene solvent, stirring and dispersing at 50 ℃ for 1h, adding 10ml of 3-aminopropyltriethoxysilane, continuing stirring for 2h, filtering, washing the precipitate with absolute ethyl alcohol and deionized water in sequence, and drying to obtain modified mesoporous composite ceramsite;
(4) preparing a graphene oxide dispersion liquid with the concentration of 5g/L by adopting a Hummer method; dispersing the prepared modified mesoporous composite ceramsite in deionized water to prepare a mesoporous composite ceramsite dispersion liquid with the concentration of 0.4g/ml, dropwise adding 20ml of the mesoporous composite ceramsite dispersion liquid into 10ml of graphene oxide dispersion liquid, stirring while dropwise adding, continuously stirring for 30min after dropwise adding is finished, then heating to 50 ℃, stirring for 1h, continuously dropwise adding 1ml of an ammonia water solution with the mass concentration of 20% and 1ml of hydrazine hydrate, stirring for 30min, transferring the prepared mixed solution into a high-pressure kettle, reacting for 10h at 120 ℃, cooling to room temperature after the reaction is finished, aging for 10h, filtering, precipitating, washing, and freeze-drying to obtain the nitrogen-removing water purifying agent.
Example 2
(1) Mixing 3g of hexadecyl trimethyl ammonium bromide and 50ml of deionized water, stirring at 60 ℃ until the solid is dissolved, then dropwise adding 10ml of 25% ammonia water solution, continuously stirring for 15min, adding 10ml of tetrabutyl titanate, stirring, hydrolyzing, cooling to room temperature, aging for 24h, filtering, and obtaining white wet gel;
(2) mixing and stirring uniformly 15g of the prepared white wet gel, 10g of plant straw powder, 30g of fly ash, 30g of clay, 10g of zeolite powder and 10g of deionized water, granulating, drying, placing in a muffle furnace, firstly carrying out heat preservation treatment at 500 ℃ for 30min, and then carrying out heat preservation treatment at 900 ℃ for 1h to prepare mesoporous composite ceramsite;
(3) dispersing 6g of the mesoporous composite ceramsite in 80ml of toluene solvent, stirring and dispersing at 60 ℃ for 2 hours, adding 10ml of 3-aminopropyltriethoxysilane, continuing stirring for 3 hours, filtering, washing precipitates by absolute ethyl alcohol and deionized water in sequence, and drying to obtain modified mesoporous composite ceramsite;
(4) preparing a graphene oxide dispersion liquid with the concentration of 5g/L by adopting a Hummer method; dispersing the prepared modified mesoporous composite ceramsite in deionized water to prepare a mesoporous composite ceramsite dispersion liquid with the concentration of 0.4g/ml, dropwise adding 30ml of the mesoporous composite ceramsite dispersion liquid into 10ml of graphene oxide dispersion liquid, stirring while dropwise adding, continuously stirring for 30min after dropwise adding is finished, then heating to 60 ℃, stirring for 2h, continuously dropwise adding 1ml of an ammonia water solution with the mass concentration of 20% and 1ml of hydrazine hydrate, stirring for 50min, transferring the prepared mixed solution into a high-pressure kettle, reacting for 15h at 150 ℃, cooling to room temperature after the reaction is finished, aging for 15h, filtering, precipitating, washing, and freeze-drying to obtain the nitrogen-removing water purifying agent.
Example 3
(1) Mixing 1.5g of hexadecyl trimethyl ammonium bromide and 50ml of deionized water, stirring at 50 ℃ until the solid is dissolved, then dropwise adding 8ml of 25% ammonia water solution, continuously stirring for 15min, adding 10ml of tetrabutyl titanate, stirring, hydrolyzing, cooling to room temperature, aging for 21h, and filtering to obtain white wet gel;
(2) mixing and stirring 11g of the prepared white wet gel, 10g of plant straw powder, 22g of fly ash, 30g of clay, 6g of zeolite powder and 10g of deionized water uniformly, granulating, drying, placing in a muffle furnace, firstly carrying out heat preservation treatment at 500 ℃ for 30min, and then carrying out heat preservation treatment at 900 ℃ for 1h to prepare mesoporous composite ceramsite;
(3) dispersing 3g of the mesoporous composite ceramsite in 80ml of toluene solvent, stirring and dispersing at 50 ℃ for 1h, adding 10ml of 3-aminopropyltriethoxysilane, continuing stirring for 3h, filtering, washing precipitates by absolute ethyl alcohol and deionized water in sequence, and drying to obtain modified mesoporous composite ceramsite;
(4) preparing a graphene oxide dispersion liquid with the concentration of 5g/L by adopting a Hummer method; dispersing the prepared modified mesoporous composite ceramsite in deionized water to prepare a mesoporous composite ceramsite dispersion liquid with the concentration of 0.4g/ml, dropwise adding 25ml of the mesoporous composite ceramsite dispersion liquid into 10ml of graphene oxide dispersion liquid, stirring while dropwise adding, continuously stirring for 30min after dropwise adding is finished, then heating to 60 ℃, stirring for 1h, continuously dropwise adding 1ml of an ammonia water solution with the mass concentration of 20% and 1ml of hydrazine hydrate, stirring for 40min, transferring the prepared mixed liquid into a high-pressure kettle, reacting for 11h at 130 ℃, cooling to room temperature after the reaction is finished, aging for 12h, filtering, precipitating, washing, and freeze-drying to obtain the nitrogen-removing water purifying agent.
Example 4
(1) Mixing 2g of hexadecyl trimethyl ammonium bromide and 50ml of deionized water, stirring at 55 ℃ until the solid is dissolved, then dropwise adding 9ml of ammonia water solution with the mass concentration of 20%, continuously stirring for 10min, adding 10ml of tetrabutyl titanate, stirring, hydrolyzing, cooling to room temperature, aging for 22h, filtering, and preparing white wet gel;
(2) mixing and stirring 12g of the prepared white wet gel, 10g of plant straw powder, 25g of fly ash, 30g of clay, 7g of zeolite powder and 10g of deionized water uniformly, granulating, drying, placing in a muffle furnace, firstly carrying out heat preservation treatment at 500 ℃ for 30min, and then carrying out heat preservation treatment at 900 ℃ for 1h to prepare mesoporous composite ceramsite;
(3) dispersing 4g of the mesoporous composite ceramsite in 80ml of toluene solvent, stirring and dispersing at 50 ℃ for 2 hours, adding 10ml of 3-aminopropyltriethoxysilane, continuing stirring for 3 hours, filtering, washing precipitates by absolute ethyl alcohol and deionized water in sequence, and drying to obtain modified mesoporous composite ceramsite;
(4) preparing a graphene oxide dispersion liquid with the concentration of 5g/L by adopting a Hummer method; dispersing the prepared modified mesoporous composite ceramsite in deionized water to prepare a mesoporous composite ceramsite dispersion liquid with the concentration of 0.4g/ml, dropwise adding 30ml of the mesoporous composite ceramsite dispersion liquid into 10ml of graphene oxide dispersion liquid, stirring while dropwise adding, continuously stirring for 30min after dropwise adding is finished, then heating to 50 ℃, stirring for 1h, continuously dropwise adding 1ml of an ammonia water solution with the mass concentration of 20% and 1ml of hydrazine hydrate, stirring for 30min, transferring the prepared mixed solution into a high-pressure kettle, reacting for 13h at 140 ℃, cooling to room temperature after the reaction is finished, aging for 12h, filtering, precipitating, washing, and freeze-drying to obtain the nitrogen-removing water purifying agent.
Example 5
(1) Mixing 3g of hexadecyl trimethyl ammonium bromide and 50ml of deionized water, stirring at 60 ℃ until the solid is dissolved, then dropwise adding 10ml of ammonia water solution with the mass concentration of 20%, continuously stirring for 14min, adding 10ml of tetrabutyl titanate, stirring, hydrolyzing, cooling to room temperature, aging for 23h, and filtering to obtain white wet gel;
(2) mixing and stirring 14g of the prepared white wet gel, 10g of plant straw powder, 25g of fly ash, 30g of clay, 8g of zeolite powder and 10g of deionized water uniformly, granulating, drying, placing in a muffle furnace, firstly carrying out heat preservation treatment at 500 ℃ for 30min, and then carrying out heat preservation treatment at 900 ℃ for 1h to prepare mesoporous composite ceramsite;
(3) dispersing 5g of the mesoporous composite ceramsite in 80ml of toluene solvent, stirring and dispersing at 50 ℃ for 1h, adding 10ml of 3-aminopropyltriethoxysilane, continuing stirring for 2h, filtering, washing the precipitate with absolute ethyl alcohol and deionized water in sequence, and drying to obtain modified mesoporous composite ceramsite;
(4) preparing a graphene oxide dispersion liquid with the concentration of 5g/L by adopting a Hummer method; dispersing the prepared modified mesoporous composite ceramsite in deionized water to prepare a mesoporous composite ceramsite dispersion liquid with the concentration of 0.4g/ml, dropwise adding 30ml of the mesoporous composite ceramsite dispersion liquid into 10ml of graphene oxide dispersion liquid, stirring while dropwise adding, continuously stirring for 30min after dropwise adding is finished, then heating to 50 ℃, stirring for 1h, continuously dropwise adding 1ml of an ammonia water solution with the mass concentration of 20% and 1ml of hydrazine hydrate, stirring for 40min, transferring the prepared mixed solution into a high-pressure kettle, reacting for 15h at 140 ℃, cooling to room temperature after the reaction is finished, aging for 10h, filtering, precipitating, washing, and freeze-drying to obtain the nitrogen-removing water purifying agent.
The effect of the denitrification water purifier prepared by the method when used for denitrification treatment of wastewater is shown in Table 1, and the comparative examples are zeolite powder:
TABLE 1
| Specific surface area, m2/g | Ammonia nitrogen removal rate% | Nitre and nitrogen removal rate% | |
| Example 1 | 323 | 98.5 | 95.7 |
| Example 2 | 325 | 98.9 | 96.2 |
| Example 3 | 322 | 98.6 | 95.8 |
| Example 4 | 325 | 98.8 | 95.9 |
| Example 5 | 323 | 98.8 | 96.2 |
| Comparative example | 309 | 78.5 | 63.9 |
From the test results, compared with zeolite powder, the nitrogen removal water purifier prepared by the invention not only has larger specific surface area, but also can well remove ammonia nitrogen and nitrate nitrogen in wastewater.
Although specific embodiments of the invention have been described, many other forms and modifications of the invention will be apparent to those skilled in the art. It is to be understood that the appended claims and this invention generally cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.
Claims (9)
1. The preparation method of the nitrogen-removing water purifying agent is characterized by comprising the following steps:
(1) mixing cetyl trimethyl ammonium bromide and deionized water, stirring at 50-60 deg.C until solid is dissolved, then dropwise adding ammonia water solution, stirring for 10-15min, adding tetrabutyl titanate, stirring for hydrolysis, cooling to room temperature, aging for 20-24 hr, and filtering to obtain white wet gel;
(2) mixing and stirring the prepared white wet gel, plant straw powder, fly ash, clay, zeolite powder and deionized water uniformly, granulating, drying, and placing in a muffle furnace for sintering treatment to prepare mesoporous composite ceramsite;
(3) dispersing the mesoporous composite ceramsite in a toluene solvent, stirring and dispersing for 1-2h at 50-60 ℃, adding 3-aminopropyltriethoxysilane, continuing stirring for 2-3h, filtering, washing precipitates with absolute ethyl alcohol and deionized water in sequence, and drying to obtain modified mesoporous composite ceramsite;
(4) preparing a graphene oxide dispersion liquid by adopting a Hummer method; dispersing the prepared modified mesoporous composite ceramsite in deionized water to prepare mesoporous composite ceramsite dispersion, dropwise adding the mesoporous composite ceramsite dispersion into graphene oxide dispersion while stirring, continuously stirring for 30min after dropwise adding, then heating to 50-60 ℃, stirring for 1-2h, continuously dropwise adding an ammonia water solution and hydrazine hydrate, stirring for 30-50min, transferring the prepared mixed solution into a high-pressure kettle, reacting for 10-15h at 120-150 ℃, cooling to room temperature after the reaction is finished, aging for 10-15h, filtering, precipitating, washing, and freeze-drying to obtain the nitrogen-removing water purifying agent.
2. The method for preparing the water purifying agent for removing nitrogen according to claim 1, which is characterized in that: in the step (1), the mass concentration of the ammonia water solution is 20-25%.
3. The method for preparing the water purifying agent for removing nitrogen according to claim 1, which is characterized in that: in the step (1), the dosage ratio of the hexadecyl trimethyl ammonium bromide to the deionized water to the ammonia water solution to the tetrabutyl titanate is (1-3) g: 50 ml: (8-10) ml: 10 ml.
4. The method for preparing the water purifying agent for removing nitrogen according to claim 1, which is characterized in that: in the step (2), the mass ratio of the white wet gel, the plant straw powder, the fly ash, the clay, the zeolite powder and the deionized water is (10-15): 10: (20-30): 30: (5-10): 10.
5. the method for preparing the water purifying agent for removing nitrogen according to claim 1, which is characterized in that: in the step (2), the sintering treatment conditions are as follows: firstly, the heat preservation treatment is carried out for 30min at 500 ℃, and then the heat preservation treatment is carried out for 1h at 900 ℃.
6. The method for preparing the water purifying agent for removing nitrogen according to claim 1, which is characterized in that: in the step (3), the dosage ratio of the mesoporous composite ceramsite to the 3-aminopropyltriethoxysilane is (1-3) g: 5 ml.
7. The method for preparing the water purifying agent for removing nitrogen according to claim 1, which is characterized in that: in the step (4), the concentration of the graphene oxide dispersion liquid is 5 g/L; the concentration of the mesoporous composite ceramsite dispersion liquid is 0.4 g/ml.
8. The method for preparing the water purifying agent for removing nitrogen according to claim 1, which is characterized in that: in the step (4), the volume ratio of the graphene oxide dispersion liquid to the mesoporous composite ceramsite dispersion liquid to the ammonia water solution to the hydrazine hydrate is 1: (2-3): 0.1:0.1.
9. A water purifying agent for removing nitrogen, which is characterized by being prepared by the preparation method of the water purifying agent for removing nitrogen according to any one of claims 1 to 8.
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| CN117125808A (en) * | 2023-09-28 | 2023-11-28 | 青岛鑫源环保集团有限公司 | Special nitrogen-removing composite modified filler for water purification treatment and preparation method thereof |
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