CN114315293A - Nitrogen and phosphorus removal baking-free ceramsite and preparation method and application thereof - Google Patents
Nitrogen and phosphorus removal baking-free ceramsite and preparation method and application thereof Download PDFInfo
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- CN114315293A CN114315293A CN202210018307.9A CN202210018307A CN114315293A CN 114315293 A CN114315293 A CN 114315293A CN 202210018307 A CN202210018307 A CN 202210018307A CN 114315293 A CN114315293 A CN 114315293A
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to the technical field of water treatment, and particularly discloses nitrogen and phosphorus removal unfired ceramsite and a preparation method and application thereof. The nitrogen and phosphorus removal baking-free ceramsite comprises the following components in percentage by mass: 65-75% of rare earth modified fly ash, 5-15% of modified corncob, 1-5% of pore-forming agent and 10-20% of cement-based binder. According to the invention, the rare earth modified fly ash is selected as a main raw material, so that anions in sewage can be effectively adsorbed, and the phosphorus removal effect of the unfired ceramsite is obviously enhanced; meanwhile, the high molecular polymer coated modified corncob is added to serve as a slow-release carbon source, the denitrification effect of microorganisms is enhanced, the corncob can also serve as a fiber reinforced material to inhibit cracking and shrinkage of the non-sintered ceramsite, the overall strength and durability of the non-sintered ceramsite are improved, the corncob is used as a filter material of a denitrification filter, the effects of releasing the carbon source to enhance denitrification and adsorption dephosphorization can be achieved at the same time, and the corncob has high popularization and application values.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to nitrogen and phosphorus removal unfired ceramsite and a preparation method and application thereof.
Background
The domestic sewage treatment in rural areas plays an important role in the construction of new rural areas, and the conventional treatment process is generally a sewage treatment process of a septic tank, such as a Sequencing Batch Reactor (SBR), a continuous flow nitrification and denitrification reactor (A/O) or a contact oxidation reactor. In recent years, with the change of dietary consumption structures of people, the concentration of nitrogen-containing pollutants in domestic sewage is higher and higher, and due to the fact that a large amount of low-concentration raw water such as vegetable washing water and bath water is mixed into the domestic sewage, the carbon source in the domestic sewage is insufficient, and therefore rural domestic sewage tends to have the characteristics of high nitrogen and low carbon. In view of the above problems, denitrification processes represented by denitrification filters are increasing at the end of the existing conventional biochemical treatment. However, the process needs additional equipment investment, and the propagation of the microorganisms is easily limited by a carbon source deficiency and a plurality of factors such as temperature, residence time, pH and the like, the treatment stability is poor, and the practical application is greatly limited.
The adsorption method has the advantages of small occupied area, simple process, stable effect, small amount of sludge produced, convenient operation and the like, and is widely concerned by people. In the prior art, the method for preparing the non-sintered ceramsite by adopting the raw materials such as the fly ash and the like is available, but when the non-sintered ceramsite prepared by taking the fly ash as the raw material is used for treating high-nitrogen low-carbon domestic sewage, the treatment effect is not ideal. Therefore, there is a need to develop a non-sintered ceramsite with excellent treatment effect on high-nitrogen low-carbon domestic sewage, which has an extremely important significance on rural domestic sewage treatment and social and economic sustainable development requirements.
Disclosure of Invention
In view of the above, the invention provides a nitrogen and phosphorus removal baking-free ceramsite and a preparation method and application thereof. The invention takes rare earth modified fly ash as a main raw material, adds modified corncobs as a slow-release carbon source, and simultaneously adds a binder and a pore-forming agent as auxiliary agents to prepare the baking-free ceramsite which is used as a filter material of a denitrification filter tank, and can synchronously realize the effects of carbon release and nitrogen removal and adsorption and phosphorus removal.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the nitrogen and phosphorus removal baking-free ceramsite comprises the following components in percentage by mass: 65-75% of rare earth modified fly ash, 5-15% of modified corncob, 1-5% of pore-forming agent and 10-20% of cement-based binder;
wherein the modified corncob comprises corncob particles and a high polymer layer coated outside the corncob particles; the material of the high polymer layer is at least one of polyether, polysulfone or polyvinylidene chloride.
Compared with the prior art, the rare earth modified fly ash is selected as the main raw material, so that anions in sewage can be effectively adsorbed, and the phosphorus removal effect of the non-sintered ceramsite is obviously enhanced; meanwhile, the high molecular polymer coated modified corncobs are added as a slow-release carbon source, so that a stable carbon source can be provided for the denitrification reaction of sewage in the denitrification filter, the denitrification effect of microorganisms is enhanced, the corncobs can be used as a fiber reinforced material to inhibit the cracking and shrinkage of a cement-based binder, and the overall strength and durability of the unfired ceramsite are improved.
The non-sintered ceramsite provided by the invention takes industrial waste and agricultural waste as raw materials, has wide sources and low price, has strong adsorption effect, can be used as a filter material of a denitrification filter tank, can simultaneously achieve the effects of releasing a carbon source, strengthening denitrification and adsorption dephosphorization, does not need to additionally arrange a chemical dephosphorization device at the tail end of the denitrification filter tank, can achieve the high-efficiency removal of nitrogen and phosphorus in domestic sewage by only periodically replacing the filter material, realizes the resource utilization of the waste, is economic and high-efficiency, and has high practical application value.
Preferably, the preparation method of the modified corncob comprises the following steps:
step a, drying and crushing corncobs to obtain corncob particles;
and b, adding the corncob particles and the high molecular polymer into an organic solvent, uniformly mixing, preserving the heat for 12-24 h at the temperature of 60-90 ℃, then transferring into a mold for molding, washing, drying, freezing and crushing to obtain the modified corncob.
Polyether, polysulfone and polyvinylidene fluoride are selected as high polymer molecules to coat corncob particles as a slow-release carbon source, so that the prepared carbon source structure is more stable, a layer of blended embedding material is coated on the surface of a denitrification carbon source layer, the denitrification carbon source is slowly released through micropores and gaps of the coating, the release rate of the carbon source is controlled, the carbon source is utilized by microorganisms, a long-acting stable carbon source is provided for denitrification reaction, the released carbon source is more easily utilized by the microorganisms, the utilization rate and the denitrification efficiency of the denitrification carbon source are improved, the coated carbon source is more easily and uniformly mixed with other materials after being frozen and crushed, and the uniformity of components of the baking-free ceramsite is improved; the components are mutually cooperated, so that the prepared non-sintered ceramsite has the characteristics of large specific surface area, porosity, looseness and high strength, and meets the use requirements of domestic sewage treatment.
Preferably, in the step a, the fineness of the corn cob particles is less than or equal to 500 meshes.
Preferably, in step b, the organic solvent is one or both of dimethylformamide and dimethylacetamide.
Further preferably, in step b, the organic solvent is added in an amount to control the viscosity of the dissolved system to be 500 to 3000mPas, so as to facilitate the subsequent formation of a film-shaped material in the mold.
Preferably, in the step b, the mass ratio of the corncob particles to the high molecular polymer is 1: 1-1: 3.
Preferably, in the step b, the fineness of the frozen and crushed material is 300 to 700 meshes.
In the step b, for example, the washing is performed by soaking and washing with deionized water, and the soaking and washing time is 48-60 hours.
In the step b, the drying is performed in a vacuum drying manner, and the drying temperature is 60 ℃ to 80 ℃.
In the step b, the freezing and crushing are carried out by a freezing and crushing machine, the temperature of the freezing and crushing is controlled to be-15 ℃ to-5 ℃, and the freezing medium is one or two of ethylene glycol or glycerol.
Preferably, the preparation method of the rare earth modified fly ash comprises the following steps: adding the fly ash into a rare earth salt solution with the mass concentration of 0.2-0.5%, dipping for 12-24 h, and drying to obtain the rare earth modified fly ash.
Further preferably, the rare earth salt solution is at least one of a cerium sulfate solution, a cerium chloride solution or an iron chloride solution.
Preferably, the impregnation temperature is 20 ℃ to 30 ℃.
The rare earth metal ions are adopted to perform impregnation modification on the fly ash, so that the positive electricity of the surface of the fly ash is increased, the anions in sewage are effectively adsorbed, and the phosphorus removal capability is improved.
Preferably, the fineness of the rare earth modified fly ash is less than or equal to 40 meshes.
Preferably, the pore-forming agent is at least one of gelatin, bone glue or hide glue.
The optimized pore-forming agent can form developed open pore channels in the ceramsite, and the specific surface area of the material is increased, so that the adsorption effect on nitrogen and phosphorus organic matters is enhanced.
Preferably, the cement-based binder is light mullite, mullite hollow spheres, high bauxite and calcium aluminate cement in a mass ratio of 1: 0.8-1.0: 1.0-1.1: 0.5.
The light mullite Al2O333 to 35 percent of Fe2O3Content is less than or equal to 0.80 percent, K2O+Na2The O content is less than or equal to 0.80 percent, and the fineness is 150-320 meshes.
The mullite hollow sphere Al2O360-65% of Fe2O3Content is less than or equal to 1.50 percent, K2O+Na2The O content is less than or equal to 0.50 percent, and the fineness is 100-150 meshes.
The high alumina bauxite Al2O3The content is 55 to 61 percent, and SiO is2The content is less than or equal to 25 percent, and the fineness is 100-150 meshes.
The calcium aluminate cement Al2O3The content is more than or equal to 69 percent, the CaO content is less than or equal to 30 percent, and the specific surface area is not less than 300m2/kg。
The optimized binder can effectively bind all the components, is favorable for blank forming, can destroy the proportional body structure of the fly ash, increases the specific surface area of the ceramsite, and can improve the activity of the fly ash, thereby effectively improving the adsorption performance of the ceramsite.
The invention also provides a preparation method of the nitrogen and phosphorus removal baking-free ceramsite, which comprises the following steps:
weighing the components according to the design ratio, adding the weighed components into water, uniformly mixing, adding into a granulator to prepare a blank with the diameter of 4-6 mm, and then aging, drying and steam maintaining the blank to obtain the nitrogen and phosphorus removal burning-free ceramsite.
The preparation method of the nitrogen and phosphorus removal baking-free ceramsite provided by the invention has the advantages of rough surface, high film forming speed, large specific surface area, large adsorption capacity and porosity, excellent adsorption and phosphorus removal and nitrogen removal effects, simple preparation process, convenience in operation and low cost, and is suitable for industrial scale production and application.
Preferably, the adding amount of the water is 8-12% of the total mass of the unfired ceramsite raw material.
Preferably, the aging temperature is 20-30 ℃, and the aging time is 12-24 h.
Preferably, the steam maintenance temperature is 95-100 ℃, and the time is 12-15 h.
Illustratively, steam maintenance is performed using a pressurized steam sterilizer.
The invention also provides application of the nitrogen and phosphorus removal baking-free ceramsite in domestic sewage treatment.
The nitrogen and phosphorus removal non-sintered ceramsite prepared by the invention can be used as a filter material of a denitrification filter tank, can be combined with filter bed materials such as pebbles, quartz sand and the like, can be directly used as a filler for water body restoration, can be directly added into a river channel, has low preparation cost, does not need high-temperature sintering, and has wide application prospect.
Drawings
FIG. 1 is a graph showing the variation curve of total nitrogen and total amount of inlet and outlet water when the non-sintered ceramsite prepared in example 1 of the present invention is applied to a denitrification filter.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
The fly ash used in the following examples is produced by Jiangsu Wuxi certain thermal power plant.
Example 1
The embodiment of the invention provides nitrogen and phosphorus removal baking-free ceramsite which comprises the following components in percentage by mass: 70% of rare earth modified fly ash, 15% of modified corncob, 2% of gelatin and 13% of cement-based binder;
wherein the cement-based binder is light mullite, mullite hollow spheres, high bauxite and calcium aluminate cement in a mass ratio of 1:0.8:1: 0.5.
The light mullite Al2O333 to 35 percent of Fe2O3Content is less than or equal to 0.80 percent, K2O+Na2The O content is less than or equal to 0.80 percent, and the fineness is 150-320 meshes.
The mullite hollow sphere Al2O360-65% of Fe2O3Content is less than or equal to 1.50 percent, K2O+Na2The O content is less than or equal to 0.50 percent, and the fineness is 100-150 meshes.
The high alumina bauxite Al2O3The content is 55 to 61 percent, and SiO is2The content is less than or equal to 25 percent, and the fineness is 100-150 meshes.
The calcium aluminate cement Al2O3The content is more than or equal to 69 percent, the CaO content is less than or equal to 30 percent, and the specific surface area is not less than 300m2/kg。
The preparation method of the nitrogen and phosphorus removal baking-free ceramsite specifically comprises the following steps:
(1) preparing rare earth modified fly ash:
sieving fly ash collected by an electricity factory with a 40-mesh sieve, weighing 130g of the sieved fly ash, adding the weighed fly ash into a cerium sulfate solution with the mass concentration of 0.3%, soaking for 18h at 20 ℃, and drying in a 105 ℃ oven to obtain the rare earth modified fly ash.
(2) Preparing modified corncobs:
taking corncobs collected in rural areas, drying and crushing the corncobs, sieving the corncobs by a 500-mesh sieve, taking 30g of sieved corncob particles and 30g of polysulfone, adding the corncob particles and the polysulfone into 100mL of dimethylformamide, heating the obtained mixture in a water bath at 80 ℃ for 12h, detecting the liquid viscosity to be 1500mPas, pouring the liquid into a sheet mold to form a sheet film, soaking and washing the sheet film by deionized water for 48h, drying the sheet film in a vacuum oven at 60 ℃, putting the dried sheet film into a freezing crusher for crushing, and obtaining the modified corncobs with the granularity of 700 meshes at the temperature of freezing and crushing, wherein the temperature of the freezing and crushing is-15 ℃.
(3) Preparing baking-free ceramsite:
weighing the rare earth modified fly ash, the modified corncobs, the pore-forming agent and the cement-based binder according to the proportion, adding water accounting for 10 percent of the total mass of the non-sintered ceramsite, uniformly mixing, balling the uniformly mixed materials by using a disk granulator, wherein the diameter of the balling is 5mm, aging the molded spheres for 12 hours at room temperature, drying the spheres in an oven at 105 ℃ for 2 hours, finally transferring the spheres into a pressure steam sterilizer, and preserving heat at 100 ℃ for 12 hours to obtain the non-sintered ceramsite for removing nitrogen and phosphorus.
Example 2
The embodiment of the invention provides nitrogen and phosphorus removal baking-free ceramsite which comprises the following components in percentage by mass: 65% of rare earth modified fly ash, 14% of modified corncob, 1% of sheath rubber and 20% of cement-based binder;
wherein the cement-based binder is light mullite, mullite hollow spheres, high bauxite and calcium aluminate cement in a mass ratio of 1:0.9:1.1: 0.5.
The light mullite Al2O333 to 35 percent of Fe2O3Content is less than or equal to 0.80 percent, K2O+Na2The O content is less than or equal to 0.80 percent, and the fineness is 150-320 meshes.
The mullite hollow sphere Al2O360-65% of Fe2O3Content is less than or equal to 1.50 percent, K2O+Na2The O content is less than or equal to 0.50 percent, and the fineness is 100-150 meshes.
The high alumina bauxite Al2O3The content is 55 to 61 percent, and SiO is2The content is less than or equal to 25 percent, and the fineness is 100-150 meshes.
The calcium aluminate cement Al2O3The content is more than or equal to 69 percent, the CaO content is less than or equal to 30 percent, and the specific surface area is not less than 300m2/kg。
The preparation method of the nitrogen and phosphorus removal baking-free ceramsite specifically comprises the following steps:
(1) preparing rare earth modified fly ash:
sieving fly ash collected by an electricity factory with a 40-mesh sieve, weighing 130g of the sieved fly ash, adding the weighed fly ash into a cerium chloride solution with the mass concentration of 0.2%, soaking for 12h at 28 ℃, and drying in a 105 ℃ oven to obtain the rare earth modified fly ash.
(2) Preparing modified corncobs:
taking corncobs collected in rural areas, drying and crushing the corncobs, sieving the corncobs by a 500-mesh sieve, taking 30g of sieved corncob particles and 60g of polyether, adding the corncob particles and the polyether into 60mL of dimethylformamide, heating the obtained mixture in 70 ℃ water bath for 20h, detecting the liquid viscosity to be 2000mPas, then pouring the liquid into a sheet-shaped mould to form a sheet-shaped film, soaking and washing the sheet-shaped film by deionized water for 48h, drying the obtained product in a vacuum oven at 60 ℃, putting the dried product into a freezing crusher for crushing, and obtaining the modified corncobs with the granularity of 500 meshes at the temperature of-10 ℃ after freezing and crushing.
(3) Preparing baking-free ceramsite:
weighing the rare earth modified fly ash, the modified corncobs, the pore-forming agent and the cement-based binder according to the proportion, adding water accounting for 8 percent of the total mass of the non-sintered ceramsite, uniformly mixing, balling the uniformly mixed materials by using a disk granulator, wherein the diameter of the balling is 5mm, aging the molded spheres for 16h at room temperature, drying the spheres in an oven at 105 ℃ for 2h, finally transferring the spheres into a pressure steam sterilizer, and preserving heat at 100 ℃ for 14h to obtain the non-sintered ceramsite for removing nitrogen and phosphorus.
Example 3
The embodiment of the invention provides nitrogen and phosphorus removal baking-free ceramsite which comprises the following components in percentage by mass: 75% of rare earth modified fly ash, 5% of modified corncob, 5% of gelatin and 15% of cement-based binder;
wherein the cement-based binder is light mullite, mullite hollow spheres, high bauxite and calcium aluminate cement in a mass ratio of 1:1:1: 0.5.
The light mullite Al2O333 to 35 percent of Fe2O3Content is less than or equal to 0.80 percent, K2O+Na2The O content is less than or equal to 0.80 percent, and the fineness is 150-320 meshes.
The mullite hollow sphere Al2O360-65% of Fe2O3Content is less than or equal to 1.50 percent, K2O+Na2The O content is less than or equal to 0.50 percent, and the fineness is 100-150 meshes.
The high alumina bauxite Al2O3The content is 55 to 61 percent, and SiO is2The content is less than or equal to 25 percent, and the fineness is 100-150 meshes.
The calcium aluminate cement Al2O3The content is more than or equal to 69 percent, and the content of CaO is less than or equal to 30 percentSpecific surface area of not less than 300m2/kg。
The preparation method of the nitrogen and phosphorus removal baking-free ceramsite specifically comprises the following steps:
(1) preparing rare earth modified fly ash:
sieving fly ash collected by an electricity factory with a 40-mesh sieve, weighing 130g of the sieved fly ash, adding the weighed fly ash into a ferric chloride solution with the mass concentration of 0.4%, soaking for 24h at 25 ℃, and drying in an oven at 105 ℃ to obtain the rare earth modified fly ash.
(2) Preparing modified corncobs:
taking corncobs collected in rural areas, drying and crushing the corncobs, sieving the corncobs by a 500-mesh sieve, taking 30g of sieved corncob particles and 90g of polyvinylidene chloride, adding the corncob particles and the polyvinylidene chloride into 100mL of dimethylformamide, heating the mixture in a 60 ℃ water bath for 24h, detecting the liquid viscosity to be 500mPas, pouring the liquid into a sheet mold to form a sheet film, soaking and washing the sheet film by deionized water for 60h, drying the water in a 80 ℃ vacuum oven, putting the sheet film into a freezing crusher for crushing, and obtaining the modified corncobs with the granularity of 600 meshes at the temperature of freezing and crushing of-15 ℃.
(3) Preparing baking-free ceramsite:
weighing the rare earth modified fly ash, the modified corncobs, the pore-forming agent and the cement-based binder according to the proportion, adding water accounting for 12% of the total mass of the non-sintered ceramsite, uniformly mixing, balling the uniformly mixed materials by using a disk granulator, wherein the diameter of the balling is 5mm, aging the molded spheres for 20h at room temperature, drying the spheres in an oven at 105 ℃ for 2h, finally transferring the spheres into a pressure steam sterilizer, and preserving heat at 100 ℃ for 13h to obtain the non-sintered ceramsite for removing nitrogen and phosphorus.
Example 4
The embodiment of the invention provides nitrogen and phosphorus removal baking-free ceramsite which comprises the following components in percentage by mass: 74% of rare earth modified fly ash, 13% of modified corncob, 3% of bone glue and 10% of cement-based binder;
wherein the cement-based binder is light mullite, mullite hollow spheres, high bauxite and calcium aluminate cement in a mass ratio of 1:1.0:1.1: 0.5.
The light mullite Al2O333 to 35 percent of Fe2O3Content is less than or equal to 0.80 percent, K2O+Na2The O content is less than or equal to 0.80 percent, and the fineness is 150-320 meshes.
The mullite hollow sphere Al2O360-65% of Fe2O3Content is less than or equal to 1.50 percent, K2O+Na2The O content is less than or equal to 0.50 percent, and the fineness is 100-150 meshes.
The high alumina bauxite Al2O3The content is 55 to 61 percent, and SiO is2The content is less than or equal to 25 percent, and the fineness is 100-150 meshes.
The calcium aluminate cement Al2O3The content is more than or equal to 69 percent, the CaO content is less than or equal to 30 percent, and the specific surface area is not less than 300m2/kg。
The preparation method of the nitrogen and phosphorus removal baking-free ceramsite specifically comprises the following steps:
(1) preparing rare earth modified fly ash:
sieving fly ash collected by an electricity factory with a 40-mesh sieve, weighing 130g of the sieved fly ash, adding the weighed fly ash into a cerium sulfate solution with the mass concentration of 0.5%, soaking for 16h at 30 ℃, and drying in a 105 ℃ oven to obtain the rare earth modified fly ash.
(2) Preparing modified corncobs:
taking corncobs collected in rural areas, drying and crushing the corncobs, sieving the corncobs by a 500-mesh sieve, taking 30g of sieved corncob particles and 75g of polysulfone, adding the corncob particles and the polysulfone into 30mL of dimethylacetamide, heating the corncob particles in a 90 ℃ water bath for 12h, detecting the liquid viscosity to be 3000mPas, pouring the liquid into a sheet-shaped mold to form a sheet-shaped film, soaking and washing the sheet-shaped film for 55h by deionized water, drying the water in a 70 ℃ vacuum oven, and crushing the sheet-shaped film in a freezing crusher at the temperature of-5 ℃ to obtain the modified corncobs with the granularity of 300 meshes.
(3) Preparing baking-free ceramsite:
weighing the rare earth modified fly ash, the modified corncobs, the pore-forming agent and the cement-based binder according to the proportion, adding water accounting for 9% of the total mass of the non-sintered ceramsite, uniformly mixing, balling the uniformly mixed materials by using a disk granulator, wherein the diameter of the balling is 5mm, aging the molded spheres for 24h at room temperature, drying the spheres in an oven at 105 ℃ for 2h, finally transferring the spheres into a pressure steam sterilizer, and keeping the temperature at 100 ℃ for 15h to obtain the non-sintered ceramsite for removing nitrogen and phosphorus.
The non-sintered ceramsite prepared in example 1 is taken to test that the specific surface area of the non-sintered ceramsite is 7.5m2The specific surface area is much higher than that of artificial ceramsite filter material for water treatment (CJT299-2008) by 0.5m2(ii) in terms of/g. The sum of the crushing rate and the wear rate of the baking-free ceramsite prepared according to the CJT299-2008 standard test<4%, hydrochloric acid solubility of 1.55% and porosity of 41.23%.
The unburned ceramsite prepared in example 1 is applied to a filler of a denitrification filter to test the removal effect of nitrogen and phosphorus. The operating conditions of the denitrification filter tank are as follows: a cylindrical organic glass reactor with the diameter of 0.1m is adopted, pebbles with the height of 0.3m are paved on the lower layer to serve as a bearing layer, the specification of the pebbles is 16-25mm, the non-fired ceramsite prepared in the embodiment 1 is paved on the upper layer of the pebbles, and the filling height is 2 m. The daily treated water amount is 0.8m3The empty bed hydraulic retention time of the filter is 28 min. The water was run for 50 days under the above conditions and the total nitrogen and total phosphorus content of the inlet and outlet water was monitored weekly. The graph of the change of total nitrogen and total amount of inlet and outlet water is shown in figure 1.
As can be seen from the figure 1, under the above operating conditions, when the total nitrogen of the inlet water of the denitrification filter is 20-30 mg/L, the total nitrogen of the outlet water is basically controlled below 15 mg/L; when the average value of the total phosphorus of the inlet water is 1.1mg/L, the average value of the total phosphorus of the outlet water is 0.42mg/L, and the average value of the total phosphorus of the outlet water reaches the limit value requirement of the first class A. And the operation reaches about 50 days, and the reduction of the total nitrogen removal efficiency of the effluent is not obvious, so that the baking-free ceramsite prepared in the embodiment 1 of the invention has better capability of releasing a carbon source for a long time.
The non-sintered ceramsite prepared in the examples 2 to 4 can achieve the technical effects of nitrogen and phosphorus removal basically equivalent to those of the ceramsite prepared in the example 1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The nitrogen and phosphorus removal baking-free ceramsite is characterized by comprising the following components in percentage by mass: 65-75% of rare earth modified fly ash, 5-15% of modified corncob, 1-5% of pore-forming agent and 10-20% of cement-based binder;
wherein the modified corncob comprises corncob particles and a high polymer layer coated outside the corncob particles; the material of the high polymer layer is at least one of polyether, polysulfone or polyvinylidene chloride.
2. The nitrogen and phosphorus removal baking-free ceramsite of claim 1, wherein the preparation method of the modified corncob comprises the following steps:
step a, drying and crushing corncobs to obtain corncob particles;
and b, adding the corncob particles and the high molecular polymer into an organic solvent, uniformly mixing, preserving the heat for 12-24 h at the temperature of 60-90 ℃, then transferring into a mold for molding, washing, drying, freezing and crushing to obtain the modified corncob.
3. The nitrogen and phosphorus removal baking-free ceramsite of claim 2, wherein in the step a, the fineness of the corncob particles is less than or equal to 500 meshes; and/or
In the step b, the mass ratio of the corncob particles to the high molecular polymer is 1: 1-1: 3; and/or
In the step b, the fineness of the frozen and crushed material is 300-700 meshes.
4. The nitrogen and phosphorus removal baking-free ceramsite of claim 1, wherein the preparation method of the rare earth modified fly ash comprises the following steps: adding the fly ash into a rare earth salt solution with the mass concentration of 0.2-0.5%, dipping for 12-24 h, and drying to obtain the rare earth modified fly ash.
5. The nitrogen and phosphorus removal unfired ceramsite of claim 4, wherein the rare earth salt solution is at least one of a cerium sulfate solution, a cerium chloride solution or an iron chloride solution.
6. The nitrogen and phosphorus removal baking-free ceramsite of claim 1, wherein the pore-forming agent is at least one of gelatin, bone glue or hide glue; and/or
The cement-based binder is light mullite, mullite hollow spheres, high bauxite and calcium aluminate cement in a mass ratio of 1: 0.8-1.0: 1.0-1.1: 0.5.
7. The preparation method of the nitrogen and phosphorus removal baking-free ceramsite according to any one of claims 1-6, which is characterized by comprising the following steps:
weighing the components according to the design ratio, adding the weighed components into water, uniformly mixing, adding into a granulator to prepare a blank with the diameter of 4-6 mm, and then aging, drying and steam maintaining the blank to obtain the nitrogen and phosphorus removal burning-free ceramsite.
8. The method for preparing nitrogen and phosphorus removal baking-free ceramsite of claim 7, wherein the aging temperature is 20-30 ℃, and the aging time is 12-24 h.
9. The method for preparing baking-free ceramsite for nitrogen and phosphorus removal as defined in claim 7, wherein the temperature for steam maintenance is 95-100 ℃ for 12-15 h.
10. The application of the nitrogen and phosphorus removal baking-free ceramsite of any one of claims 1-6 in domestic sewage treatment.
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| CN116102359A (en) * | 2023-04-14 | 2023-05-12 | 元素科技服务(沧州)有限公司 | Lightweight high-strength ceramsite and preparation method thereof |
| CN117229078A (en) * | 2023-11-13 | 2023-12-15 | 天津包钢稀土研究院有限责任公司 | Method for reducing sintering temperature of high-refractoriness ceramsite by utilizing rare earth oxide |
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