CN119240891A - A slow-release phosphorus removal material and its preparation method and application - Google Patents
A slow-release phosphorus removal material and its preparation method and application Download PDFInfo
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Abstract
本申请涉及缓释除磷材料技术领域，具体公开了一种缓释除磷材料及其制备方法、应用。一种缓释除磷材料，由包含以下重量份的原料制成：无害化铝铵矾渣95‑105份；激发剂1‑3份；固化剂5‑8份；水2‑3份；其制备方法为：将无害化铝铵矾渣和激发剂进行混合研磨，得到铝基微粉；将铝基微粉与固化剂、水混合铺设于模具中，进行冷压成型得到预制胚体；对预制胚体进行热压烧结，先将温度在30min内升至300‑400℃保温4‑6min，接着在20min内升至500‑600℃保温4‑6min，冷却后脱模得到缓释除磷材料。本申请的缓释除磷材料在应用时，不仅能够形成化学除磷和物理吸附除磷的有机协同，兼具化学法和物理法的优点，还能够实现缓慢释放铝的作用，提升除磷过程铝离子的利用率以及除磷的持续性。
The present application relates to the technical field of slow-release phosphorus removal materials, and specifically discloses a slow-release phosphorus removal material and its preparation method and application. A slow-release phosphorus removal material is made of the following raw materials in parts by weight: 95-105 parts of harmless aluminum ammonium alum slag; 1-3 parts of activator; 5-8 parts of curing agent; 2-3 parts of water; its preparation method is: mixing and grinding the harmless aluminum ammonium alum slag and the activator to obtain aluminum-based micropowder; mixing the aluminum-based micropowder with the curing agent and water and laying them in a mold, cold-pressing and forming a prefabricated embryo; hot-pressing and sintering the prefabricated embryo, first raising the temperature to 300-400℃ within 30min and keeping it warm for 4-6min, then raising it to 500-600℃ within 20min and keeping it warm for 4-6min, and demolding after cooling to obtain the slow-release phosphorus removal material. When used, the slow-release phosphorus removal material of the present application can not only form an organic synergy of chemical phosphorus removal and physical adsorption phosphorus removal, combining the advantages of chemical and physical methods, but also can achieve the effect of slowly releasing aluminum, thereby improving the utilization rate of aluminum ions in the phosphorus removal process and the sustainability of phosphorus removal.
Description
Technical Field
The application relates to the technical field of sustained-release dephosphorization materials, in particular to a sustained-release dephosphorization material, a preparation method and application thereof.
Background
Eutrophication is one of the common pollution phenomena of water, and can not only affect the water quality of the water and reduce the transparency of the water, but also seriously destroy the ecological environment of the water. The main reason for eutrophication of water is the presence of excessive phosphorus in the water. The second national pollution census in 2020 indicates that the national water pollutant phosphorus discharge amount is 31.54 ten thousand tons, so that the reduction of the phosphorus concentration in the water body is one of effective means for preventing the nutrition of the water body.
At present, a series of mature phosphorus-containing sewage treatment modes represented by biological/ecological combined technology have been explored in China, but according to the operation investigation result of established sewage treatment facilities, the phenomena of low treatment efficiency of sewage treatment terminals, excessive effluent quality and the like are common due to lack of technical reserves and strict emission standards. At present, the aluminum adsorption material is widely researched for dephosphorization, and the aluminum-based compound dephosphorization has the advantages of stable water outlet, simple process flow, economy and the like.
The principle of the aluminum ammonium alum slag is that the aluminum ammonium alum slag is eluted with beryllium by deep water to obtain harmless aluminum ammonium alum slag, and the harmless aluminum ammonium alum slag is further roasted and the roasted product is acid-dissolved to prepare polyaluminium chloride for use as water purifying agent. However, when the water purifying agent material obtained by the method is used for removing phosphorus in sewage, the defects of slow generation of aluminum salt flocs, light flocs, slow sedimentation speed and the like exist. In the prior art document (CN 110304703B), nano magnesium carbonate, alumina and calcium carbonate are added to modify and calcine aluminum ash to generate a polyaluminium chloride water purifying agent product with stronger adsorption capacity and good stability, but the calcination temperature is higher than 1400 ℃, so that the energy consumption is high, and the production cost is greatly increased; the prior art document (CN 111085166B) provides a novel preparation method of a dephosphorization adsorption material, which has a very good effect on the adsorption of phosphorus, but the method adopts industrial waste gas ash and coal gangue as main raw materials, so that the recycling of the aluminum-based hazardous waste can not be realized.
Therefore, there is a need to propose a solution to the above technical problems.
Disclosure of Invention
In order to improve the utilization rate of aluminum ions in harmless aluminum ammonium alum slag, bring about a better dephosphorization effect and realize a more excellent environment-friendly effect, the application provides a slow-release dephosphorization material and a preparation method and application thereof.
In a first aspect, the application provides a sustained-release dephosphorization material, which adopts the following technical scheme:
a sustained-release dephosphorization material is prepared from the following raw materials in parts by weight:
95-105 parts of harmless aluminum ammonium alum slag;
1-3 parts of an exciting agent;
5-8 parts of curing agent;
2-3 parts of water;
the excitant is one or a combination of a plurality of silicate, aluminate or calcium salt;
The curing agent is cement ash;
And mixing the raw materials, performing cold press molding in a mold to obtain a prefabricated blank, performing hot press sintering on the prefabricated blank, firstly raising the temperature to 300-400 ℃ for 4-6min in 30min, then raising the temperature to 500-600 ℃ for 4-6min in 20min, and finally performing cooling and demoulding to obtain the slow-release dephosphorization material.
By adopting the technical scheme, the harmless aluminum ammonium alum slag is adopted as a main raw material, contains a large amount of aluminum components, has remarkable effect of removing phosphorus, and by adding the chemical exciting agent, the novel aluminum-based mineral is generated to be attached to the surface, thereby blocking the path of aluminum active ion reaction, reducing the activity of aluminum, slowing down the reaction speed quickly, realizing the effect of slowly releasing aluminum, and improving the utilization rate of aluminum ions and the persistence of phosphorus removal in the phosphorus removal process.
The slow-release dephosphorization material can be directly placed in phosphorus-containing wastewater, and surface corrosion is carried out by utilizing OH < - > or H < + > in the wastewater, so that Al in the material is released into the water to form aluminum ions, the purpose of slow-release aluminum is achieved, the aluminum ions react with phosphate radicals or hydrogen phosphate radicals to precipitate, the purpose of capturing phosphorus is achieved, and the slow-release dephosphorization material has high practicability. And after the harmless aluminum ammonium alum slag is chemically activated by an exciting agent, the aluminum ammonium alum slag is heated, bonded and shaped under the action of a curing agent to form the multi-void phosphorus capturing material which can be directly used for removing phosphorus in sewage. Therefore, when the obtained slow-release dephosphorization material is applied, the organic synergy of chemical dephosphorization and physical adsorption dephosphorization can be formed, and the slow-release dephosphorization material has the advantages of a chemical method and a physical method, thereby greatly improving the dephosphorization efficiency and simplifying the dephosphorization step.
Meanwhile, the precipitate obtained by dephosphorization contains a large amount of phosphate, mainly aluminum is released into sewage to form aluminum ions, phosphate radicals and hydrogen phosphate radicals to react chemically to form precipitate, and the phosphorus-rich precipitate is collected and reprocessed to prepare the phosphate fertilizer required by municipal garden green plants and flowers, so that the whole-flow resource closed loop of the slow-release dephosphorization material 'manufacturing-using-recycling' is realized, and the slow-release dephosphorization material is an environment-friendly slow-release dephosphorization material with strong economical efficiency and wide applicability.
Preferably, the raw materials are also added with 1-4 parts by weight of functional auxiliary agents, and the functional auxiliary agents are prepared by the following method:
S1, mixing methyltrioxysilane and tetraethoxysilane, adding dimethyldiethoxysilane and absolute ethanol solution for mixing, adding hydrochloric acid for mixing reaction, and adding ammonia water for mixing reaction to obtain functional gel;
s2, mixing basalt fibers with the functional gel obtained in the step S1, drying, and performing high-temperature treatment to obtain the functional auxiliary agent.
According to the technical scheme, in the preparation of the functional auxiliary agent, the functional gel containing the Si-O-C structure is prepared firstly, then basalt fibers are dispersed in the functional gel, holes of the functional gel are increased in size and form a structure which is adhered with the basalt fibers mutually in the high-temperature treatment process, meanwhile, the basalt fibers can change in structure at high temperature, the hole structure of the basalt fibers can be expanded into large holes, and then the large holes are matched with the change of the functional gel to form a better fit, and when the obtained functional auxiliary agent is applied to a slow-release phosphorus removing material, an excellent matching system can be formed with harmless aluminum ammonium alum slag, so that good optimization of uniform distribution of micropore structures in the slow-release phosphorus removing material is brought, and further, the slow-release phosphorus removing material is enabled to release aluminum ions in a water body slowly, the stability is better, and the overall phosphorus removing effect is remarkably enhanced.
Preferably, in step S2, the weight ratio of basalt fiber to functional gel is (0.03-0.05): 1.
Through adopting above-mentioned technical scheme, when mixing the application, the basalt fiber of above-mentioned proportion and functional gel, in the high temperature treatment in-process, the change that both take place can produce stronger suitability, and the function auxiliary agent that obtains also can be more suitable for when using with the effect combination between innocuous aluminum ammonium alum sediment, and then guarantee that the sustained release dephosphorization material that obtains has the microporous structure of uniform distribution, and use the excellent stability of sustained release chloride ion effect, the dephosphorization effect that shows is also stronger.
Preferably, in the step S2, the high temperature treatment is carried out by heating to 150-200 ℃ at 3-5 ℃ per min, keeping the temperature for 15-25min, heating to 400-450 ℃ at 2-3 ℃ per min, keeping the temperature for 25-35min, heating to 1000-1100 ℃ at 3-5 ℃ per min, and keeping the temperature for 100-120min.
Through adopting above-mentioned technical scheme, above-mentioned high temperature treatment process can make basalt fiber and function gel take place comparatively stable structural change, and guarantees that more fracture damage is difficult for appearing in the in-process, and then guarantees that the functional auxiliary agent that obtains can exert comparatively excellent stable corresponding effect in the compounding system of slowly-releasing dephosphorization material after using.
Preferably, the excitant is one or a combination of a plurality of silicate, aluminate or calcium salt;
The curing agent is cement ash.
By adopting the technical scheme, the activator and the curing agent are both suitable for preparing the slow-release dephosphorization material, and can stably play a role per se, so that the slow-release dephosphorization material with excellent and stable application quality is obtained.
In a second aspect, the application provides a preparation method of a sustained-release dephosphorization material, which adopts the following technical scheme:
the preparation method of the slow-release dephosphorization material comprises the following steps:
(1) Preparing raw materials comprising harmless aluminum ammonium alum slag, an exciting agent, a curing agent and water according to a proportion;
(2) Mixing and grinding the harmless aluminum ammonium alum slag and the exciting agent in the step (1) to obtain aluminum-based micro powder;
(3) Mixing the aluminum-based micro powder in the step (2) with a curing agent and water, paving the mixture in a mold, and performing cold press molding to obtain a prefabricated blank;
(4) And (3) performing hot-pressing sintering on the prefabricated blank in the step (3), firstly raising the temperature to 300-400 ℃ within 30min, preserving heat for 4-6min, then raising the temperature to 500-600 ℃ within 20min, preserving heat for 4-6min, cooling, and demoulding to obtain the slow-release dephosphorization material.
By adopting the technical scheme, in the operation of the preparation method, the harmless aluminum ammonium alum slag is subjected to chemical activation and then is subjected to heating adhesion molding, so that the multi-void phosphorus capturing material is formed, the whole operation is convenient, the process is simple, and the large-scale industrial production is convenient. Meanwhile, in the hot-press sintering process, the temperature and time are controlled, so that the obtained slow-release dephosphorization material has a rough outer surface and uniform micropore structure distribution, and further aluminum ions can be slowly released in a water body, and the slow-release dephosphorization material has a better dephosphorization effect. In addition, the slow-release dephosphorization material obtained by the preparation method is processed and manufactured by adopting a die, can be used by being filled into a sedimentation tank before sewage water is discharged in a modularized manner, and can be used for simply cleaning the tank or directly filling the modularized material again after the material is consumed, so that the phosphate in the sewage water is continuously removed, the operation is simple and convenient, personnel operation and management are not needed until the material is consumed, no personnel cost, no mechanical equipment cost and no power electricity consumption cost are needed.
Preferably, the particle size of the harmless aluminum ammonium alum slag is less than or equal to 6mm, and the mass ratio of the aluminum-based micro powder to the material with the particle size of less than or equal to 0.074mm is more than or equal to 90%.
By adopting the technical scheme, the particle size of the harmless aluminum ammonium alum slag can be selected so that the harmless aluminum ammonium alum slag can be quickly and fully activated in the mixing and grinding process of the exciting agent, and the particle size and the mass ratio of the obtained aluminum-based micro powder can be selected, so that the effect of excellent slow release of aluminum can be realized, a stable multi-gap structure can be formed in the subsequent processing process by mixing the aluminum-based micro powder with a curing agent and water, and finally the slow release dephosphorization material is rough in outer surface, uniform in micropore structure distribution and better in overall application quality.
Preferably, the die in the step (3) is in a cuboid grid shape, the thickness is 3-5cm, and the mesh number is more than or equal to 100 meshes.
By adopting the technical scheme, the slow-release dephosphorization material obtained by the mould with the specification can exert stable and better dephosphorization effect on phosphorus-containing sewage when in use, and the modularized slow-release dephosphorization material is obtained, is easy to fill and replace, and has better usability.
In a third aspect, the application provides an application of a slow-release dephosphorization material in sewage dephosphorization, which adopts the following technical scheme:
an application of a slow-release dephosphorization material in dephosphorization of sewage.
Preferably, the slow-release dephosphorization material is arranged in a sedimentation tank before sewage water is discharged, and is horizontally stacked in a multi-layer manner at an angle of 45 degrees along the water flow direction or is longitudinally arranged at intervals.
By adopting the technical scheme, the slow-release dephosphorization material is applied to the sewage dephosphorization, and the slow-release dephosphorization material is used in the arrangement mode, so that chemical dephosphorization and physical adsorption dephosphorization brought by the application of the slow-release dephosphorization material have better synergism, and the overall treatment effect is excellent. Meanwhile, after the modularized slow-release dephosphorization material is consumed, phosphorus-rich precipitate obtained after dephosphorization is collected and reprocessed to prepare the phosphate fertilizer required by municipal garden green plants and flowers.
In summary, the application has the following beneficial effects:
1. the application is based on the recycling of harmless aluminum ammonium alum slag, and the dried harmless aluminum ammonium alum slag is heated, adhered and shaped after chemical activation to form a multi-gap phosphorus capturing slow-release phosphorus removal material, and the slow-release aluminum release effect is achieved through the organic cooperation of chemical phosphorus removal and physical adsorption phosphorus removal, so that the utilization rate of aluminum ions and the persistence of phosphorus removal in the phosphorus removal process are improved, and further the excellent phosphorus removal effect is exerted;
2. the slow-release dephosphorization material can be used by being filled in a settling tank before sewage is discharged through modularization, and after the material is consumed, the modularized material can be simply cleaned or directly filled again, so that phosphate in the sewage is continuously removed, the operation is simple and convenient, personnel operation and management are not needed until the material is consumed, no personnel cost, no mechanical equipment cost and no power electricity consumption cost are needed;
3. After the dephosphorization of the slow-release dephosphorization material is finished, the generated phosphate precipitate can be processed into phosphate fertilizer required by municipal garden green plants and flowers again, and can be used as a seedling planting compound fertilizer after being processed as an organic fertilizer additive, the treatment route is clear, no secondary pollution is generated, and the slow-release dephosphorization material belongs to an environment-friendly functional material;
4. the special prepared functional auxiliary agent is further added to be applied to the slow-release dephosphorization material, and an excellent matching system is formed by the functional auxiliary agent and the harmless aluminum ammonium alum slag, so that good optimization of uniform micropore structure distribution in the slow-release dephosphorization material is brought, and further the slow-release dephosphorization material has better effect and stability of slowly releasing aluminum ions in a water body, and the overall dephosphorization effect is remarkably enhanced.
Drawings
FIG. 1 is a scanning electron microscope image of a slow-release dephosphorizing material obtained in example 1 and comparative example 1 of the present application;
FIG. 2 shows the change of the concentration of aluminum ions in a water body of the sustained-release dephosphorizing material obtained in example 1 and comparative example 2 of the present application.
Detailed Description
The present application will be described in further detail with reference to preparation examples, examples and comparative examples.
The raw materials used in each of the preparation examples, examples and comparative examples of the present application are commercially available except for the specific description:
the harmless aluminum ammonium alum slag is obtained by eluting beryllium from raw aluminum ammonium alum slag by deep water;
Cement ash was purchased from delphinidia cement ash 425R, a company of Shanghai Jingzhi industries, limited;
Basalt fiber was purchased from tham huge fiber limited, model xwy-16.
Examples of preparation of starting materials and/or intermediates
Preparation example 1
A functional auxiliary agent is prepared by the following method:
S1, mixing methyltrioxysilane and tetraethoxysilane, adding dimethyldiethoxysilane and absolute ethanol solution for mixing, adding hydrochloric acid for mixing reaction, and adding ammonia water for mixing reaction to obtain functional gel;
S2, mixing basalt fibers with the functional gel obtained in the step S1, drying, performing high-temperature treatment, heating to 175 ℃ at 4 ℃ per min, preserving heat for 20min, heating to 425 ℃ at 2.5 ℃ per min, preserving heat for 30min, heating to 1050 ℃ at 4 ℃ per min, and preserving heat for 110min to obtain the functional auxiliary agent.
Note that in the above operation, the weight ratio of methyltrioxysilane, tetraethyl orthosilicate and dimethyldiethoxysilane was 2:3:4, the anhydrous ethanol solution was obtained by mixing anhydrous ethanol and distilled water at a weight ratio of 4:3, the weight ratio of the anhydrous ethanol solution and dimethyldiethoxysilane was 5:2, hydrochloric acid was added to the mixed solution to pH 3, the molar ratio of ammonia water and dimethyldiethoxysilane was 1:1, and the weight ratio of basalt fiber and functional gel was 0.04:1.
Preparation example 2
A functional auxiliary agent is different from the preparation example 1 in that in the step S2, the high temperature treatment process is that the temperature is firstly increased to 150 ℃ at 3 ℃ per minute, the temperature is kept for 25min, then the temperature is increased to 400 ℃ at 2 ℃ per minute, the temperature is kept for 35min, and finally the temperature is increased to 1000 ℃ at 3 ℃ per minute, and the temperature is kept for 120min.
Preparation example 3
The functional auxiliary agent is different from the preparation example 1 in that in the step S2, the high temperature treatment process is that the temperature is firstly increased to 200 ℃ at 5 ℃ per minute, the temperature is kept for 15min, then is increased to 450 ℃ at 3 ℃ per minute, the temperature is kept for 25min, and finally is increased to 1100 ℃ at 5 ℃ per minute, and the temperature is kept for 100min.
Preparation example 4
A functional auxiliary agent is different from preparation example 1 in that the weight ratio of basalt fiber to functional gel is 0.03:1.
Preparation example 5
A functional auxiliary agent is different from preparation example 1 in that the weight ratio of basalt fiber to functional gel is 0.05:1.
Examples
Example 1
The slow release dephosphorization material is prepared from the following raw materials in parts by weight as shown in table 1:
(1) Preparing raw materials comprising harmless aluminum ammonium alum slag, an exciting agent, a curing agent and water according to a proportion;
(2) Mixing and grinding the harmless aluminum ammonium alum slag and the exciting agent in the step (1) to obtain aluminum-based micro powder;
(3) Mixing the aluminum-based micro powder in the step (2) with a curing agent and water, paving the mixture in a mold, and performing cold press molding to obtain a prefabricated blank;
(4) And (3) performing hot-pressing sintering on the prefabricated blank in the step (3), firstly heating to 350 ℃ for 5min, then heating to 550 ℃ for 15min, cooling, and demolding to obtain the slow-release dephosphorization material.
In the operation, the exciting agent is sodium silicate, the curing agent is cement ash, the particle size of the harmless aluminum ammonium alum slag is 5.5mm, the mass ratio of the aluminum-based micro powder with the particle size less than or equal to 0.074mm is 95%, the die in the step (3) is in a cuboid grid shape, the thickness is 4cm, and the mesh number is 100.
Examples 2 to 3
A sustained-release dephosphorizing material is different from example 1 in that the raw materials used for the preparation and the corresponding weights are shown in Table 1.
Table 1 raw materials and parts by weight (kg/part) for preparing the sustained-release dephosphorization materials in examples 1 to 3
Example 4
A slow-release dephosphorization material is different from the embodiment 1 in that the step (4) is specifically that the prefabricated blank in the step (3) is subjected to hot-pressing sintering, the temperature is firstly increased to 300 ℃ for 6min, then the temperature is increased to 50 ℃ for 15min, the temperature is kept for 6min, and the slow-release dephosphorization material is obtained after cooling and demoulding.
Example 5
A slow-release dephosphorization material is different from the embodiment 1 in that the step (4) is specifically that the prefabricated blank in the step (3) is subjected to hot-pressing sintering, the temperature is firstly increased to 400 ℃ for 4min, then the temperature is increased to 600 ℃ for 15min, the temperature is kept for 4min, and the slow-release dephosphorization material is obtained after cooling and demoulding.
Example 6
The slow release dephosphorization material is different from the embodiment 1 in that the die in the step (3) is in a cuboid grid shape, the thickness is 3cm, and the mesh number is 100 meshes.
Example 7
The slow release dephosphorization material is different from the embodiment 1 in that the die in the step (3) is in a cuboid grid shape, the thickness is 5cm, and the mesh number is 100 meshes.
Example 8
A slow-release dephosphorizing material is different from the embodiment 1 in that 2.5 parts by weight of functional auxiliary agent is added into the raw material, the functional auxiliary agent is obtained in the preparation embodiment 1, and the functional auxiliary agent and the curing agent are added together.
Example 9
A sustained-release dephosphorization material is different from example 8 in that the functional auxiliary agent is added in 1 part by weight.
Example 10
A sustained-release dephosphorization material is different from example 8 in that the functional auxiliary agent is added in 4 parts by weight.
Example 11
A sustained-release dephosphorizing material is different from example 8 in that a functional auxiliary agent is obtained in preparation example 2.
Example 12
A sustained-release dephosphorizing material is different from example 8 in that a functional auxiliary agent is obtained in preparation example 3.
Example 13
A sustained-release dephosphorizing material is different from example 8 in that a functional auxiliary agent is obtained in preparation example 4.
Example 14
A sustained-release dephosphorizing material is different from example 8 in that a functional auxiliary agent is obtained in preparation example 5.
Example 15
A sustained-release dephosphorizing material is different from example 8 in that the functional auxiliary agent and the like are replaced by functional gel.
Example 16
A slow-release dephosphorization material is different from the embodiment 8 in that the functional auxiliary agent is replaced by basalt fiber in equal mass.
Comparative example
Comparative example 1
A slow-release dephosphorization material is different from the embodiment 1 in that the step (4) is specifically provided, wherein the prefabricated blank in the step (3) is subjected to hot-press sintering, the temperature is raised to 550 ℃ for 5min, and the slow-release dephosphorization material is obtained after cooling and demoulding.
Comparative example 2
A sustained-release dephosphorizing material, which is different from example 1 in that it is prepared by the following steps:
(1) Preparing raw materials comprising harmless aluminum ammonium alum slag, curing agent and water according to a proportion;
(2) Mixing the harmless aluminum ammonium alum slag obtained in the step (1), a curing agent and water, paving the mixture in a mold, and performing cold press molding to obtain a prefabricated blank;
(3) And (3) carrying out hot-pressing sintering on the prefabricated blank in the step (2), firstly raising the temperature to 350 ℃ for 5min, then raising the temperature to 550 ℃ for 5min, cooling and demolding to obtain the slow-release dephosphorization material.
Application example
Application example 1
The application of the slow-release dephosphorization material in the sewage dephosphorization is that the slow-release dephosphorization material is placed in a sedimentation tank before sewage water is discharged, and is horizontally stacked in a multi-layer manner or longitudinally spaced at an angle of 45 degrees along the water flow direction, and the gap between adjacent slow-release dephosphorization materials is larger than 3cm.
Performance test
Test sample the slow release dephosphorization material obtained in example 1-16 was used as test sample 1-16, and the slow release dephosphorization material obtained in comparative example 1-2 was used as control sample 1-2.
The test method comprises the steps of loading the slow-release dephosphorization materials into a 3L reactor, placing the slow-release dephosphorization materials in the mode of application example 1, setting the gap between adjacent slow-release dephosphorization materials to be 5cm, placing three slow-release dephosphorization materials in the reactor, adding 2L of water sample to be treated, and enabling the water sample in the reactor to circularly flow through a water pump. In the above operation, the initial orthophosphate concentration of the water sample to be treated is measured first, denoted as A1, the initial orthophosphate concentration of the water sample to be treated is measured again after 7 hours of circulating flow, denoted as A2, and finally the orthophosphate removal rate is calculated. Wherein, the water sample to be treated is respectively selected from the sewage of Jiangsu Yangzhou (No. 1 sewage) and the sewage of Hunan Jiangling (No. 2 sewage), and test samples 1-16 and control samples 1-2 are sequentially used for completing the above test, and the test results are correspondingly recorded in Table 2.
TABLE 2 test results for test samples 1-16 and control samples 1-2
As can be seen from (a) in FIG. 1, the phosphorus removal slow release material obtained in the sintering step in the embodiment 1 has a rough outer surface and uniform micropore structure distribution, and the phosphorus removal slow release material obtained in the comparative embodiment 1 shown in (b) in FIG. 1, which is not subjected to heat preservation at 300-400 ℃ for 4-6min and is directly heated to the sintering temperature, has a rough outer surface, has a regular agglomeration form and does not form an effective micropore structure. Therefore, in the preparation of the phosphorus removal slow release material, the formation of the porous trapping phosphorus during the formation of the pores is controlled to play a key role.
As can be seen from fig. 2, the slow release material obtained in example 2 slowly releases aluminum ions in a water body, the slow release dephosphorization material obtained in comparative example 2 releases aluminum ions rapidly at an initial stage in the water body, the release is basically complete within 3 hours, a large amount of aluminum ions in the water body do not react with phosphorus in time, aluminum waste is caused, the service life of a material module is reduced, phosphorus is difficult to effectively remove, and out-of-standard phosphorus easily occurs.
It can be seen from the combination of examples 1-3 and comparative example 2 and the combination of table 2 that if the activator is not used, the removal rate of the orthophosphate in the sewage obtained by the above test of the slow-release dephosphorization material is obviously reduced, and the combination of fig. 2 and the above analysis shows that the use of the activator has a remarkable effect on the effective utilization of aluminum in the harmless aluminum ammonium alum slag, which can ensure that the slow-release dephosphorization material obtained by the application has the slow-release property, can also effectively utilize the harmless aluminum ammonium alum slag resource, and brings about a remarkable effect on the dephosphorization of the sewage.
By combining examples 1, 4-5 and comparative example 1 and combining table 2, it can be seen that the preformed blank in step (3) is hot pressed and sintered, the temperature is raised to 300-400 ℃ for 4-6min in 30min, then raised to 500-600 ℃ for 4-6min in 20min, the obtained slow-release dephosphorization material has rough outer surface and uniform micropore structure distribution, and further can slowly release aluminum ions in water body, thereby having better dephosphorization effect, while if the temperature is raised to sintering temperature directly without 300-400 ℃ for 4-6min in the above operation, the removal rate of the sewage orthophosphate obtained by testing the obtained slow-release dephosphorization material is obviously reduced, and then based on the analysis in combination with fig. 2, the above temperature control is proved to be particularly important for obtaining the slow-release dephosphorization material with special structure.
As can be seen from the combination of the embodiment 1 and the embodiments 6-7 and the table 2, the die in the step (3) is in a cuboid grid shape, the thickness is 3-5cm, the mesh number is more than or equal to 100 meshes, and the sustained-release dephosphorization material obtained by the die with the specification can exert a stable and better dephosphorization effect on the phosphorus-containing sewage when being applied.
As can be seen by combining example 1 and examples 8-14 and combining table 2, the application of further adding the special prepared functional auxiliary agent to the slow-release dephosphorization material can bring about further improvement of the orthophosphate removal rate of the sewage, which indicates that the slow-release dephosphorization material has better effect and stability of slowly releasing aluminum ions in the water body, and the overall dephosphorization effect is obviously enhanced. As can be seen from the combination of examples 15 to 16 and table 2, if either basalt fiber or functional gel is used alone as a functional auxiliary agent, the removal rate of orthophosphate in the sewage obtained by the test is found to be improved, but the sum of the lifting effects caused by the independent use of the basalt fiber or functional gel is far less than that of the functional auxiliary agent obtained by the compound preparation of the basalt fiber or functional gel, so that the special combination of the basalt fiber and the functional gel can bring about the remarkable lifting effect of 1+1>2, and further bring about the remarkable enhancement of the dephosphorization effect of the sewage.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (9)
1. The slow-release dephosphorization material is characterized by being prepared from the following raw materials in parts by weight:
95-105 parts of harmless aluminum ammonium alum slag;
1-3 parts of an exciting agent;
5-8 parts of curing agent;
2-3 parts of water;
the excitant is one or a combination of a plurality of silicate, aluminate or calcium salt;
The curing agent is cement ash;
And mixing the raw materials, performing cold press molding in a mold to obtain a prefabricated blank, performing hot press sintering on the prefabricated blank, firstly raising the temperature to 300-400 ℃ for 4-6min in 30min, then raising the temperature to 500-600 ℃ for 4-6min in 20min, and finally performing cooling and demoulding to obtain the slow-release dephosphorization material.
2. The sustained-release dephosphorization material according to claim 1, wherein the raw materials are further added with 1-4 parts by weight of functional auxiliary agent, and the functional auxiliary agent is prepared by the following method:
S1, mixing methyltrioxysilane and tetraethoxysilane, adding dimethyldiethoxysilane and absolute ethanol solution for mixing, adding hydrochloric acid for mixing reaction, and adding ammonia water for mixing reaction to obtain functional gel;
s2, mixing basalt fibers with the functional gel obtained in the step S1, drying, and performing high-temperature treatment to obtain the functional auxiliary agent.
3. The sustained-release dephosphorizing material according to claim 2, wherein the weight ratio of basalt fiber to functional gel in the step S2 is (0.03-0.05): 1.
4. The sustained-release dephosphorizing material according to claim 2, wherein in the step S2, the high-temperature treatment is carried out by heating to 150-200 ℃ at 3-5 ℃ per min, keeping the temperature for 15-25min, heating to 400-450 ℃ at 2-3 ℃ per min, keeping the temperature for 25-35min, heating to 1000-1100 ℃ at 3-5 ℃ per min, and keeping the temperature for 100-120min.
5. The method for preparing the sustained-release dephosphorization material as claimed in claim 1, which is characterized by comprising the following steps:
(1) Preparing raw materials comprising harmless aluminum ammonium alum slag, an exciting agent, a curing agent and water according to a proportion;
(2) Mixing and grinding the harmless aluminum ammonium alum slag and the exciting agent in the step (1) to obtain aluminum-based micro powder;
(3) Mixing the aluminum-based micro powder in the step (2) with a curing agent and water, paving the mixture in a mold, and performing cold press molding to obtain a prefabricated blank;
(4) And (3) performing hot-pressing sintering on the prefabricated blank in the step (3), firstly raising the temperature to 300-400 ℃ within 30min, preserving heat for 4-6min, then raising the temperature to 500-600 ℃ within 20min, preserving heat for 4-6min, cooling, and demoulding to obtain the slow-release dephosphorization material.
6. The method for preparing the sustained-release dephosphorization material according to claim 5, wherein the particle size of the harmless aluminum ammonium alum slag is less than or equal to 6mm, and the mass ratio of the aluminum-based micro powder with the particle size of less than or equal to 0.074mm is more than or equal to 90%.
7. The method for preparing a sustained-release dephosphorization material according to claim 5, wherein the die in the step (3) is in a rectangular grid shape, the thickness is 3-5cm, and the mesh number is more than or equal to 100 meshes.
8. The use of the slow release dephosphorization material of claim 1 in the dephosphorization of sewage.
9. The application of the slow-release dephosphorization material in the wastewater dephosphorization according to claim 8, wherein the slow-release dephosphorization material is arranged in a sedimentation tank before wastewater effluent, and is horizontally stacked in a plurality of layers or longitudinally spaced at an angle of 45 degrees along the water flow direction.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005224710A (en) * | 2004-02-13 | 2005-08-25 | Kansai Electric Power Co Inc:The | Manufacturing method of phosphorus removing water purification material, and phosphorus removing water purification material |
| RU2345834C1 (en) * | 2007-07-23 | 2009-02-10 | Государственное образовательное учреждение высшего профессионального образования "Алтайский государственный технический университет им. И.И. Ползунова" (АлтГТУ) | Method for preparation of filter-sorption material |
| JP2009189955A (en) * | 2008-02-14 | 2009-08-27 | Housetec Inc | Method for producing solid phosphorus removing agent |
| CN111377498A (en) * | 2020-03-17 | 2020-07-07 | 郑州大学 | A kind of new multifunctional composite high-efficiency phosphorus removal filler and preparation method thereof |
| CN115724525A (en) * | 2022-11-25 | 2023-03-03 | 北京师范大学 | Synchronous nitrogen and phosphorus removal slow-release filler and preparation method thereof |
| CN118459154A (en) * | 2024-04-30 | 2024-08-09 | 安徽久吾天虹环保科技有限公司 | Preparation method and application of self-active denitrification and dephosphorization functional filler |
-
2024
- 2024-12-04 CN CN202411766862.5A patent/CN119240891B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005224710A (en) * | 2004-02-13 | 2005-08-25 | Kansai Electric Power Co Inc:The | Manufacturing method of phosphorus removing water purification material, and phosphorus removing water purification material |
| RU2345834C1 (en) * | 2007-07-23 | 2009-02-10 | Государственное образовательное учреждение высшего профессионального образования "Алтайский государственный технический университет им. И.И. Ползунова" (АлтГТУ) | Method for preparation of filter-sorption material |
| JP2009189955A (en) * | 2008-02-14 | 2009-08-27 | Housetec Inc | Method for producing solid phosphorus removing agent |
| CN111377498A (en) * | 2020-03-17 | 2020-07-07 | 郑州大学 | A kind of new multifunctional composite high-efficiency phosphorus removal filler and preparation method thereof |
| CN115724525A (en) * | 2022-11-25 | 2023-03-03 | 北京师范大学 | Synchronous nitrogen and phosphorus removal slow-release filler and preparation method thereof |
| CN118459154A (en) * | 2024-04-30 | 2024-08-09 | 安徽久吾天虹环保科技有限公司 | Preparation method and application of self-active denitrification and dephosphorization functional filler |
Non-Patent Citations (2)
| Title |
|---|
| TUAN VAN TRUONG等: "Recovery of aluminum from water treatment sludge for phosphorus removal by combined calcination and extraction", JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY, vol. 103, 27 July 2021 (2021-07-27), pages 195 - 204, XP086766924, DOI: 10.1016/j.jiec.2021.07.033 * |
| 王磊;黄勇;郭召海;: "钾明矾缓释除磷剂处理分散式农村生活污水", 环境工程学报, no. 12, 5 December 2017 (2017-12-05) * |
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