Preparation method of organic cation polymeric flocculant modified silicon-based material

Abstract

The invention discloses a preparation method of an organic cation polymeric flocculant modified silicon-based material. The method comprises the following steps: compounding a modified silicon-based material with an organic cation polymeric flocculant, so that valence bonds between molecular groups of the flocculant and active sites on the surface of the modified silicon-based material are combined, and further preparing the organic cation polymeric flocculant modified silicon-based material. The raw materials are low in cost, natural silicon-based minerals or water sediments which are wide and easy to obtain are utilized, solid waste recycling is achieved, the process is simple, and economical efficiency is high; and the selected organic flocculant is an eco-friendly polymer, is non-toxic and harmless, does not introduce secondary pollution after being added, has no adverse effect on aquatic organisms, has efficient treatment performance and high biological safety, and is suitable for the fields of water purification and algae control.

Description

Technical Field

[0001] This invention belongs to the field of water environment treatment technology, specifically relating to a method for preparing a silicon-based material modified with an organic cationic polymeric flocculant. Background Technology

[0002] In recent years, with the rapid development of industry and agriculture and the acceleration of urbanization, large amounts of nitrogen and phosphorus-containing nutrients have been discharged into natural water bodies, leading to increasingly prominent eutrophication problems in surface waters such as lakes and reservoirs, and frequent outbreaks of algal blooms, including cyanobacteria and green algae. Excessive algal growth not only causes decreased water transparency, depletion of dissolved oxygen, and damage to aquatic ecosystems, but also releases algal toxins, seriously threatening drinking water safety and public health. Therefore, developing efficient, economical, and environmentally friendly technologies for the synergistic control of algae and nutrients has become an important research direction in the field of water pollution control.

[0003] Currently, commonly used algae removal technologies mainly include physical harvesting, chemical algae control, and bioremediation. Among them, chemical flocculation is widely used due to its simple operation and rapid effect. However, traditional inorganic flocculants such as aluminum salts and iron salts have problems such as the introduction of residual metal ions, easy resuspension of flocs, and poor adaptability to low-turbidity, high-algae water. Some synthetic organic polymer flocculants have limitations such as difficult degradation and potential ecotoxicity.

[0004] In recent years, researchers have begun to focus on the feasibility of using natural mineral materials (such as clay and diatomaceous earth) as flocculants. These materials have played a crucial role in algae control both domestically and internationally due to their high efficiency, environmental friendliness, and broad applicability. However, the large amount of modified clay required consumes a significant amount of precious clay resources, which is detrimental to ecological protection. Summary of the Invention

[0005] To overcome the above-mentioned defects, this invention proposes a method for preparing silicon-based materials modified with organic cationic polymeric flocculants, aiming to construct a novel water treatment material that combines high-efficiency flocculation, broad-spectrum adsorption, and environmental compatibility.

[0006] To achieve the above objectives, the method for preparing the organic cationic polymeric flocculant-modified silicon-based material of the present invention includes the following steps: combining the modified silicon-based material with an organic cationic polymeric flocculant, so that the flocculant molecular groups and the active sites on the surface of the modified silicon-based material are bonded by valence bonds, thereby obtaining the organic cationic polymeric flocculant-modified silicon-based material.

[0007] Furthermore, the modified silicon-based material is prepared by heating the silicon-based material at 600~800℃ for 4-12 hours.

[0008] Furthermore, the silicon-based material includes, but is not limited to, water sediments, fly ash, and diatomaceous earth.

[0009] Furthermore, the modified silicon-based material and the organic cationic polymeric flocculant are mixed at a mass ratio of 3 to 24:1, and then stirred in an acidic solution for 0.5 to 2 hours.

[0010] Furthermore, the organic cationic polymeric flocculant (OCPF) includes, but is not limited to, chitosan, quaternary ammonium salts, and polyacrylamide.

[0011] Furthermore, the acidic solution is a hydrochloric acid solution with a pH of 2 to 4.

[0012] Compared with the prior art, the present invention has the following advantages: 1. Highly efficient flocculation and synergistic algae removal capabilities: This invention utilizes the composite modification of a silicon-based carrier and an organic cationic flocculant to form a stable surface structure with high positive charge, which can quickly neutralize the negative charge on the surface of algal cells and suspended particles, achieving highly efficient flocculation and sedimentation.

[0013] 2. Simultaneous purification of multiple pollutants: The material provided by this invention not only has an excellent removal effect on algae, but also adsorbs soluble phosphates, some nitrogen-containing pollutants and organic matter in water through surface active sites, realizing the synergistic effect of "flocculation-adsorption", comprehensively reducing the turbidity and nutrient concentration of water, and inhibiting algae regeneration from the source.

[0014] 3. Low raw material cost and realization of solid waste resource utilization: This invention uses widely available natural silicon-based minerals (such as clay and diatomaceous earth) or water sediments as the main raw materials. After high-temperature calcination and activation, they are combined with common polymer flocculants. The process is simple and the cost is significantly lower than that of traditional chemical algaecides, which has good economic benefits and promotion potential.

[0015] 4. High environmental compatibility and ecological safety: The selected organic flocculants, such as chitosan, are eco-friendly polymers. The overall material is non-toxic and harmless, does not introduce secondary pollution after addition, and has no adverse effects on aquatic organisms. It has both high treatment efficiency and high biological safety. Attached Figure Description

[0016] Figure 1 The processed silicon-based material.

[0017] Figure 2 To prepare an organic cationic polymeric flocculant to modify a silicon-based material.

[0018] Figure 3 The effect of different ratios of modified sediment to chitosan on algae removal rate. Detailed Implementation

[0019] The embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

[0020] In the description of this invention, it should be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0021] The terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, unless otherwise stated, "a plurality of" means two or more.

[0022] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "joining" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal communication between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0023] The method of this invention first activates and modifies natural silicon-based materials, such as water sediments, clay, or diatomaceous earth, by calcining at 600-800°C for 4-12 hours. Then, the calcined modified silicon-based material is stirred in a hydrochloric acid solution with pH=2-4 at a mass ratio of (3-24):1 with an organic cationic polymeric flocculant (such as chitosan, quaternary ammonium salt, or polyacrylamide) for 0.5-2 hours, so that the flocculant molecular groups and the active sites on the surface of the silicon-based material are bonded by valence bonds to form a stable composite modified material.

[0024] This invention utilizes readily available natural silicon-based minerals or aquatic sediments to achieve solid waste resource utilization. The process is simple and highly economical. Furthermore, the selected organic flocculant is an eco-friendly polymer that is non-toxic and harmless. It does not introduce secondary pollution after addition and has no adverse effects on aquatic organisms. It combines high-efficiency treatment performance with high biological safety, making it suitable for water purification and algae control.

[0025] Example 1 The mineral raw material used in the method of this invention is dredged river sediment, and the specific preparation method is as follows: Step 1: After drying the salvaged river sediment, crush it, sieve it, and place it in a muffle furnace, calcine it at 650℃ for 6 hours to obtain modified bottom mud. Step 2: Take the calcined and modified bottom mud and mix it with chitosan powder in the following mass ratios: 3:1, 6:1, 12:1 and 24:1. Step 3: Place the mixed powder in a hydrochloric acid solution with pH=3 and stir for 2 hours. After precipitation for 0.5 hours, discard the supernatant to obtain the crude product of organic cationic polymeric flocculant modified silicon-based material. Step 4: After drying the crude product with hot air at 60-80℃, crush and sieve it to obtain the finished product of organic cationic polymeric flocculant modified silicon-based material.

[0026] The usage method is as follows: Mix the finished product with water at a mass ratio of 1:8~10, and then spray the mixture into the algae-containing water body at a dosage of 0.2~0.5 kg / m³.

[0027] like Figure 3 As shown, the higher the amount of chitosan and the higher the proportion of modified sediment, the better the algae removal effect. However, in actual use, when the ratio of m(chitosan):m(modified sediment) = 1:24 is reached, some sediment does not combine with chitosan and remains suspended in the water, resulting in a decrease in water turbidity.

[0028] The present invention has been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described above. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention. Many other changes and modifications made without departing from the concept and scope of the present invention should be considered within the scope of protection of the present invention.

[0029] In the description of this specification, specific features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments or examples.

[0030] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing a silicon-based material modified with an organic cationic polymeric flocculant, characterized in that, The method includes the following steps: combining a modified silicon-based material with an organic cationic polymeric flocculant, such that the flocculant molecular groups are bonded to the active sites on the surface of the modified silicon-based material, thereby obtaining an organic cationic polymeric flocculant-modified silicon-based material.

2. The method for preparing organic cationic polymeric flocculant-modified silicon-based materials according to claim 1, characterized in that, The modified silicon-based material is prepared by heating the silicon-based material at 600~800℃ for 4-12 hours.

3. The method for preparing organic cationic polymeric flocculant-modified silicon-based materials according to claim 2, characterized in that, The silicon-based materials include, but are not limited to, water sediments, fly ash, and diatomaceous earth.

4. The method for preparing silicone-based materials modified with organic cationic polymeric flocculants according to claim 1, characterized in that, The modified silicon-based material and the organic cationic polymeric flocculant are mixed at a mass ratio of 3 to 24:1, and then stirred in an acidic solution for 0.5 to 2 hours.

5. The method for preparing silicone-based materials modified with organic cationic polymeric flocculants according to claim 1, characterized in that, The organic cationic polymeric flocculant (OCPF) includes, but is not limited to, chitosan, quaternary ammonium salts, and polyacrylamide.

6. The method for preparing the organic cationic polymeric flocculant-modified silicon-based material according to claim 4, characterized in that, The acidic solution is a hydrochloric acid solution with a pH of 2 to 4.

Images