Inorganic-organic hybrid amphoteric flocculant as well as preparation method and application thereof

Abstract

The invention relates to an inorganic-organic hybrid amphoteric flocculant as well as a preparation method and application thereof, the flocculant mainly comprises a component A and a component B. The component A is a polysilicic acid-based inorganic-organic hybrid flocculant, and the component B is an inorganic-organic hybrid cationic flocculant. The inorganic-organic hybrid amphoteric flocculant provided by the invention has the functions of both an inorganic-organic hybrid flocculant and an amphoteric flocculant, shows excellent flocculation performance, and is low in dosage and good in stability.

Description

Technical Field

[0001] The invention belongs to the technical field of composite materials for environmental treatment, and in particular relates to an inorganic-organic hybrid amphoteric flocculant, a preparation method and an application thereof. Background Art

[0002] Flocculants are a widely used agent in the current field of wastewater treatment and water conservation and reuse engineering technology. Based on the charge of the functional groups in the flocculant structure, they are divided into anionic, cationic, and amphoteric flocculants. Amphoteric flocculants contain both anionic and cationic groups and are suitable for treating wastewater systems where positively and negatively charged pollutants coexist, and they have a wider applicable pH range. In actual application, when faced with complex wastewater systems, the use of amphoteric flocculants can effectively avoid the simultaneous addition of anionic and cationic flocculants, thereby improving treatment results and reducing treatment costs.

[0003] CN115785441A discloses an amphoteric flocculant for treating oilfield oily wastewater and its preparation method. The method comprises reacting methyl acrylate, a polyamine or diamine, a quaternary ammonium salt monomer, carbon disulfide, and a strong base. The methyl acrylate and the polyamine or diamine are first reacted to form a polyamide-amine. The polyamide-amine and the quaternary ammonium salt monomer are then subjected to a substitution reaction or Michael addition reaction to form a hyperbranched cationic polymer. Finally, an alkali solution and carbon disulfide are added dropwise to the resulting polymer solution to produce the amphoteric flocculant for treating oilfield oily wastewater. However, the flocculant contains only organic components and has limited electrical neutralization and precipitation trapping capabilities, thereby affecting the overall flocculation performance of the flocculant.

[0004] CN108864363A discloses an amphoteric flocculant and its preparation method. The method involves preparing an amphoteric polymer aqueous solution by solution polymerization using dimethyldiallylammonium chloride and sodium allylsulfonate as raw materials, sodium formate as a chain transfer agent, and potassium persulfate as an initiator. An acidity regulator is then added to obtain the amphoteric flocculant. This flocculant can be used to treat produced wastewater from polymer flooding in offshore oilfields, but its viscosity is relatively low, and its stability needs to be improved.

[0005] At present, there are few reports on research on amphoteric flocculants containing both inorganic and organic components. Based on the performance advantages of amphoteric flocculants, the research on multifunctional new inorganic-organic amphoteric flocculants is of great significance. Summary of the Invention

[0006] In response to the shortcomings of the existing technology, the present invention provides an inorganic-organic hybrid amphoteric flocculant and its preparation method and application. The inorganic-organic hybrid amphoteric flocculant provided by the present invention combines the functions of an inorganic-organic hybrid flocculant and an amphoteric flocculant, exhibits excellent flocculation performance, has a low dosage, and has good stability.

[0007] The first aspect of the present invention provides an inorganic-organic hybrid amphoteric flocculant, which mainly includes component A and component B, wherein component A is a polysilicic acid-based inorganic-organic hybrid flocculant, and component B is an inorganic-organic hybrid cationic flocculant.

[0008] In the present invention, the volume ratio of component A to component B is 5:1-1:2, preferably 2:1-1:1.

[0009] In the present invention, the component A polysilicic acid-based inorganic-organic hybrid flocculant is a copolymer of polysilicic acid and poly(carboxylic acid-sulfonic acid), the carboxylic acid is at least one of acrylic acid, methacrylic acid or maleic acid, and the sulfonic acid is at least one of vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, etc.

[0010] In the present invention, a preferred method for preparing component A polysilicic acid-based inorganic-organic hybrid flocculant comprises the following steps:

[0011] (1) preparing a sodium silicate solution, adjusting the pH to 3-6, and activating the solution to obtain a mixed solution I;

[0012] (2) preparing an organic monomer solution, wherein the organic monomers are carboxylic acid monomers and sulfonic acid monomers, and adjusting the pH to 3-6 to obtain a mixed solution II;

[0013] (3) Mixing the mixed solutions I and II, placing them in a constant temperature water bath, adding an initiator under an inert atmosphere, and carrying out a polymerization reaction to obtain a polysilicic acid-based inorganic-organic hybrid flocculant.

[0014] In the preparation method of component A, the sodium silicate solution in step (1) is prepared with a Si molar concentration of 0.1-0.5 mol / L.

[0015] In the preparation method of component A, the pH is adjusted in step (1) using an inorganic acid or an organic acid. The inorganic acid may be at least one of hydrochloric acid, sulfuric acid, phosphoric acid, or hydrobromic acid, preferably phosphoric acid. The organic acid may be at least one of citric acid, oxalic acid, formic acid, or acetic acid, preferably acetic acid. The inorganic acid or organic acid is used at a concentration of 0.1-1 mol / L.

[0016] In the preparation method of component A, after adjusting the pH in step (1), an activation reaction is carried out at room temperature, and the reaction time is 0.5-1 h.

[0017] In the preparation method of component A, the carboxylic acid monomer in step (2) can be at least one of acrylic acid, methacrylic acid or maleic acid, and the concentration of the carboxylic acid monomer solution is 0.5-2.0 mol / L.

[0018] In the preparation method of component A, the sulfonic acid monomer in step (2) can be at least one of vinyl sulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid, and the mass ratio of the sulfonic acid monomer to the carboxylic acid monomer is 1:9-1:1.

[0019] In the preparation method of component A, in step (2), an alkali solution is added dropwise to adjust the pH while stirring at a rate of 200-500 rpm and a dropwise addition rate of 0.1-0.5 mL / min. The alkali solution may be at least one of NaOH, KOH, or NH3·H2O, and the concentration of the alkali solution is 0.1-1.0 mol / L.

[0020] In the preparation method of component A, in step (3), mixed solutions I and II are mixed at a volume ratio of 5:1-50:1. The temperature of the constant temperature water bath is 40-90°C.

[0021] In the preparation method of component A, the inert atmosphere in step (3) is in the presence of nitrogen or an inert gas, and the inert gas is at least one of helium, argon, etc.

[0022] In the preparation method of component A, the initiator in step (3) can be at least one of a redox initiator or an azo initiator. The redox initiator can be at least one of ammonium persulfate and sodium bisulfite, potassium persulfate and sodium bisulfite, etc. The azo initiator can be at least one of azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, etc., preferably an azo initiator.

[0023] In the preparation method of component A, the mass ratio of the initiator to the organic monomer in step (3) is 1:1000-1:50, and the polymerization reaction time is 8-24 hours.

[0024] In the present invention, the preparation method of the component B inorganic-organic hybrid cationic flocculant comprises the following steps:

[0025] (a) preparing an inorganic flocculant or an inorganic flocculant colloidal solution, adding an inorganic salt for modification, and then adding an organic monomer to obtain a mixed solution;

[0026] (b) placing the mixed solution in a constant temperature water bath, introducing nitrogen or an inert gas, and then adding an initiator to start a polymerization reaction, and obtaining an inorganic-organic hybrid polymer gel after the reaction is completed;

[0027] (c) dissolving the inorganic-organic hybrid polymer gel into a flocculant solution with a mass concentration of 10 wt % to obtain the inorganic-organic hybrid cationic flocculant.

[0028] In the preparation method of component B, the inorganic flocculant in step (a) is at least one of aluminum hydroxide, ferric hydroxide, polyaluminum chloride, polyferric sulfate, polyaluminum silicate, polyaluminum ferric silicate, etc., preferably at least one of aluminum hydroxide, polyaluminum chloride, polyaluminum silicate, polyaluminum ferric silicate, and more preferably a mixture of aluminum hydroxide and polyaluminum silicate in a mass ratio of (2-5):1.

[0029] In the preparation method of component B, the concentration of the inorganic flocculant or the inorganic flocculant colloidal solution in step (a) is 0.05-2 mol / L, calculated as the molar concentration of Al or Fe.

[0030] In the preparation method of component B, the inorganic salt in step (a) is an inorganic oxyacid ion, specifically selected from at least one of soluble salts containing phosphate, monohydrogen phosphate, dihydrogen phosphate, metaphosphate, hypophosphite, citrate, borate, tartrate, acetate, ethylenediaminetetraacetic acid, etc., preferably at least one of the soluble sodium salts containing phosphate, more preferably a mixture of disodium hydrogen phosphate and sodium dihydrogen phosphate in a mass ratio of (1-5): 1.

[0031] In the preparation method of component B, the amount of the inorganic salt in step (a) is 0.5% to 10% of the mass of the organic monomer. Preferably, the inorganic salt is added dropwise for 10 to 60 minutes.

[0032] In the preparation method of component B, the organic monomer in step (a) comprises a cationic quaternary ammonium salt monomer and acrylamide in a mass ratio of 1:9-1:1, wherein the cationic quaternary ammonium salt monomer is selected from at least one of dimethyldiallylammonium chloride, acryloylethoxytrimethylammonium chloride, methacryloylethoxytrimethylammonium chloride, (3-acrylamidopropyl)-trimethylammonium chloride and N,N,N-trimethyl-3-(2-methylallylamino)-1-propylammonium chloride, and preferably a mixture of dimethyldiallylammonium chloride and (3-acrylamidopropyl)-trimethylammonium chloride in a mass ratio of (6-9):1.

[0033] In the preparation method of component B, the mass ratio of the inorganic flocculant to the organic monomer in step (a) is 1:9-2:1.

[0034] In the preparation method of component B, the temperature of the constant temperature water bath in step (a) is 25-90°C. Furthermore, the mixed solution is preferably placed in a constant temperature water bath at 25-50°C for polymerization. After 5-120 minutes of reaction, the water bath temperature is raised to 40-90°C and the reaction is continued for 1-6 hours. After completion of the reaction, an inorganic-organic hybrid polymer gel is obtained.

[0035] In the preparation method of component B, the inert gas in step (b) is selected from any one of helium, argon, etc., or a combination of at least two of them.

[0036] In the preparation method of component B, the initiator in step (b) is a redox initiator, the oxidizing agent is selected from ammonium persulfate and / or potassium persulfate, and the reducing agent is selected from sodium bisulfite. The mass ratio of the oxidizing agent to the reducing agent is 1.05:1-2:1. The mass of the initiator is 0.01%-3% of the mass of the organic monomer. The polymerization reaction time is 2-8 hours.

[0037] In the preparation method of component B, the inorganic-organic hybrid polymer gel in step (c) is dissolved in deionized water.

[0038] The second aspect of the present invention provides a method for preparing the above-mentioned inorganic-organic hybrid amphoteric flocculant, which comprises preparing component A and component B separately and mixing the two in a volume ratio of 5:1-1:2, preferably 2:1-1:1.

[0039] The third aspect of the present invention provides an application of the above-mentioned inorganic-organic hybrid amphoteric flocculant in wastewater treatment, which is used to efficiently remove charged suspended particulate matter in wastewater, and is particularly suitable for wastewater containing both positively charged suspended particulate matter and negatively charged suspended particulate matter, such as wastewater containing both positively charged bauxite and negatively charged silicon micropowder particles.

[0040] In the application of the present invention, the turbidity of the wastewater used is generally 10-1000 NTU. After addition, the turbidity of the wastewater can be reduced to below 10 NTU.

[0041] In the application of the present invention, the dosage of the inorganic-organic hybrid amphoteric flocculant is 5-50 mg / L.

[0042] In the application of the present invention, after the amphoteric flocculant of the present invention is introduced, it is preferably controlled in three stages: in the first stage, the stirring rate is 400-500 rpm and the stirring time is 1-2 min; in the second stage, the stirring rate is 200-300 rpm and the stirring time is 5-8 min; in the third stage, it is left to stand for 10-30 min.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] (1) The inorganic-organic hybrid amphoteric flocculant of the present invention contains both positively charged inorganic and organic functional groups and negatively charged inorganic and organic functional groups, which facilitates the efficient synergistic flocculation effects of charge neutralization, precipitation capture, and adsorption bridging. It can reduce wastewater turbidity to below 10 NTU at low dosages, demonstrating excellent flocculation performance. Furthermore, the flocculant has good storage stability, maintaining a turbidity removal rate of over 90% after long-term storage.

[0045] (2) The present invention separately prepares a polysilicic acid-based inorganic-organic hybrid flocculant and an inorganic-organic hybrid cationic flocculant, and then mixes the two in proportion to obtain an amphoteric flocculant. This effectively prevents the agglomeration of the inorganic components, achieving uniform recombination of the inorganic and organic components, and also avoids the problem of low molecular weight of the flocculant caused by copolymerization of anionic and cationic monomers. The inorganic-organic hybrid amphoteric flocculant is obtained by a physical mixing method, which is simple to prepare, and the resulting amphoteric flocculant has a high molecular weight and strong adsorption and bridging ability.

[0046] (3) The amphoteric flocculant of the present invention is used for the simultaneous removal of positively and negatively charged suspended particles. Since it can capture both positively and negatively charged suspended matter at the same time, forming flocs with larger particle sizes, it can achieve rapid and efficient sedimentation of suspended particles, significantly reduce the turbidity of wastewater, reduce interference with subsequent membrane treatment, catalytic oxidation and other processes, and ensure the long-term stable operation of the entire water treatment process. DETAILED DESCRIPTION

[0047] The technical solution of the present invention and its effects are further illustrated below with reference to specific examples. The examples are implemented based on the technical solution of the present invention, and provide detailed implementation methods and specific operating processes, but the scope of protection of the present invention is not limited to the following examples.

[0048] The experimental methods in the following examples, unless otherwise specified, are all conventional methods in the art. The experimental materials used in the following examples, unless otherwise specified, were purchased from conventional biochemical reagent stores.

[0049] In the present invention, the turbidity of the wastewater was measured by means of a turbidity meter (TL2300EPA, Hach, USA).

[0050] Example 1

[0051] (1) Preparation of inorganic-organic hybrid amphoteric flocculants

[0052] Preparation of component A: prepare a sodium silicate solution with a molar concentration of SiO2 of 0.2 mol / L, adjust the pH value to 4 with the help of 0.5 mol / L hydrochloric acid solution, and activate the reaction at room temperature for 1 hour to obtain a mixed solution I; prepare acrylic acid and vinyl sulfonic acid solutions, control the concentration of the acrylic acid solution to 0.5 mol / L, and the mass ratio of vinyl sulfonic acid to acrylic acid to be 1:5, and slowly add 0.5 mol / L NaOH solution at a rate of 0.3 mL / min under stirring at 300 rpm, and the pH at the end point of the addition is 4 to obtain a mixed solution II; the mixed solutions I and II are mixed in a volume ratio of 10:1, placed in a constant temperature water bath at 70°C, and nitrogen is introduced for 0.5 hour, and azobisisobutylamidine hydrochloride initiator is added, and the mass ratio of the initiator to the organic monomer is controlled to be 1:200, and a polymerization reaction is carried out for 10 hours to obtain a polysilicic acid-based inorganic-organic hybrid flocculant.

[0053] Preparation of Component B: Prepare an Al(OH)3 colloidal solution with a concentration of 0.4 mol / L (based on the molar concentration of Al). Add sodium phosphate (Na3PO4) as a modifier dropwise over a 20-minute period. After the addition is complete, add acrylamide (AM) and dimethyldiallyl ammonium chloride (DMDAAC) to form a mixed solution. The mass ratio of aluminum hydroxide to organic monomer is 1:9, the mass ratio of DMDAAC to AM is 1:9, and the mass of Na3PO4 is 1% of the mass of the organic monomer. The mixed solution is placed in a 25°C constant-temperature water bath and aerated with high-purity nitrogen for approximately 30 minutes. Then, add a mixture of ammonium persulfate ((NH4)2S2O8) and sodium bisulfite (NaHSO3). The reaction system is sealed and the polymerization reaction is continued for 3 hours to yield an inorganic-organic hybrid polymer gel. The mass of the initiator is 0.1% of the mass of the organic monomer, and the mass ratio of (NH4)2S2O8 to NaHSO3 is 1.5:1. The inorganic-organic hybrid cationic polymer gel is dissolved in deionized water to form a flocculant solution with a mass concentration of 10 wt%, namely, an inorganic-organic hybrid cationic flocculant.

[0054] Component A and component B are mixed in a volume ratio of 1:1 to obtain an inorganic-organic hybrid amphoteric flocculant.

[0055] (2) Application effect of inorganic-organic hybrid amphoteric flocculants

[0056] The wastewater to be treated contained positively charged bauxite and negatively charged silica particles, with a turbidity of 189 NTU. A flocculant dosage of 20 mg / L was applied, followed by stirring at 300 rpm for 7 minutes and then stabilization for 20 minutes. Testing revealed that the turbidity dropped to 1.67 NTU.

[0057] Example 2

[0058] (1) Preparation of inorganic-organic hybrid amphoteric flocculants

[0059] Preparation of component A: prepare a sodium silicate solution with a molar concentration of SiO2 of 0.5 mol / L, adjust the pH value to 3 with the help of 1 mol / L sulfuric acid solution, and activate the reaction at room temperature for 45 minutes to obtain a mixed solution I; prepare maleic acid and vinyl sulfonic acid solutions, control the concentration of the maleic acid solution to 2 mol / L, and the mass ratio of vinyl sulfonic acid to maleic acid to be 1:9, and slowly add 1 mol / L KOH solution at a rate of 0.5 mL / min under stirring at 500 rpm, and control the pH at the end point of the addition to be 6 to obtain a mixed solution II; the mixed solutions I and II are mixed in a volume ratio of 50:1, placed in a constant temperature water bath at 90°C, and nitrogen is introduced for 0.5 h, and azobisisobutylimidazoline hydrochloride initiator is added, and the mass ratio of the initiator to the organic monomer is controlled to be 1:1000, and a polymerization reaction is carried out for 8 hours to obtain a polysilicic acid-based inorganic-organic hybrid flocculant.

[0060] Preparation of Component B: Prepare a polyferric sulfate solution with a concentration of 0.4 mol / L (based on the molar concentration of Fe) and add a sodium phosphate (Na3PO4) modifier dropwise over 20 minutes. After the addition is complete, add acrylamide (AM) and dimethyldiallylammonium chloride (DMDAAC) to form a mixed solution. The mass ratio of polyferric sulfate to organic monomer is 1:9, the mass ratio of DMDAAC to AM is 1:9, and the mass of Na3PO4 is 1% of the mass of the organic monomer. The mixed solution is placed in a 25°C constant-temperature water bath and aerated with high-purity nitrogen for approximately 30 minutes. Subsequently, a mixture of ammonium persulfate ((NH4)2S2O8) and sodium bisulfite (NaHSO3) is added. The reaction system is sealed and the polymerization reaction is continued for 3 hours to yield an inorganic-organic hybrid polymer gel. The mass of the initiator is 0.1% of the mass of the organic monomer, and the mass ratio of (NH4)2S2O8 to NaHSO3 is 1.5:1. The inorganic-organic hybrid cationic polymer gel is dissolved in deionized water to form a flocculant solution with a mass concentration of 10 wt%, namely, an inorganic-organic hybrid cationic flocculant.

[0061] Component A and component B are mixed in a volume ratio of 1:1 to obtain an inorganic-organic hybrid amphoteric flocculant.

[0062] (2) Application effect of inorganic-organic hybrid amphoteric flocculants

[0063] The wastewater to be treated contained positively charged bauxite and negatively charged silica particles, with a turbidity of 752 NTU. A flocculant dosage of 50 mg / L was applied, followed by stirring at 300 rpm for 7 minutes and then stabilization for 20 minutes. Testing revealed that the turbidity dropped to 9.82 NTU.

[0064] Example 3

[0065] (1) Preparation of inorganic-organic hybrid amphoteric flocculants

[0066] Preparation of component A: Prepare a sodium silicate solution with a molar concentration of SiO2 of 0.1 mol / L, adjust the pH value to 6 with the help of 0.1 mol / L formic acid solution, and activate the reaction at room temperature for 0.5 h to obtain a mixed solution I; prepare a mixed solution of methacrylic acid and vinyl sulfonic acid, control the concentration of the methacrylic acid solution to be 1 mol / L, and the mass ratio of vinyl sulfonic acid to methacrylic acid to be 1:1, and slowly add 0.1 mol / L NH3·H2O solution at a rate of 0.1 mL / min under stirring at 200 rpm, and control the pH at the end point of the addition to be 3, to obtain a mixed solution II; mix the mixed solutions I and II in a volume ratio of 30:1, place in a constant temperature water bath at 40°C, and introduce argon for 0.5 h, add azobisisobutylamidine hydrochloride as an initiator, and control the mass ratio of the initiator to the organic monomer to be 1:50, and carry out a polymerization reaction for 24 h to obtain a polysilicic acid-based inorganic-organic hybrid flocculant.

[0067] Preparation of component B: A polyaluminium silicate solution with a concentration of 0.4 mol / L (based on the molar concentration of Al) was prepared. Sodium phosphate (Na3PO4) as a modifier was added dropwise over a 20-minute period. After the addition was complete, acrylamide (AM) and dimethyldiallyl ammonium chloride (DMDAAC) were added to form a mixed solution. The mass ratio of polyaluminium silicate to organic monomer was 1:9, the mass ratio of DMDAAC to AM was 1:9, and the mass of Na3PO4 was 1% of the mass of the organic monomer. The mixed solution was placed in a 25°C water bath and aerated with high-purity nitrogen for approximately 30 minutes. A mixture of ammonium persulfate ((NH4)2S2O8) and sodium bisulfite (NaHSO3) was then added. The reaction system was sealed and the polymerization reaction continued for 3 hours to yield an inorganic-organic hybrid polymer gel. Among them, the mass of the initiator is 0.1% of the mass of the organic monomer, and the mass ratio of (NH4)2S2O8 and NaHSO3 is 1.5:1; the inorganic-organic hybrid cationic polymer gel is dissolved with the help of deionized water to form a flocculant solution with a mass concentration of 10wt%, that is, an inorganic-organic hybrid cationic flocculant.

[0068] Component A and component B are mixed in a volume ratio of 1:1 to obtain an inorganic-organic hybrid amphoteric flocculant.

[0069] (2) Application effect of inorganic-organic hybrid amphoteric flocculants

[0070] The wastewater to be treated contained positively charged bauxite and negatively charged silica particles, with a turbidity of 380 NTU. A flocculant dosage of 30 mg / L was applied, followed by stirring at 300 rpm for 7 minutes and then stabilization for 20 minutes. Testing revealed that the turbidity dropped to 6.03 NTU.

[0071] Example 4

[0072] The same method as Example 3, except that the flocculant was prepared at a volume ratio of 1:2 between component A and component B. After treatment, the turbidity was reduced to 9.31 NTU.

[0073] Example 5

[0074] The same method as Example 3, except that the flocculant was prepared at a volume ratio of 5:1 between component A and component B. After treatment, the turbidity was reduced to 9.54 NTU.

[0075] Example 6

[0076] The same method as Example 3 was used, except that after the introduction of the amphoteric flocculant of the present invention, the stirring was controlled in three stages: the first stage was agitation at 450 rpm for 1 minute; the second stage was agitation at 250 rpm for 6 minutes; and the third stage was allowed to stand for 20 minutes. After treatment, the turbidity was reduced to 4.23 NTU.

[0077] Example 7

[0078] The same method as Example 3 was used except that the amphoteric flocculant prepared in Example 3 was stored for 2 months before use, and the dosage was the same. After treatment, the turbidity was tested to be reduced to 18.4 NTU.

[0079] Comparative Example 1

[0080] Same as Example 3, except that only component A was added at a dosage of 30 mg / L. After treatment, the turbidity was reduced to 42.2 NTU.

[0081] Comparative Example 2

[0082] Same as Example 3, except that only component B was added at a dosage of 30 mg / L. After treatment, the turbidity was reduced to 51.7 NTU.

[0083] Comparative Example 3

[0084] Same as Example 3, except that a mixture of polyacrylamide and polysilicic acid (volume ratio 1:1) was used instead of the flocculant of the present invention, at a dosage of 150 mg / L. After treatment, the turbidity was reduced to 19.5 NTU. After storage for two months and use, the turbidity was 106.5 NTU after treatment.

Claims

1. An inorganic-organic hybrid amphoteric flocculant, characterized in that: The invention mainly comprises component A and component B, wherein component A is a polysilicic acid-based inorganic-organic hybrid flocculant, and component B is an inorganic-organic hybrid cationic flocculant.

2. The flocculant according to claim 1, characterized in that: The volume ratio of component A to component B is 5:1-1:2, preferably 2:1-1:

1.

3. The flocculant according to claim 1, characterized in that: The component A polysilicic acid-based inorganic-organic hybrid flocculant is a copolymer of polysilicic acid and poly (carboxylic acid-sulfonic acid), the carboxylic acid is at least one of acrylic acid, methacrylic acid or maleic acid, and the sulfonic acid is at least one of vinyl sulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid.

4. The flocculant according to claim 1 or 3, characterized in that: The preparation method of a polysilicic acid-based inorganic-organic hybrid flocculant comprises the following steps: (1) preparing a sodium silicate solution, adjusting the pH to 3-6, and activating the solution to obtain a mixed solution I; (2) preparing an organic monomer solution, wherein the organic monomers are carboxylic acid monomers and sulfonic acid monomers, adjusting the pH to 3-6, and obtaining a mixed solution II; (3) mixing the mixed solutions I and II, placing the mixed solutions in a constant temperature water bath, adding an initiator under an inert atmosphere, and conducting a polymerization reaction to obtain a polysilicic acid-based inorganic-organic hybrid flocculant.

5. The flocculant according to claim 4, characterized in that: The sodium silicate solution in step (1) is prepared with a Si molar concentration of 0.1-0.5 mol / L.

6. The flocculant according to claim 4, characterized in that: In step (1), the pH is adjusted by means of an inorganic acid or an organic acid, wherein the inorganic acid is at least one of hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid, preferably phosphoric acid; the organic acid is at least one of citric acid, oxalic acid, formic acid or acetic acid, preferably acetic acid; the inorganic acid or organic acid is configured to a concentration of 0.1-1 mol / L for use.

7. The flocculant according to claim 4, characterized in that: After adjusting the pH in step (1), the activation reaction is carried out at room temperature for 0.5-1 h.

8. The flocculant according to claim 4, characterized in that: The carboxylic acid monomer in step (2) is at least one of acrylic acid, methacrylic acid or maleic acid, and the concentration of the carboxylic acid monomer solution is 0.5-2.0 mol / L.

9. The flocculant according to claim 4, characterized in that: The sulfonic acid monomer in step (2) is at least one of vinyl sulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid, and the mass ratio of the sulfonic acid monomer to the carboxylic acid monomer is 1:9-1:

1.

10. The flocculant according to claim 4, characterized in that: In step (2), alkali solution is added dropwise under stirring to adjust the pH, the stirring rate is 200-500 rpm, and the dropwise addition rate is 0.1-0.5 mL / min; the alkali is at least one of NaOH, KOH or NH3·H2O, and the concentration of the alkali solution is 0.1-1.0 mol / L.

11. The flocculant according to claim 4, characterized in that: In step (3), the mixed solutions I and II are mixed in a volume ratio of 5:1-50:1; the temperature of the constant temperature water bath is 40-90°C.

12. The flocculant according to claim 4, characterized in that: The initiator in step (3) may be at least one of a redox initiator or an azo initiator; the redox initiator may be at least one of ammonium persulfate and sodium bisulfite, or potassium persulfate and sodium bisulfite; the azo initiator may be at least one of azobisisobutylamidine hydrochloride and azobisisobutylimidazoline hydrochloride, preferably an azo initiator.

13. The flocculant according to claim 4, characterized in that: In step (3), the mass ratio of the initiator to the organic monomer is 1:1000-1:50; and the polymerization reaction time is 8-24 hours.

14. The flocculant according to claim 1, characterized in that: The preparation method of the inorganic-organic hybrid cationic flocculant comprises the following steps: (a) preparing an inorganic flocculant or an inorganic flocculant colloidal solution, adding an inorganic salt for modification, and then adding an organic monomer to obtain a mixed solution; (b) placing the mixed solution in a constant temperature water bath, introducing nitrogen or an inert gas, and then adding an initiator to start a polymerization reaction, and obtaining an inorganic-organic hybrid polymer gel after the reaction is completed; and (c) dissolving the inorganic-organic hybrid polymer gel into a flocculant solution with a mass concentration of 10wt% to obtain the inorganic-organic hybrid cationic flocculant.

15. The flocculant according to claim 14, characterized in that: The inorganic flocculant in step (a) is at least one of aluminum hydroxide, ferric hydroxide, polyaluminum chloride, polyferric sulfate, polyaluminum silicate, and polyaluminum ferric silicate, preferably at least one of aluminum hydroxide, polyaluminum chloride, polyaluminum silicate, and polyaluminum ferric silicate, more preferably a mixture of aluminum hydroxide and polyaluminum silicate in a mass ratio of (2-5):

1.

16. The flocculant according to claim 14, characterized in that: The concentration of the inorganic flocculant or inorganic flocculant colloidal solution in step (a) is 0.05-2 mol / L, calculated as the molar concentration of Al or Fe.

17. The flocculant according to claim 14, characterized in that: The inorganic salt in step (a) is an inorganic oxygen-containing acid ion, specifically selected from at least one of phosphate, monohydrogen phosphate, dihydrogen phosphate, metaphosphate, hypophosphite, citrate, borate, tartrate, acetate, and ethylenediaminetetraacetic acid, preferably at least one soluble sodium salt of phosphate, more preferably a mixture of disodium hydrogen phosphate and sodium dihydrogen phosphate in a mass ratio of (1-5):

1.

18. The flocculant according to claim 14, characterized in that: The amount of the inorganic salt in step (a) is 0.5%-10% of the mass of the organic monomer; the inorganic salt is added dropwise for 10-60 minutes.

19. The flocculant according to claim 14, characterized in that: The organic monomer in step (a) comprises a cationic quaternary ammonium salt monomer and acrylamide in a mass ratio of 1:9-1:1, wherein the cationic quaternary ammonium salt monomer is selected from at least one of dimethyldiallylammonium chloride, acryloylethoxytrimethylammonium chloride, methacryloylethoxytrimethylammonium chloride, (3-acrylamidopropyl)-trimethylammonium chloride and N,N,N-trimethyl-3-(2-methylallylamino)-1-propylammonium chloride, and preferably a mixture of dimethyldiallylammonium chloride and (3-acrylamidopropyl)-trimethylammonium chloride in a mass ratio of (6-9):1; the mass ratio of the inorganic flocculant to the organic monomer is 1:9-2:

1.

20. The flocculant according to claim 14, characterized in that: The temperature of the constant temperature water bath in step (a) is 25-90°C; further, the mixed solution is preferably placed in a constant temperature water bath at 25-50°C for polymerization reaction. After the reaction for 5-120 minutes, the water bath temperature is increased to 40-90°C and the reaction is continued for 1-6 hours. After the reaction is completed, an inorganic-organic hybrid polymer gel is obtained.

21. The flocculant according to claim 14, characterized in that: The initiator in step (b) is an oxidation-reduction initiator, the oxidizing agent is selected from ammonium persulfate and / or potassium persulfate, and the reducing agent is selected from sodium bisulfite; the mass ratio of the oxidizing agent to the reducing agent is 1.05:1-2:1; the mass of the initiator is 0.01%-3% of the mass of the organic monomer; and the polymerization reaction time is 2-8 hours.

22. A method for preparing the inorganic-organic hybrid amphoteric flocculant according to any one of claims 1 to 21, characterized in that: Prepare component A and component B separately, and mix the two in a volume ratio of 5:1-1:2, preferably 2:1-1:

1.

23. Use of the inorganic-organic hybrid amphoteric flocculant according to any one of claims 1 to 21 or the inorganic-organic hybrid amphoteric flocculant according to claim 22 in wastewater treatment for efficiently removing charged suspended particulate matter in wastewater, and is particularly suitable for wastewater containing both positively charged suspended particulate matter and negatively charged suspended particulate matter.

24. The use according to claim 23, characterized in that: The turbidity of the wastewater used is 10-1000 NTU; the dosage of the inorganic-organic hybrid amphoteric flocculant is 5-50 mg / L.

25. The use according to claim 23, characterized in that: After the introduction of the amphoteric flocculant, the control is divided into three stages. In the first stage, the stirring rate is 400-500 rpm and the stirring time is 1-2 minutes; in the second stage, the stirring rate is 200-300 rpm and the stirring time is 5-8 minutes; in the third stage, it is left to stand for 10-30 minutes.