CN111377498A - Multifunctional novel composite efficient phosphorus removal filler and preparation method thereof - Google Patents
Multifunctional novel composite efficient phosphorus removal filler and preparation method thereof Download PDFInfo
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- CN111377498A CN111377498A CN202010184758.0A CN202010184758A CN111377498A CN 111377498 A CN111377498 A CN 111377498A CN 202010184758 A CN202010184758 A CN 202010184758A CN 111377498 A CN111377498 A CN 111377498A
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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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Abstract
The invention discloses a multifunctional novel composite efficient phosphorus removal filler which comprises, by weight, 30-50 parts of slag portland cement, 40-60 parts of PAC residues, 7-9 parts of bentonite, 1-2 parts of a slow-release carbon source and a weight ratio of a solid raw material to water of 1: 0.4-0.7. Simultaneously discloses a preparation method of the dephosphorization filler. The dephosphorization filler of the invention takes the portland slag cement as the adhesive, and the portland slag cement and the bentonite as the PAC residue dephosphorization reinforcer, and the dephosphorization filler has the function of synchronously slowly releasing the carbon source while efficiently dephosphorizing. The multifunctional novel composite efficient phosphorus removal filler prepared by the invention has the advantages of strong phosphorus adsorption capacity, good removal rate and high adsorption capacity, and can greatly improve the problems of poor biodegradability of a water body, insufficient denitrification carbon source and the like.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a multifunctional novel composite efficient phosphorus removal filler and a preparation method thereof.
Background
In recent years, with the rapid development of economy in China, water pollution is increasingly severe, and according to the report of Chinese environmental condition bulletin of 2017 of the national ministry of ecological environment, although the total phosphorus concentration of surface water in China is reduced by 11.5% in proportion, the proportion of an overproof section is 19.1%, and the overproof section exceeds chemical oxygen demand and ammonia nitrogen, so that the water pollution becomes a main pollutant influencing the water quality of the surface water in China. This indicates that water eutrophication, especially phosphorus removal in water, is a major problem to be solved urgently.
At present, the common phosphorus removal method at home and abroad comprises the following steps: chemical, biological, and adsorption methods, etc. Although the chemical method has the advantages of stable operation, simple process, good phosphorus removal efficiency and high removal rate of 75-85%, the investment cost is high, the pH value of the wastewater is increased due to the addition of chemical agents, a large amount of chemical sludge is generated, and secondary pollution is easy to occur. The biological method has low investment cost, can remove organic matters while removing phosphorus, has the removal rate of up to 90 percent, is easily influenced by pH and temperature greatly, has poor stability, ensures that phosphorus absorbed and utilized by microorganisms is always in the dynamic change process of continuous absorption and release, and ensures that almost all phosphorus forming the cell bodies of the microorganisms is quickly decomposed and released after the microorganisms die and then returns to the water body again. The adsorption method is to utilize the larger specific surface area and more pores of the adsorbent to make phosphorus physically adsorbed, surface precipitated or ion exchanged on the surface of the adsorbent, thereby realizing phosphorus separation. The adsorption method has stable dephosphorization effect, is widely applied to wastewater dephosphorization, the selection of the adsorbent is the key of the adsorption method, and the fly ash, the feed water sludge, the activated carbon, the zeolite, the medical stone and the modified or synthesized material are the most widely applied adsorbents.
Currently, the coagulants most widely applied in China are aluminum salts and iron salts, wherein polyaluminium chloride (PAC) has the characteristics of high adsorption activity, short sediment clarification time, wide application range, no influence of water temperature and the like, and is widely applied. The total production amount of the Chinese polyaluminium chloride in 2016 reaches 140.3 ten thousand tons, and at present, the main production process of the domestic polyaluminium chloride uses aluminum hydroxide and water treatment agent and uses calcium aluminate as raw materials, wherein the calcium aluminate powder can generate at least 15 percent (calculated by absolute dryness) of filter pressing residue (PACR) in the production process. Although the part of residue is regarded as general solid waste in management, the part of residue still needs landfill treatment in general, and a large amount of land resources are occupied, and the treatment of PAC residue becomes a burden of production enterprises along with the improvement of environmental awareness of people and the continuous expansion of coagulant industry. Therefore, a novel environment-friendly treatment mode is sought, waste residues are effectively treated, the PAC residues are recycled, and the method has important significance for green development of economy in China.
Current research situation of recycling PAC residues: the patent application No. 201410804590.3 discloses a method for co-producing poly-silicon aluminum ferric sulfate and wastewater treatment powder by using PAC residues; the patent application No. 201010245490.3 discloses a method for extracting an aluminiferous acid solution from polyaluminium chloride reaction residues by using an inorganic mixed acid, and reusing the aluminiferous acid solution in the production of polyaluminium chloride; at present, the recycling of PAC residues is usually to prepare wastewater treatment powder after modification and reinforcement, or to recover useful components thereof through acid liquor, and the waste water treatment powder is rarely used for preparing ceramsite, and the preparation of baking-free composite filler is not reported. Therefore, the preparation of the efficient phosphorus removal filler by using the PAC residues becomes a necessary trend for the future recycling treatment of the PAC residues.
The artificial wetland is an artificial simulation strengthened sewage treatment technology developed in the 70 s of the 20 th century, and is widely applied to the field of sewage treatment by virtue of the advantages of high purification efficiency, low investment cost, low operating cost and the like. In order to ensure the normal operation of the wetland, withered and aged plants need to be harvested, and the harvested plants are generally treated as garbage, so that a large amount of land is occupied, and the treatment cost is increased. The constructed wetland has high plant cellulose content, organic substances released by decomposition can be used as a denitrification carbon source to improve the denitrification efficiency, and the constructed wetland has the characteristic of long-term slow release, and effectively overcomes the defects that the adding amount of liquid organic carbon sources such as ethanol, acetic acid and the like added in the prior art is difficult to control, the carbon release period is short, the cost is high and the like. The harvested wetland plants are pretreated to be used as a slow-release carbon source, so that the wetland plants are effectively recycled, the development of the artificial wetland treatment technology is greatly promoted, and a new thought is provided for solving the problem of artificial wetland plant treatment.
Disclosure of Invention
In order to recycle PAC residue waste and plants harvested from a wetland, the invention aims to provide a preparation method of a multifunctional novel composite efficient phosphorus removal filler, which comprises the steps of crushing PAC residue, uniformly mixing the crushed PAC residue with slag portland cement, bentonite, a pretreated slow-release carbon source and the like, spraying a proper amount of water, preparing a filler with the diameter of 10-60 mm by using a granulator or a press, and maintaining for 3-9 days to ensure stable strength.
The multifunctional novel composite efficient phosphorus removal filler prepared by the invention has the advantages of strong phosphorus adsorption capacity, good removal rate and high adsorption capacity, and can greatly improve the problems of poor biodegradability of a water body, insufficient denitrification carbon source and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
the multifunctional novel composite efficient phosphorus removal filler comprises, by weight, 30-50 parts of slag portland cement, 40-60 parts of polyaluminium chloride (PAC) residues, 7-9 parts of bentonite, 1-2 parts of a slow-release carbon source and a weight ratio of a solid raw material to water of 1: 0.4-0.7. The dephosphorization filler of the invention takes the portland slag cement as the adhesive, and the portland slag cement and the bentonite as the PAC residue dephosphorization reinforcer, and the dephosphorization filler has the function of synchronously slowly releasing the carbon source while efficiently dephosphorizing.
A preparation method of a multifunctional novel composite efficient phosphorus removal filler comprises the following steps:
(1) naturally drying and crushing PAC residues, and sieving the PAC residues with a 100-mesh sieve;
(2) the method comprises the steps of measuring the PAC residues, slag portland cement, bentonite, a slow-release carbon source and water according to a formula ratio, uniformly stirring to prepare slurry, preparing the uniformly mixed slurry into uniform spherical particles according to needs through a centrifugal effect in a granulator, or pressing the uniformly mixed slurry into uniform cake-shaped particles through a mold, and then spraying water for curing for 3-9 days to form the phosphorus removal filler containing a large amount of uniform and fine air holes under the environmental conditions that the temperature is 20 +/-5 ℃ and the humidity is 45% -65%.
Further, the bentonite is calcium bentonite. When the cement is Portland slag cement, the composite filler has good dephosphorization effect and high strength. Bentonite, portland slag cement and other raw materials greatly enhance the dephosphorization effect of the PAC residues; the removal rate of the prepared composite phosphorus removal filler in the simulated wastewater with the phosphorus concentration of 100mg/L is up to more than 99.95 percent.
Further, the carbon source is prepared by preprocessing plants harvested by the artificial wetland, and the selected plants are one or more of Siberian iris, cress, reed, canna, cattail, watermifoil, hornworts, sowthistle, black algae and the like in the plants harvested by the wetland. Further, the pretreatment method comprises the following steps: cutting the plant into small strips of about 1cm, soaking in 2% NaOH solution for 30min, steaming at 120 deg.C for 20min, cooling to room temperature, washing with deionized water to neutrality, oven drying at 45 deg.C, and grinding to about 100 mesh.
The phosphorus removal filler has the particle size of 10-60 mm and is spherical or cake-shaped. The phosphorus adsorption capacity of the phosphorus removal filler is 3.00-6.00 mgP/g, and the compressive strength is 250-450N. The multipoint specific surface area of the phosphorus removal filler is 20-35 m2A specific surface area of the micropores is 20 to 30m2(ii) in terms of/g. The phosphorus removal filler has a true density of 1.5-2.5 g/cm3The bulk density is 0.50 to 0.9g/cm3. The median pore diameter of the phosphorus removal filler is 0.4-1 nm.
The multifunctional novel composite efficient phosphorus removal filler can be widely applied to ecological water treatment facilities such as artificial wetlands, biological filters, urban landscape water bodies, integrated treatment equipment and the like.
Compared with the prior art, the invention has the beneficial effects that:
1. the method has the advantages of effectively reducing the treatment cost of solid wastes and saving land resources during landfill by recycling the PAC residues as the raw materials and the plants harvested by the artificial wetland, along with wide sources of slag portland cement and bentonite, simple preparation method, economy and quickness.
2. The invention takes the PAC residues and the plants harvested by the artificial wetland as the raw materials for preparing the multifunctional novel composite efficient dephosphorization filler, provides a new idea for the treatment and disposal of the filler, realizes the reclamation of wastes and has higher engineering application value.
3. The multifunctional novel composite efficient phosphorus removal filler prepared by the invention can effectively avoid the problems that powder is easy to migrate along with water flow and is easy to block and the like.
4. The multifunctional novel composite efficient phosphorus removal filler prepared by the invention does not need high-temperature roasting, and the preparation method is simple and convenient, synchronously slowly releases a carbon source, is low-carbon and environment-friendly, and has low cost;
5. the multifunctional novel composite efficient phosphorus removal filler prepared by the invention has the advantages of strong phosphorus adsorption capacity, good removal rate and high adsorption capacity, and can greatly improve the problems of poor biodegradability of a water body, insufficient denitrification carbon source and the like.
Drawings
FIG. 1 is a spherical picture of the PAC residue composite efficient phosphorus removal filler prepared in example 1;
FIG. 2 is a pie picture of the PAC residue composite efficient phosphorus removal filler prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
The raw material ratio is as follows: by weight percentage, 30% of slag portland cement, 59% of PAC residue, 9% of bentonite, 2% of slow-release carbon source, and the weight ratio of the solid raw materials to water is 1: 0.4-0.7.
The preparation process comprises the following steps: naturally drying the PAC residues, crushing, sieving with a 100-mesh sieve, uniformly mixing with slag portland cement, bentonite, a slow-release carbon source and water, granulating by using a granulator, preparing uniform granules, and curing for 3-9 days to obtain the composite filler, wherein the composite filler is marked as material 1, as shown in figure 1. Or uniformly mixing the PAC residues with slag portland cement, bentonite, a slow-release carbon source and water, pressing into uniform cake-shaped particles through a mold, and curing for 3-9 days to obtain the composite filler, wherein the composite filler is marked as material 1, as shown in figure 2.
Example 2
The raw material ratio is as follows: 35 percent of Portland slag cement, 54.5 percent of PAC residue, 8.5 percent of bentonite, 2 percent of slow-release carbon source and the weight ratio of the solid raw materials to water is 1: 0.4-0.7.
The preparation process comprises the following steps: in the same manner as in example 1, a spherical filler as shown in FIG. 1 and a cake filler as shown in FIG. 2 were obtained, and the product was designated as Material 2.
Example 3
The raw material ratio is as follows: the slag portland cement is 40% by weight, the PAC residue is 50% by weight, the bentonite is 8% by weight, the slow-release carbon source is 2% by weight, and the weight ratio of the solid raw materials to the water is 1: 0.4-0.7.
The preparation process comprises the following steps: in the same manner as in example 1, a spherical filler as shown in FIG. 1 and a cake filler as shown in FIG. 2 were obtained, and the product was designated as Material 3.
Example 4
The raw material ratio is as follows: 44.5 percent of Portland slag cement, 45 percent of PAC residue, 8.5 percent of bentonite, 2 percent of slow-release carbon source and the weight ratio of the solid raw materials to water is 1: 0.4-0.7.
The preparation process comprises the following steps: in the same manner as in example 1, a spherical filler such as shown in FIG. 1 and a cake filler such as shown in FIG. 2 were obtained, and the product was designated as Material 4.
The composition of material 4 of this example is shown in Table 1.
TABLE 1 compositional composition of material 4
The novel composite filler has no heavy metal and meets the waste recycling standard.
Example 5
The raw material ratio is as follows: the slag portland cement-based slow-release carbon source material comprises, by weight, 50% of slag portland cement, 40% of PAC residues, 8% of bentonite, 2% of a slow-release carbon source, and the weight ratio of the solid raw materials to water is 1: 0.4-0.7.
The preparation process comprises the following steps: in the same manner as in example 1, a spherical filler as shown in FIG. 1 and a cake filler as shown in FIG. 2 were obtained, and the product was designated as Material 5.
Example 6
Evaluation of phosphorus removal performance of multifunctional novel composite efficient phosphorus removal filler
The multifunctional novel composite efficient phosphorus removal filler prepared in the above examples 1-5 and ceramsite were subjected to a control experiment. KH with initial concentration of 100mg/L is prepared2PO4The solution simulates phosphorus-containing wastewater, and specifically comprises the following steps: respectively weighing 1g of each of the prepared material 1, the material 2, the material 3, the material 4, the material 5 and the reference material, placing the weighed materials into a 250mL conical flask, adding 100mL of simulated phosphorus-containing wastewater containing 100mg/L of phosphorus, shaking the mixture at a constant temperature of 150rpm for 12 hours, and calculating the removal rate and the adsorption capacity of the phosphorus.
After the experiment, the concentration of phosphorus was measured, and the removal rate and the amount of adsorption were calculated.
The removal rate calculation formula is as follows:
in the formula (1)
-removal (%); c0，Ce-initial concentration of phosphorus before treatment and concentration of phosphorus after treatment (mg/L).
Adsorption capacity calculation formula Qe＝(C0-Ce) V/m. Formula (2)
Q in formula (2)e-adsorption capacity, mg/g; c0，Ce-initial concentration of phosphorus before treatment and concentration of phosphorus after treatment (mg/L); v-volume of solution, L; m-mass of adsorbent, g.
The results are shown in Table 2 below.
TABLE 2 phosphorous removal Performance of the composite efficient phosphorous removal packing prepared in examples 1-5
Example 7
Performance evaluation of slow-release carbon source of multifunctional novel composite efficient phosphorus removal filler
4.5kg of the prepared material 4 is placed in an organic glass column, simulated wastewater is continuously introduced into the glass column at the flow rate of 9mL/min, and water is taken out every 1d to measure the content of organic matters. The results of the measurement after 5d are shown in Table 3 below, because the amount of carbon released was unstable at the first 4 d.
Table 3 carbon source slow release performance of the multifunctional novel composite efficient phosphorus removal filler prepared in example 4
The above description is only for the purpose of illustrating preferred embodiments of the present invention and is not to be construed as limiting the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. The multifunctional novel composite efficient phosphorus removal filler is characterized by comprising, by weight, 30-50 parts of slag portland cement, 40-60 parts of PAC residues, 7-9 parts of bentonite, 1-2 parts of a slow-release carbon source and a weight ratio of a solid raw material to water of 1: 0.4-0.7.
2. A preparation method of a multifunctional novel composite efficient phosphorus removal filler is characterized by comprising the following steps:
(1) naturally drying and crushing PAC residues, and sieving the PAC residues with a 100-mesh sieve;
(2) the method comprises the steps of measuring the PAC residues, slag portland cement, bentonite, a slow-release carbon source and water according to a formula ratio, uniformly stirring to prepare slurry, preparing the uniformly mixed slurry into uniform spherical particles according to needs through a centrifugal effect in a granulator, or pressing the uniformly mixed slurry into uniform cake-shaped particles through a mold, and then spraying water for curing for 3-9 days to form the phosphorus removal filler containing a large amount of uniform and fine air holes under the environmental conditions that the temperature is 20 +/-5 ℃ and the humidity is 45% -65%.
3. The preparation method of the multifunctional novel composite efficient phosphorus removal filler as claimed in claim 2, wherein the bentonite is calcium bentonite.
4. The preparation method of the multifunctional novel composite efficient phosphorus removal filler as claimed in claim 2, wherein the carbon source is prepared by pre-treating harvested plants in the artificial wetland.
5. The method for preparing the multifunctional novel composite efficient phosphorus removal filler as claimed in claim 4, wherein the plant is one or more of Siberian iris, cress, reed, canna, cattail, Foliurus, Goldfish algae, eel grass and hydrilla verticillata in wetland harvested plants.
6. The application of the multifunctional novel composite efficient phosphorus removal filler as claimed in any one of claims 1 to 5 in ecological water treatment facilities.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112551703A (en) * | 2020-11-20 | 2021-03-26 | 苏州科技大学 | Porous slow-release carbon source filler and preparation method and application thereof |
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