Water quality clarifier, its preparation method and application

Abstract

The present application relates to a kind of water quality clarifier and its preparation method and application, the water quality clarifier includes the component as follows by mass fraction: cationic polyacrylamide 8-15 parts, polyaluminum chloride 1-5 parts, modified polyaluminum chloride 5-10 parts, carboxymethyl chitosan 1-3 parts, tannin 1-2 parts;Wherein, the modified polyaluminum chloride is the obtained by the reaction of double bond polymerization polyaluminum chloride and unsaturated monomer.This application is compounded by cationic polyacrylamide, polyaluminum chloride and modified polyaluminum chloride and other substances, effectively improves the compatibility, matching effect between components, can improve the purification, cleaning function to water body, realizes the role of efficient clarification, meets the demand of water quality treatment in the field such as swimming pool, overcomes the deficiencies and defects existing in the prior art.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, and in particular to a water clarifier, its preparation method, and its application. Background Technology

[0002] Swimming pools, as common public and recreational fitness facilities, operate in an open, circulating state. Influenced by human activity, environmental dust deposition, and water circulation disturbances, the water continuously accumulates complex pollutants such as fine suspended particles, colloidal particles, human sweat, skin flakes, residual oil from skincare products, and trace amounts of algal spores. Due to the extremely small particle size and high stability of these pollutants, conventional pool filtration equipment struggles to completely remove them. Long-term accumulation leads to water turbidity, reduced light transmittance, and a viscous texture. It also provides a breeding ground for bacteria and microorganisms, causing problems such as excessive total bacterial counts and unpleasant odors, severely impacting the appearance and safety of the pool water and failing to meet swimming pool water quality hygiene standards.

[0003] Currently, swimming pool water clarification treatment mainly relies on flocculants. The mainstream and commonly used agents in the industry are the inorganic flocculant polyaluminum chloride and the organic flocculant cationic polyacrylamide. Both are widely used in daily swimming pool water purification due to their moderate cost and good basic flocculation effect. Polyaluminum chloride possesses excellent charge neutralization capabilities, which can disrupt the colloidal stability of water, promoting the aggregation and destabilization of fine pollutants. Cationic polyacrylamide has long-chain polymer bridging adsorption properties, which can adsorb and cascade tiny flocs, achieving pollutant aggregation and sedimentation. Existing technologies often use a physical compounding method to prepare composite clarifiers, which to some extent compensates for the shortcomings of using single agents. However, under the complex water quality conditions of actual swimming pools, this traditional compound system still has many unavoidable technical defects.

[0004] In a simple mixture of polyaluminum chloride and cationic polyacrylamide, the components have poor compatibility and insufficient storage stability. Long-term storage can easily lead to stratification and efficacy attenuation. At the same time, the two components have weak synergy and cannot be specifically adapted to the complex polluted water of swimming pools containing oil, organic matter, and fine suspended particles. They are not capable of capturing difficult-to-remove fine pollutants, and the water is prone to water quality rebound and slight turbidity recurrence after clarification treatment. It is difficult to meet the high-frequency, high-flow, and high-load circulating water purification needs of commercial swimming pools.

[0005] There are also technical solutions for modifying polyaluminum chloride, such as inorganic salt modification, acid-base modification, and conventional cross-linking modification. However, these methods can only slightly optimize the basic charge neutralization performance of inorganic flocculants. They also have drawbacks such as single functional groups, poor adsorption specificity, and weak resistance to water quality interference. They are difficult to form an efficient synergistic flocculation system with cationic polyacrylamide and cannot meet the high-quality, high-efficiency, and high-safety water purification requirements of modern swimming pools.

[0006] Therefore, there is an urgent need to propose a new technical solution to address the problems existing in the current technology. Summary of the Invention

[0007] Based on this, the present invention provides a water clarifier and its preparation method. By compounding multiple substances such as cationic polyacrylamide, polyaluminum chloride and modified polyaluminum chloride, the compatibility and matching effect between the components are effectively improved, which can enhance the purification and cleaning function of water bodies, achieve efficient clarification, meet the needs of water treatment in swimming pools and other fields, and overcome the shortcomings and defects of the prior art.

[0008] One object of the present invention is to provide a water clarifier, the water clarifier comprising the following components in parts by weight: 8-15 parts of cationic polyacrylamide 1-5 parts of polyaluminum chloride 5-10 parts of modified polyaluminum chloride 1-3 parts carboxymethyl chitosan Tannins 1-2 parts; The modified polyaluminum chloride is obtained by reacting double-bonded polyaluminum chloride with unsaturated monomers.

[0009] Furthermore, the unsaturated monomers include polyethylene glycol acrylate and dimethyl diallyl ammonium chloride.

[0010] Furthermore, the double-bonded polyaluminum chloride is obtained by reacting polyaluminum chloride with an acryloyloxysilane coupling agent.

[0011] Another object of the present invention is to provide a method for preparing the above-mentioned water clarifier, the method comprising the following steps: S1. Polyaluminum chloride and acryloyloxysilane coupling agent are mixed and reacted to obtain double-bonded polyaluminum chloride; S2. The double-bonded polyaluminum chloride, unsaturated monomer, and initiator are mixed and heated under an inert gas atmosphere to obtain modified polyaluminum chloride. S3. The modified polyaluminum chloride is mixed with other components to obtain a water clarifier.

[0012] Furthermore, in step S1, the temperature of the mixing reaction is 20-50℃, and the time is 1-10 h.

[0013] Furthermore, the mass ratio of the double-bonded polyaluminum chloride to the unsaturated monomer is 1:(0.1-0.8).

[0014] Furthermore, the unsaturated monomers comprise polyethylene glycol acrylate and dimethyl diallyl ammonium chloride in a mass ratio of (0.1-0.5):(0.5-1).

[0015] Furthermore, in step S2, the heating reaction is carried out at a temperature of 40-90°C for 2-8 hours.

[0016] Another object of the present invention is to provide the application of the above-mentioned water clarifier in swimming pool cleaning.

[0017] The present invention has the following beneficial effects: The water clarifier of this invention is produced by polymerizing double-bonded polyaluminum chloride with polyethylene glycol acrylate and dimethyl diallyl ammonium chloride. The resulting modified polyaluminum chloride has a three-dimensional structure with cationic polymer segments introduced on its surface. Due to the use of polyethylene glycol acrylate as the polymer monomer, a fully cross-linked macromolecular network structure can be formed. The flexible polyethylene glycol segments can increase the degree of molecular chain extension, improve the contact and capture effect with suspended particles, and endow the product with long-range three-dimensional bridging ability. At the same time, it can also adsorb dirt in water through hydrogen bonds and van der Waals forces via polyether segments on the basis of aluminum salt and cationic adsorption, which greatly improves flocculation and purification efficiency.

[0018] This invention also uses cationic polyacrylamide, carboxymethyl chitosan, tannic acid and other substances as components. When combined with modified polyaluminum chloride, they can synergistically achieve electrical gradient neutralization and multi-level bridging, thereby improving sedimentation performance and reducing the dosage. Furthermore, the multiple components rely on the synergistic adsorption of various active sites such as aluminum hydroxyl groups, quaternary ammonium cations, polysaccharide aminocarboxyl groups and polyphenolic hydroxyl groups to achieve efficient removal of pollutants in water and achieve rapid clarification. Detailed Implementation

[0019] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0020] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0021] It should be understood that, except in any operational instance or otherwise indicated, the amounts or all figures representing ingredients used, for example, in the specification and claims, should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximate values ​​varying according to the desired performance to be obtained according to the invention.

[0022] The embodiments of the present invention use the following raw materials: Cationic polyacrylamide (CPAM) was purchased from Henan Wanli Water Purification Materials Co., Ltd.

[0023] Polyaluminum chloride: purchased from Jinan Qianqi Chemical Co., Ltd.

[0024] Polyethylene glycol diacrylate: PEG400DA, purchased from Aladdin.

[0025] In this invention, "water" refers to distilled water.

[0026] In the embodiments of this invention, "parts" refers to parts by mass. Example 1

[0027] A water clarifier, comprising the following components in parts by weight: 8 parts of cationic polyacrylamide 2 parts of polyaluminum chloride 5 parts of modified polyaluminum chloride 1.5 parts carboxymethyl chitosan 1 part tannin; The method for preparing the water clarifier includes the following steps: S1. Using 10 parts water as a solvent, add 1 part KH570, then adjust the pH of the solution to 4.0 with 5 wt% hydrochloric acid, and hydrolyze at room temperature for 12 h to obtain KH570 hydrolysate. Add 10 parts of polyaluminum chloride to 90 parts of water, then add the KH570 hydrolysate, adjust the pH of the solution to 10.0 with 0.1 mol / L sodium hydroxide solution, and react at room temperature for 2 h to obtain a double-bonded polyaluminum chloride solution; S2. Add 0.5 parts of polyethylene glycol diacrylate, 2.5 parts of dimethyl diallyl ammonium chloride and 0.03 parts of ammonium persulfate to the double-bonded polyaluminum chloride solution. Under nitrogen protection, heat to 60°C and stir for 3 h. After cooling, add ethanol to precipitate, wash and dry to obtain modified polyaluminum chloride. S3. Mix the modified polyaluminum chloride and other components evenly according to the above-mentioned mass proportions to obtain the water clarifier. Example 2

[0028] A water clarifier, comprising the following components in parts by weight: 10 parts of cationic polyacrylamide 2.5 parts polyaluminum chloride 6.5 parts of modified polyaluminum chloride 2 parts carboxymethyl chitosan Tannic acid 1.2 parts; The method for preparing the water clarifier includes the following steps: S1. Using 10 parts water as a solvent, add 1 part KH570, then adjust the pH of the solution to 4.0 with 5 wt% hydrochloric acid, and hydrolyze at room temperature for 12 h to obtain KH570 hydrolysate. Add 10 parts of polyaluminum chloride to 90 parts of water, then add the KH570 hydrolysate, adjust the pH of the solution to 10.0 with 0.1 mol / L sodium hydroxide solution, and react at room temperature for 2 h to obtain a double-bonded polyaluminum chloride solution; S2. Add 0.5 parts of polyethylene glycol diacrylate, 2.5 parts of dimethyl diallyl ammonium chloride and 0.03 parts of ammonium persulfate to the double-bonded polyaluminum chloride solution. Under nitrogen protection, heat to 60°C and stir for 3 h. After cooling, add ethanol to precipitate, wash and dry to obtain modified polyaluminum chloride. S3. Mix the modified polyaluminum chloride and other components evenly according to the above-mentioned mass proportions to obtain the water clarifier. Example 3

[0029] A water clarifier, comprising the following components in parts by weight: 12 parts of cationic polyacrylamide 3 parts of polyaluminum chloride 8 parts of modified polyaluminum chloride 2.3 parts carboxymethyl chitosan Tannic acid 1.5 parts; The method for preparing the water clarifier includes the following steps: S1. Using 10 parts water as a solvent, add 1 part KH570, then adjust the pH of the solution to 4.0 with 5 wt% hydrochloric acid, and hydrolyze at room temperature for 12 h to obtain KH570 hydrolysate. Add 10 parts of polyaluminum chloride to 90 parts of water, then add the KH570 hydrolysate, adjust the pH of the solution to 10.0 with 0.1 mol / L sodium hydroxide solution, and react at room temperature for 2 h to obtain a double-bonded polyaluminum chloride solution; S2. Add 0.5 parts of polyethylene glycol diacrylate, 2.5 parts of dimethyl diallyl ammonium chloride and 0.03 parts of ammonium persulfate to the double-bonded polyaluminum chloride solution. Under nitrogen protection, heat to 60°C and stir for 3 h. After cooling, add ethanol to precipitate, wash and dry to obtain modified polyaluminum chloride. S3. Mix the modified polyaluminum chloride and other components evenly according to the above-mentioned mass proportions to obtain the water clarifier.

[0030] Comparative Example 1 A water clarifier, the difference between this comparative example and Example 1 is that steps S1 and S2 are deleted, and modified polyaluminum chloride is replaced with: Polyaluminum chloride, polyethylene glycol (PEG400), and polydimethyldiallylammonium chloride (CAS: 26062-79-3) were mixed in a mass ratio of 10:0.5:2.5 to obtain modified polyaluminum chloride. The remaining components and preparation method were the same as in Example 1.

[0031] Comparative Example 2 A water clarifier, the difference between this comparative example and Example 1 is that in step S2, polyethylene glycol diacrylate is replaced with an equal mass of dimethyl diallyl ammonium chloride, and the remaining components and preparation method are the same as in Example 1.

[0032] Comparative Example 3 A water clarifier, the difference between this comparative example and Example 1 is that tannic acid is replaced with an equal mass of carboxymethyl chitosan, while the remaining components and preparation method are the same as in Example 1.

[0033] Test case Flocculation rate test: Add 450 ml of water to a 500 ml stoppered graduated cylinder, then add 1 g of diatomaceous earth, and replenish the total volume to 500 ml with water. Seal the cylinder and invert it to mix thoroughly. Then add 10 mg of the water clarifier prepared in the example or comparative example. Invert the graduated cylinder 30 times in 1 minute (one upright and one invert counts as one time). Let it stand and start a stopwatch at the same time. Record the height H of the floc settling interface every 60 seconds. The smaller H is, the faster the flocculation speed.

[0034] The test results are shown in Table 1.

[0035] Table 1 Flocculation Performance Test Results

[0036] The test results above show that the water clarifier prepared in the embodiments of the present invention has good cleaning and flocculation effects. The water clarifiers in Examples 1-3 have a very fast settling speed for particulate matter in water, which can meet the high-efficiency clarification function required for swimming pool cleaning. However, in Comparative Example 1, the modified polyaluminum chloride was replaced with a physical mixture of polyaluminum chloride, polyethylene glycol, and polydimethyldiallylammonium chloride, which could not improve its flocculation performance and the settling speed was significantly reduced. Comparative Example 2 did not introduce polyethylene glycol segments, so the improvement in flocculation speed was not ideal. Comparative Example 3 replaced tannic acid, which lacked phenolic hydroxyl groups to form intermolecular forces with the other components, resulting in a reduced synergistic adsorption effect and a lower flocculation speed.

[0037] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0038] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A water clarifier, characterized in that, The water clarifier comprises the following components in parts by weight: 8-15 parts of cationic polyacrylamide 1-5 parts of polyaluminum chloride 5-10 parts of modified polyaluminum chloride 1-3 parts carboxymethyl chitosan Tannins 1-2 parts; The modified polyaluminum chloride is obtained by reacting double-bonded polyaluminum chloride with unsaturated monomers; The unsaturated monomers include polyethylene glycol acrylate and dimethyl diallyl ammonium chloride; The double-bonded polyaluminum chloride is obtained by reacting polyaluminum chloride with an acryloyloxysilane coupling agent; The preparation method of the water clarifier includes the following steps: S1. Polyaluminum chloride and acryloyloxysilane coupling agent are mixed and reacted to obtain double-bonded polyaluminum chloride; S2. The double-bonded polyaluminum chloride, unsaturated monomer, and initiator are mixed and heated under an inert gas atmosphere to obtain modified polyaluminum chloride. S3. The modified polyaluminum chloride is mixed with other components to obtain a water clarifier.

2. The water clarifier according to claim 1, characterized in that, In step S1, the temperature of the mixing reaction is 20-50℃ and the time is 1-10 h.

3. The water clarifier according to claim 1, characterized in that, The mass ratio of the double-bonded polyaluminum chloride to the unsaturated monomer is 1:(0.1-0.8).

4. The water clarifier according to claim 1, characterized in that, The unsaturated monomers comprise polyethylene glycol acrylate and dimethyl diallyl ammonium chloride in a mass ratio of (0.1-0.5):(0.5-1).

5. The water clarifier according to claim 1, characterized in that, In step S2, the heating reaction is carried out at a temperature of 40-90°C for 2-8 hours.

6. The application of the water clarifier according to claim 1 in swimming pool cleaning.

Images