CN112717878A - Substrate adsorption material with nitrogen and phosphorus removal functions and preparation method and application thereof - Google Patents
Substrate adsorption material with nitrogen and phosphorus removal functions and preparation method and application thereof Download PDFInfo
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- CN112717878A CN112717878A CN202011380294.7A CN202011380294A CN112717878A CN 112717878 A CN112717878 A CN 112717878A CN 202011380294 A CN202011380294 A CN 202011380294A CN 112717878 A CN112717878 A CN 112717878A
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- fly ash
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Abstract
The invention relates to a substrate adsorption material with nitrogen and phosphorus removal functions, a preparation method and application thereof, and belongs to the technical field of waste resource utilization. In the process of preparing the matrix adsorption material, fly ash is used as a raw material, sodium hydroxide and sodium nitrate are used as an alkali salt mixture, zeolite is prepared by an alkali fusion synthesis method, clay used as a binder, starch used as a pore-forming agent and lanthanum chloride used as a modifier are simultaneously added in the process, and finally the matrix adsorption material is prepared by one-step forming. The method is simple and easy to operate, has few process flows, and can further expand the utilization of the fly ash.
Description
Technical Field
The invention belongs to the technical field of waste resource utilization, and particularly relates to a substrate adsorption material with nitrogen and phosphorus removal functions, and a preparation method and application thereof.
Background
Coal is one of the most important fossil fuels in the world. With the development of the economy of the world and the rapid increase in energy demand, electricity generation or industrial coal combustion generates a large amount of fly ash. According to statistics, the amount of fly ash generated by coal burning in China exceeds 1 hundred million tons, and the emission amount is increased year by year. The large amount of fly ash is stockpiled, which not only occupies a large amount of land resources, but also causes dust raising, air pollution, surface water and underground water pollution and damages the ecological environment.
The fly ash mainly contains oxides rich in silicon and aluminum, the zeolite mainly contains oxides of silicon and aluminum, and the chemical components of the fly ash are similar to those of fly ash, so that the possibility of synthesizing the zeolite by the fly ash is provided, and therefore, a great deal of research is focused on the application of the fly ash synthesized zeolite as an adsorbent for removing pollutants in the environment. At present, much research is focused on modifying fly ash to synthesize zeolite for nitrogen and phosphorus removal, and the zeolite is usually synthesized by a hydrothermal reaction method or an alkali fusion method to remove ammonium, or mixed with a rare earth element lanthanum, and modified fly ash to synthesize zeolite by a solid-liquid ratio mixing method so as to improve the phosphorus removal effect of zeolite. However, the process is complicated, and the processes of pH adjustment, repeated washing, drying and the like are involved in the process, so that an adjustment control device is required to be added in practical application, water and electricity are consumed, and the cost is increased. In addition, the modification treatment of the powdery fly ash is involved, and the powdery material relates to solid-liquid separation and other technical means in practice, so that the cost of the fly ash in engineering application is increased, the popularization is difficult, and the practical application value is lacked. Therefore, a method for preparing a material with nitrogen and phosphorus removal functions by using fly ash simply and at low cost and an application thereof are urgently needed.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a substrate adsorbing material with denitrification and dephosphorization functions; the second purpose is to provide a substrate adsorbing material with the functions of denitrification and dephosphorization; the third purpose is to provide the application of the substrate adsorbing material with the nitrogen and phosphorus removal function in ecological restoration.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a preparation method of a substrate adsorption material with nitrogen and phosphorus removal functions comprises the following steps:
mixing fly ash, sodium hydroxide, sodium nitrate, clay, starch and lanthanum chloride according to the mass ratio of 2-3:1:0.7-1.5:1-1.5:1:0.5, adding water to blend into paste, then granulating to obtain ceramsite, drying the ceramsite, roasting at the temperature of 300-350 ℃ for 3-4h, and then roasting at the temperature of 500-600 ℃ for 3-4 h.
Preferably, SiO in the fly ash215-60 wt% of Al2O3The content is 5-35 wt%.
Preferably, the particle size of the fly ash is 200-300 meshes.
Preferably, the clay comprises SiO240-50 wt% of Al2O3The content is 20-30 wt%.
Preferably, the ceramsite is spherical and has the particle size of 1-5 cm.
Preferably, the drying is specifically air drying for 24-48h under natural conditions.
2. The substrate adsorption material with the nitrogen and phosphorus removal function prepared by the method.
3. The matrix adsorption material is applied to ecological restoration.
Preferably, the matrix adsorption material is applied to ecological floating islands, wetlands or grass planting ditches.
The invention has the beneficial effects that: the invention provides a substrate adsorption material with nitrogen and phosphorus removal functions and a preparation method and application thereof. The method is simple and easy to operate, has few process flows, and can further expand the utilization of the fly ash.
In the process of preparing the matrix adsorbing material, the matrix adsorbing material with excellent nitrogen and phosphorus removal functions is prepared by a one-step method by reasonably controlling the mass ratio and the calcining temperature of each raw material. Wherein, SiO in the fly ash215-60 wt% of Al2O35-35 wt% of SiO in the clay240-50 wt% of Al2O3The content is 20-30 wt%, the mass ratio of the fly ash to the clay is controlled to be 2-3:1-1.5, the content of other mineral components is also controlled under the mass ratio, in the mass ratio, the ratio of glass, silicon and aluminum required by preparing zeolite with relatively large pore diameter in the period is ensured, the cohesiveness of the finally prepared matrix adsorption material can also be ensured, and if the proportion of the clay is high, the quality of the zeolite synthesized in the period is not high; on the other hand, a low proportion of clay results in poor cohesiveness of the finally prepared matrix adsorbent, inability to be made into granular materials, and low strength.
In addition, the quality of zeolite synthesis by the molten salt method depends not only on the raw materials used but also is closely related to the type of salt mixture in the system. NaOH-NaNO in the invention3The mixture has a good promoting effect on synthesizing higher-quality zeolite, wherein sodium hydroxide serves as a mineralizer and a structure stabilizer, and sodium nitrate can serve as a solvent and a structure stabilizer like water. Further optimizing NaOH-NaNO within the mass ratio control range of the fly ash and the clay3The addition ratio has an important function for enhancing the synthesis of the zeolite. Because the whole reaction is carried out in a molten state, the water content in the reaction system is less, the migration rate of molecules is greatly limited, the zeolitization can only be carried out through sodium hydroxide in a local reaction system, and if the using amount of the sodium hydroxide is low, the decomposition of silicate and aluminosilicate is insufficient, so that the formation quality of the zeolite is influenced; on the contrary, if the amount of sodium hydroxide is higher, the sodium hydroxide will be usedAll crystalline silicates and aluminosilicates are decomposed into reactive amorphous phases, causing the newly formed zeolite to decompose. Also in the melt reaction system, the migration rate of sodium nitrate molecules is greatly limited, and if the amount of sodium nitrate is too low, the zeolite synthesis is not enhanced, while if the amount is too high, sodium nitrate does not participate in the reaction system, but the amount is increased.
Lanthanum chloride modifies zeolite synthesized in the period to improve the phosphorus removal effect, if the dosage of lanthanum chloride is too small, the loading of lanthanum chloride on the surfaces and the pore channels of zeolite and clay is too small, the phosphorus removal effect of the finally prepared substrate adsorption material is reduced, and if the dosage of lanthanum chloride is too large, the loading of lanthanum chloride on the surfaces and the pore channels of zeolite and clay is too large, so that the pore channels on the surfaces are blocked, the ammonia nitrogen enters the pore channels to generate ion exchange, and the ammonia removal effect is further influenced. By reasonably controlling the using amount of the starch, the finally prepared matrix adsorbing material can be ensured to have better porosity, and the ammonia and phosphorus adsorption effect is improved.
Finally, the calcination temperature in the first stage is controlled at 350 ℃ in the range of 300 ℃ because the silicate and aluminate which are the components of the zeolite framework are poor in solubility and lower than 300 ℃, the structures of the silicate and the aluminate are not subjected to recombination change, the framework formation of the zeolite is further influenced, and the temperature higher than 350 ℃ ensures that sodium hydroxide molecules remained outside a local reaction system are diffused and erode the newly formed zeolite framework because the added sodium hydroxide and sodium nitrate are melted into liquid.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
Preparation of substrate adsorption material with nitrogen and phosphorus removal functions
Mixing SiO215 wt% of Al2O35 wt% of fly ash with the particle size of 200-300 meshes, industrial sodium hydroxide, industrial sodium nitrate and SiO240 wt% of Al2O3Mixing clay, starch and industrial-grade lanthanum chloride with the content of 20 wt% according to the mass ratio of 2:1:0.7:1:1:0.5, adding water to blend into paste, kneading the paste by using a granulator to prepare spherical ceramsite with the particle size of 1-5cm, air-drying the spherical ceramsite for 24 hours under natural conditions, roasting the spherical ceramsite for 3 hours at 300 ℃, and roasting the roasted ceramsite for 3 hours at 500 ℃ to prepare the substrate adsorbing material with the functions of nitrogen and phosphorus removal.
And (3) adding 10g of the matrix adsorbing material into 1L of nitrogen and phosphorus solution, wherein the initial ammonia nitrogen concentration of an experiment is 5mg/L, the phosphate concentration is 5mg/L, shaking is carried out for 4 hours at room temperature, and the capacity is 0.211mg/g when the ammonia nitrogen adsorption balance is determined, and the phosphorus balance adsorption capacity is 0.245 mg/g.
Example 2
Preparation of substrate adsorption material with nitrogen and phosphorus removal functions
Mixing SiO240 wt% of Al2O320 wt% of fly ash with the particle size of 200-300 meshes, industrial sodium hydroxide, industrial sodium nitrate and SiO245 wt% of Al2O3Mixing clay, starch and industrial-grade lanthanum chloride with the content of 25 wt% according to the mass ratio of 2.5:1:1:1.3:1:0.5, adding water to blend into paste, then kneading the paste by a granulator to prepare spherical ceramsite with the particle size of 1-5cm, air-drying the spherical ceramsite for 36 hours under natural conditions, roasting the spherical ceramsite for 3.5 hours at 325 ℃, and roasting the roasted ceramsite for 3.5 hours at 550 ℃ to prepare the substrate adsorbing material with the functions of nitrogen and phosphorus removal.
And (3) adding 10g of the matrix adsorbing material into 1L of nitrogen and phosphorus solution, wherein the initial ammonia nitrogen concentration of an experiment is 5mg/L, the phosphate concentration is 5mg/L, shaking is carried out for 4 hours at room temperature, and the capacity is 0.209mg/g and the phosphorus equilibrium adsorption capacity is 0.247mg/g when ammonia nitrogen adsorption equilibrium is determined.
Example 3
Preparation of substrate adsorption material with nitrogen and phosphorus removal functions
Mixing SiO260 wt% of Al2O335 wt% of fly ash with the particle size of 200-300 meshes, industrial sodium hydroxide, industrial sodium nitrate and SiO250 wt% of Al2O3Mixing clay, starch and industrial-grade lanthanum chloride with the content of 30 wt% according to the mass ratio of 3:1:1.5:1.5:1:0.5, adding water to blend into paste, kneading the paste by using a granulator to prepare spherical ceramsite with the particle size of 1-5cm, air-drying the spherical ceramsite for 48 hours under natural conditions, roasting the spherical ceramsite for 4 hours at 350 ℃, and roasting the spherical ceramsite for 4 hours at 600 ℃ to prepare the substrate adsorbing material with the functions of nitrogen and phosphorus removal.
And (3) adding 10g of the matrix adsorbing material into 1L of nitrogen and phosphorus solution, wherein the initial ammonia nitrogen concentration of an experiment is 5mg/L, the phosphate concentration is 5mg/L, shaking is carried out for 4 hours at room temperature, and the capacity is 0.207mg/g when the ammonia nitrogen adsorption balance is determined, and the phosphorus balance adsorption capacity is 0.246 mg/g.
The matrix adsorption material can be used in ecological restoration, particularly in ecological floating islands, wetlands or grass planting ditches, wherein the matrix adsorption material is placed in the ecological floating island flowerpot, the height of the filler is 10-15cm, and the particle size is 2-3 cm; placing the artificial wetland soil layer at the lower part of the artificial wetland, wherein the height of the filler is 30-50cm, and the particle size is 3-5 cm; in order to prevent rainfall runoff from scouring, the filler is placed in a bamboo tube with a pore at the lower part and an opening at the upper part (the diameter of the bamboo tube can be selected to be 20-30cm, and the height of the bamboo tube is 20-30cm), and in practical application, the bamboo tubes can be inserted into the soil layer at the lowest part row by row, and gravels are paved at the upper part.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (9)
1. A preparation method of a substrate adsorption material with nitrogen and phosphorus removal functions is characterized by comprising the following steps:
mixing fly ash, sodium hydroxide, sodium nitrate, clay, starch and lanthanum chloride according to the mass ratio of 2-3:1:0.7-1.5:1-1.5:1:0.5, adding water to blend into paste, then granulating to obtain ceramsite, drying the ceramsite, roasting at the temperature of 300-350 ℃ for 3-4h, and then roasting at the temperature of 500-600 ℃ for 3-4 h.
2. The method of claim 1, wherein the SiO in the fly ash is215-60 wt% of Al2O3The content is 5-35 wt%.
3. The method as claimed in claim 2, wherein the particle size of the fly ash is 200-300 mesh.
4. The method of claim 1, wherein the SiO in the clay240-50 wt% of Al2O3The content is 20-30 wt%.
5. The method according to claim 1, wherein the ceramsite is spherical and has a particle size of 1-5 cm.
6. The method according to claim 1, wherein the drying is specifically air drying under natural conditions for 24-48 h.
7. The substrate adsorbing material with nitrogen and phosphorus removal functions prepared by the method of any one of claims 1-6.
8. Use of the matrix adsorbent material according to claim 7 for ecological restoration.
9. Use according to claim 8, wherein the substrate adsorbent material is used in an ecological floating island, wetland or grass planting trench.
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Cited By (2)
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| CN113893820A (en) * | 2021-10-14 | 2022-01-07 | 广东韩研活性炭科技股份有限公司 | Composite adsorption activated carbon material for fish tank and preparation method thereof |
| CN115108641A (en) * | 2022-06-29 | 2022-09-27 | 青岛农业大学 | Eutrophic river channel restoration method based on aquatic plants |
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| CN113893820A (en) * | 2021-10-14 | 2022-01-07 | 广东韩研活性炭科技股份有限公司 | Composite adsorption activated carbon material for fish tank and preparation method thereof |
| CN115108641A (en) * | 2022-06-29 | 2022-09-27 | 青岛农业大学 | Eutrophic river channel restoration method based on aquatic plants |
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