Spherical filler device for swimming pool water treatment as well as preparation method and application of spherical filler device

Abstract

The invention belongs to the technical field of water treatment, particularly relates to a spherical filler device for swimming pool water treatment and a preparation method and application thereof, and can effectively solve the problems of flocculant residue and swimming pool water pollution through combined use of a prepared spherical flocculant and a filler device. And meanwhile, the device has a good flocculation effect on excessive cyanuric acid, and the concentration of the residual cyanuric acid can be controlled by changing the quantity of flocculants filled in the device.

Description

Technical Field

[0001] The invention belongs to the technical field of water treatment, and in particular relates to a spherical filler device for swimming pool water treatment and a preparation method and application thereof. Background Art

[0002] Swimming is one of the most popular sports in summer. The pollutants introduced into the pool water by swimmers can be divided into suspended matter, colloids, microorganisms and soluble substances. When the pool is overloaded, white turbidity will appear, seriously affecting the use of the pool. The most effective way to deal with white turbidity is to increase the dosage of disinfectants. Currently, almost all swimming pools are disinfected with chlorine-containing disinfectants. The pollutants released by swimmers and the natural organic matter in the swimming pool water react with chlorine to form various harmful disinfection by-products, such as trihalomethanes and haloacetic acids. Excessive addition of disinfectants increases the risk for swimmers.

[0003] Flocculation is a fast and effective sewage treatment method. Adding organic or inorganic flocculants can aggregate and bind colloidal particles, causing large molecular pollutants and suspended solids in the water to settle quickly. It can work well with disinfectants to treat seriously polluted swimming pool water. However, the residual flocculants after flocculation may not only cause harm to the human body, but also pollute the water body.

[0004] Cyanuric acid is a disinfection byproduct of the disinfectants dichloroisocyanuric acid and trichloroisocyanuric acid. It can maintain a stable concentration of hypochlorous acid in water, thus producing a long-lasting disinfection effect. However, since cyanuric acid is not easy to decompose and remove, it is easy to accumulate in water. When its concentration increases to a certain level, it will seriously inhibit the disinfection effect of hypochlorous acid and increase bacteria. At present, the main method for this situation is to add more trichloro, but this will lead to higher cyanuric acid in the water, forming a vicious circle and seriously affecting people's health. At the same time, if the concentration of cyanuric acid is too low, it will be difficult to maintain a good disinfection effect. Therefore, how to control the appropriate concentration of cyanuric acid is one of the difficulties in swimming pool water treatment. Summary of the invention

[0005] The purpose of the present invention is to provide a spherical filler device for swimming pool water treatment, and a preparation method and application thereof. By preparing spherical flocculants and filling the device, the problem of flocculant residue and pollution of swimming pool water can be effectively solved. At the same time, the device has a good flocculation effect on excess cyanuric acid, and the residual cyanuric acid concentration can be controlled by changing the amount of flocculants filled in the device.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is: A method for preparing a spherical filler for swimming pool water treatment comprises the following steps: S1. Dissolve polyvinyl alcohol and SA (sodium alginate) in boiling water at 100°C and stir continuously to form a mixed solution; S2. In a 60℃ hot water bath and with constant stirring, add 0.5 mol / L FeSO 4 7H 2 O and 0.5 mol / L ZrOCl 2 8H 2 Slowly add 1 mol / L NaOH to the mixed solution to complete the hydroxylation and generate hydrated iron dioxide precipitation. The end point of the reaction is that no precipitation is generated. Adding sodium hydroxide is to provide an alkaline environment for the reaction to make the hydroxylation proceed faster. S3. Add the hydrated iron dioxide precipitate and clinoptilolite powder obtained in step S2 to the mixed solution of polyvinyl alcohol and SA in step S1 to form gel balls coated with hydrated iron dioxide precipitate and clinoptilolite powder. This treatment is to coat the hydrated iron dioxide and clinoptilolite powder with adsorption effect in the gel balls formed by crosslinking PVA and SA, so as to have better adsorption effect; S4. The gel ball solution prepared in step S3 was added dropwise to 5 wt% H 3 BO 3 and 2 wt% CaCl 2 A cross-linking reaction is carried out in the mixed solution to obtain a spherical flocculant PVA / SA-CFZ, which is a spherical filler.

[0007] Furthermore, the post-treatment of the flocculant prepared in step S4 includes rinsing with deionized water until there is no solvent and unreacted reactants on the surface of the flocculant, and then ultra-vacuum freeze-drying at -18°C and storing at room temperature for future use.

[0008] A spherical filler device for swimming pool water treatment, the spherical filler prepared above is filled in a reaction filter column, the reaction filter column inlet is connected to the swimming pool water to be treated through a pump, the reaction filter column outlet is connected to the bottom of the sand cylinder, and the sand cylinder top outlet is connected to the swimming pool water. Ordinary swimming pool water is filtered only by a sand cylinder. This patent uses a filler column and a sand cylinder together, first through the filler column, the prepared spherical filler is coated with clinoptilolite, clinoptilolite has a honeycomb structure, a huge internal surface area, and can flocculate organic matter, suspended matter, etc. in swimming pool water, and the core-shell structure prepared by polyvinyl alcohol / sodium alginate is used to coat it, which can avoid the escape of flocculants and cause secondary pollution to the water body. Then use a sand cylinder to filter out the flocculated macromolecular particles, which can effectively avoid the problem that the single sand cylinder medium has large gaps and cannot effectively remove small molecular suspended matter and organic matter.

[0009] The invention discloses an application of a spherical filler, which is used for reducing the turbidity of swimming pool water and reducing the concentration of organic matter and cyanuric acid in swimming pool water.

[0010] The advantages of the present invention are as follows: the use of the PVA / SA-CFZ spherical flocculant prepared by the present invention in combination with a filler device can not only effectively reduce the turbidity of swimming pool water, but also reduce the concentration of organic matter and cyanuric acid in swimming pool water during the swimming pool water treatment process, and has good pertinence to swimming pool water treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 It is a schematic structural diagram of the spherical filler device of the present invention.

[0012] Figure 2 yes Figure 1 Schematic diagram of the structure of the reaction filter column with medium spherical flocculants.

[0013] Figure 3 This is a diagram showing the turbidity removal effect of the spherical flocculant prepared in Experimental Example 1.

[0014] Figure 4 This is a diagram showing the cyanuric acid removal effect of the spherical flocculant prepared in Experimental Example 2.

[0015] Figure 5 This is a comparison chart of the cyanuric acid removal effect of the spherical flocculant prepared in Experimental Example 3.

[0016] Figure 6 This is the EDS analysis result of the swimming pool water sample. DETAILED DESCRIPTION Example

[0017] A method for preparing a spherical filler for swimming pool water treatment comprises the following steps: S1. Dissolve 10 g of polyvinyl alcohol and 2 g of SA in boiling water at 100 ° C and stir continuously to form a mixed solution; S2. In a 60℃ hot water bath and with constant stirring, add 0.5 mol / L FeSO 4 7H 2 O and 0.5 mol / L ZrOCl 2 8H 2 Slowly add 1 mol / L NaOH to the mixed solution to complete the hydroxylation and generate hydrated iron dioxide precipitation; S3. The hydrated iron dioxide precipitate obtained in step S2 and 20 g of clinoptilolite powder are added to the mixed solution of polyvinyl alcohol and SA in step S1 to form gel balls coated with hydrated iron dioxide precipitate and clinoptilolite powder; S4. The gel ball solution prepared in step S3 was added dropwise to 5 wt% H 3 BO 3 and 2 wt% CaCl 2The cross-linking reaction is carried out in the mixed solution to obtain a spherical flocculant PVA / SA-CFZ, which is a spherical filler; the flocculant prepared in step S4 is then rinsed with deionized water until there is no solvent and unreacted reactants on the surface of the flocculant, and then ultra-vacuum freeze-dried at -18°C and stored at room temperature for use.

[0018] A spherical filler device for swimming pool water treatment is provided. The spherical filler prepared above is filled in a reaction filter column. The reaction filter column inlet is connected to the swimming pool water to be treated through a pump, the reaction filter column outlet is connected to the bottom of a sand tank, and the top outlet of the sand tank is connected to the swimming pool water.

[0019] The invention discloses an application of a spherical filler, which is used for reducing the turbidity of swimming pool water and reducing the concentration of organic matter and cyanuric acid in swimming pool water.

[0020] Experimental Example 1 (1) Preparation of simulated water samples. Kaolin, as a deflocculating substance, can be suspended in fresh water for a long time and is difficult to precipitate. Therefore, it is often used as a model flocculation object for flocculation experiments. Take 0.01g of kaolin and dissolve it in 1000g of water. Mix well to prepare a kaolin solution with a mass fraction of 0.001%. Add appropriate amounts of urea, creatinine and other drugs to simulate turbid swimming pool water samples. The initial turbidity is 6.98 NTU.

[0021] (2) Flocculation experiment steps: A portable multi-parameter water quality analyzer was used to measure the turbidity index. 100 mL of simulated turbid swimming pool water sample was passed through the PVA / SA-CFZ spherical flocculant filler device at a flow rate of 55 mL / h (0.92 mL / min), and the changes in the effluent turbidity were recorded.

[0022] (3) The results of Experimental Example 1 show that the flocculation effect of the PVA / SA-CFZ spherical flocculant filler device is significantly different for different dosages. The flocculation effect is best when the dosage is 0.2%, and the turbidity removal rate of the kaolin solution can reach 89%. The surface structure of the composite flocculant after the flocculation experiment was characterized, and the results are as follows: Figure 3 As shown, a large number of kaolin particle agglomerates are attached to the surface of the flocculant and in the cavities. The agglomerates formed by the flocculation reaction have a dense structure and a large coverage area, indicating that the flocculant has a good flocculation effect.

[0023] Experimental Example 2 (1) Prepare a 100 mg / L cyanuric acid solution, add 0.001% kaolin solution, and add appropriate amounts of urea, creatinine and other drugs to simulate swimming pool water. The initial turbidity of the simulated water sample is 6.98 NTU.

[0024] (2) Flocculation experiment steps: 100 mL of simulated turbid swimming pool water sample was passed through the PVA / SA-CFZ spherical flocculant filler device at a flow rate of 55 mL / h (0.92 mL / min). The concentration of cyanuric acid was tested by ultraviolet spectrophotometry. Ultraviolet spectrophotometry is a commonly used method for determining the concentration of cyanuric acid. It performs quantitative analysis based on the absorption characteristics of cyanuric acid at a specific wavelength.

[0025] (3) Experimental results are as follows Figure 4 As shown in the figure, the cyanuric acid concentration of tap water and purified water is 0, the cyanuric acid concentration of the original water is 90.4 mg / L, the cyanuric acid concentration after passing through a single sand tank is 70 mg / L, and the cyanuric acid concentration after passing through the PVA / SA-CFZ spherical flocculant filler device is 35.6 mg / L. According to the GB374882019 standard, the cyanuric acid concentration standard in swimming pool water should be maintained within the range of ≤50 mg / L, and this result fully meets the national standard requirements. This shows that the designed PVA / SA-CFZ spherical flocculant filler device has a good flocculation effect on cyanuric acid and is targeted at swimming pool water treatment.

[0026] Experimental Example 3: Comparison of flocculation effects of different flocculants in different devices (1) Prepare a 100 mg / L cyanuric acid solution, add 0.001% kaolin solution, and add appropriate amounts of urea, creatinine and other drugs to simulate swimming pool water. The initial turbidity of the simulated water sample is 6.98 NTU.

[0027] (2) Flocculation experiment steps: 100 mL of simulated turbid swimming pool water sample was passed through the PVA / SA-CFZ spherical flocculant filler device at a flow rate of 55 mL / h (0.92 mL / min), through a single sand cylinder, through a common sand cylinder after flocculation using the flocculant polyaluminium chloride, and through a common sand cylinder after flocculation using the PAM-CS flocculant with better turbidity adsorption effect, to compare the cyanuric acid adsorption effects of different flocculants. The cyanuric acid concentration test was carried out by ultraviolet spectrophotometry, which is a commonly used method for determining the concentration of cyanuric acid. It is based on the absorption characteristics of cyanuric acid at a specific wavelength for quantitative analysis.

[0028] (3) Experimental results are as follows Figure 5As shown, the cyanuric acid concentration of tap water and purified water is 0, the cyanuric acid concentration of the original water is 82.3 mg / L, the cyanuric acid concentration after passing through a single sand tank is 55.6 mg / L, the cyanuric acid concentration after flocculation using polyaluminium chloride and passing through an ordinary sand tank is 54.1 mg / L, the cyanuric acid concentration after flocculation using PAM-CS flocculant and passing through an ordinary sand tank is 53.2 mg / L, and the cyanuric acid concentration after passing through the PVA / SA-CFZ spherical flocculant filler device is 35.6 mg / L. This shows that the designed PVA / SA-CFZ spherical flocculant filler device has unique advantages in treating cyanuric acid compared to other flocculants, can greatly improve the treatment effect of swimming pool water, and solve the current problem of cyanuric acid treatment difficulties.

[0029] Application example 4: Flocculation effect on actual swimming pool water (1) The actual source of the swimming pool water sample: a swimming pool in Zhengzhou. Before sampling, the swimming pool water was cloudy and had a pungent odor. The water sample was analyzed using EDS and other analytical methods. The results are as follows: Figure 6 As shown, the main reason for the turbidity of swimming pool water is calcium carbonate, and the pungent smell comes from the excessive use of chlorine-containing disinfectants.

[0030] (2) Flocculation experiment steps: The actual swimming pool water sample was passed through the PVA / SA-CFZ spherical flocculant packing device and only through a single sand cylinder at a flow rate of 55 mL / h (0.92 mL / min) to examine the treatment effect of the packing device on swimming pool water.

[0031] (3) The experimental results are shown in Table 1. The cyanuric acid concentration of the original swimming pool water is 625 mg / L, the turbidity is 0.37 NTU, the urea concentration is 2 mg / L, and the hardness is 89.6 mg / L; after passing through a single sand tank, the cyanuric acid concentration is 260 mg / L, the turbidity is 0.26 NTU, the urea concentration is 0.13 mg / L, and the hardness is 76.2 mg / L; after passing through the PVA / SA-CFZ spherical flocculant filler device, the cyanuric acid concentration is 10.1 mg / L, the turbidity is 0.21 NTU, the urea concentration is 0.06 mg / L, and the hardness is 33.4 mg / L. All indicators can meet the requirements of GB374882019 national standard swimming pool water. This shows that the designed PVA / SA-CFZ spherical flocculant filler device can not only effectively reduce the turbidity of swimming pool water, but also reduce the concentration of organic matter and cyanuric acid in swimming pool water during swimming pool water treatment, and has good pertinence for swimming pool water treatment. The specific results are shown in Table 1.

Claims

1. A method for preparing a spherical filler for swimming pool water treatment, characterized in that: The following steps are involved: S1. Dissolve polyvinyl alcohol and sodium alginate in boiling water at 100°C and stir continuously to form a mixed solution; S2. Slowly add 1 mol / L NaOH to the mixed solution of 0.5 mol / L FeSO4·7H2O and 0.5 mol / L ZrOCl2·8H2O in a 60℃ hot water bath with constant stirring to complete the hydroxylation and generate hydrated iron dioxide precipitation; S3. The hydrated iron dioxide precipitate and clinoptilolite powder obtained in step S2 are added to the mixed solution of polyvinyl alcohol and SA in step S1 to form gel balls coated with hydrated iron dioxide precipitate and clinoptilolite powder; S4. Dropping the gel ball solution obtained in step S3 into a mixed solution of 5 wt% H3BO3 and 2 wt% CaCl2 to perform a cross-linking reaction, thereby obtaining a spherical flocculant PVA / SA-CFZ, which is a spherical filler.

2. The method for preparing the spherical filler for swimming pool water treatment according to claim 1, characterized in that: The post-treatment of the flocculant prepared in step S4 includes washing with deionized water until there is no solvent and unreacted reactants on the surface of the flocculant, and then ultra-vacuum freeze-drying at -18°C and storing at room temperature for future use.

3. A spherical filler device for swimming pool water treatment, characterized in that: The spherical filler prepared according to any one of claims 1 to 2 is filled in a reaction filter column, the inlet of the reaction filter column is connected to the swimming pool water to be treated through a pump, the outlet of the reaction filter column is connected to the bottom of the sand tank, and the top outlet of the sand tank is connected to the swimming pool water.

4. The use of the spherical filler prepared by the preparation method according to any one of claims 1 to 2, characterized in that: It is used in swimming pool water to reduce the turbidity of swimming pool water and reduce the concentration of organic matter and cyanuric acid in swimming pool water.

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