WO2022233094A1 - 一种疏水改性阳离子淀粉絮凝剂及其制备方法和应用 - Google Patents

一种疏水改性阳离子淀粉絮凝剂及其制备方法和应用 Download PDF

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WO2022233094A1
WO2022233094A1 PCT/CN2021/108551 CN2021108551W WO2022233094A1 WO 2022233094 A1 WO2022233094 A1 WO 2022233094A1 CN 2021108551 W CN2021108551 W CN 2021108551W WO 2022233094 A1 WO2022233094 A1 WO 2022233094A1
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preparation
hydrophobically modified
cationic starch
modified cationic
flocculants
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French (fr)
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杨琥
胡潘
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南京大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
    • C02F11/147—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/08—Ethers
    • C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
    • C08B31/125—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch having a substituent containing at least one nitrogen atom, e.g. cationic starch

Definitions

  • the invention belongs to the cross technical field of polymer chemical synthesis and environmental protection, and particularly relates to a hydrophobically modified cationic starch flocculant and a preparation method and application thereof.
  • sludge As a by-product of sewage treatment, sludge contains toxic and harmful substances, such as pathogens, heavy metals, and some organic substances. If it is directly discharged, it will cause harm to the ecological environment. Severe pollution requires proper treatment and disposal of sludge to reduce its harm to the environment. On the other hand, the moisture content of the untreated sludge is generally above 92%, and the sludge needs to be dewatered to reduce the volume of the sludge and reduce its storage and transportation costs.
  • the high water content of the sludge is due to the fact that the surface of the sludge particles will be wrapped with a hydration layer to form a stable colloidal suspension. These particles are negatively charged and repel each other, resulting in poor settling performance and dewatering performance, and the solid-liquid separation of sludge is difficult.
  • the organic components in the sludge especially the extracellular polymer (EPS), will affect the sludge dewatering performance and increase the difficulty of sludge dewatering.
  • Sludge dewatering takes mechanical dewatering as the mainstream process, which is affected by the composition characteristics of sludge. It is difficult to achieve good dewatering effect if mechanical dewatering is carried out directly. Therefore, before mechanical dehydration, sludge needs to be pretreated to facilitate subsequent efficient dehydration.
  • Coagulation/flocculation is one of the conventional sludge pretreatment technologies, and the coagulation/flocculation process lays an important foundation for the subsequent mechanical dewatering to reduce the sludge volume.
  • Coagulation/flocculation method has been widely used in wastewater treatment due to its advantages of simple operation, low cost, wide application range and good treatment effect, and the selection of coagulation/flocculant has become the key and core of wastewater treatment technology.
  • synthetic organic polymer flocculants such as polyacrylamide (PAM) and inorganic coagulants such as iron salts and aluminum salts are widely used in the market.
  • the present invention designs a hydrophobically modified cationic starch flocculant that can control the degree of hydrophobicity, which can more effectively reduce the moisture content of the mud cake and improve the sludge disposal performance.
  • the present invention provides a hydrophobically modified cationic starch flocculant, a preparation method and application thereof.
  • the hydrophobicity and hydrophobicity of the flocculant can be easily adjusted, and can better interact with amphiphilic EPS in sludge colloid, and can be obtained by graft copolymerization.
  • the method improves the molecular weight and the number of functional groups of the flocculant, and enhances the flocculation and sludge dewatering performance.
  • the present invention provides the following technical solutions:
  • a hydrophobically modified cationic starch flocculant the structural formula of the hydrophobically modified cationic starch flocculant is as follows:
  • n can be any integer from 1-12.
  • the present invention also provides a preparation method of the hydrophobically modified cationic starch flocculant, comprising the following steps:
  • Step 1 Mix organic solvent, methacryloyloxyethyldimethylammonium bromide and 1-bromoalkyl compound, stir, add organic solvent to elute to obtain white product;
  • Step 2 adding sodium hydroxide to the starch to carry out alkalization and gelatinization reaction, then adding 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution to continue the reaction, adjusting pH, to obtain etherified modified starch;
  • Step 3 under nitrogen atmosphere, add ammonium persulfate to the etherified modified starch, then add acrylamide and the white product, stir, after the reaction is completed, add a precipitant to precipitate, filter, dry, pulverize, and then use Soxhlet extraction with acetone solution and drying to obtain hydrophobically modified cationic starch flocculant.
  • reaction equation for preparing the hydrophobically modified cationic starch flocculant is as follows:
  • CTA stands for 3-chloro-2-hydroxypropyltrimethylammonium chloride
  • AM stands for acrylamide
  • DMRs stands for cationic monomers with different alkane chain lengths
  • CS-DMRs stands for grafted monomers with different alkane chain lengths
  • APS ammonium persulfate.
  • the white products are DMRs, including: DMR3, DMR5 and DMR7.
  • the obtained hydrophobically modified cationic starch flocculants are CS-DMRs, including CS-DMR3, CS-DMR5 and CS-DMR7.
  • the 1-bromoalkyl compound in step 1 includes one of 1-bromopropane, 1-bromopentane and 1-bromoheptane; the organic solvent is acetone.
  • step 1 is stirring at a temperature of 30-60° C. for 24-72 hours.
  • the total molar ratio of the organic solvent described in step 1 to the 1-bromoalkyl compound and methacryloyloxyethyldimethylammonium bromide is 2:(1-2).
  • the organic solvent is acetone.
  • the reaction time is 1-3h, the reaction temperature is 40-100° C.; the continuous reaction time is 2-5h; and the pH is 5-10.
  • the mass fraction of the etherified modified starch in step 3 is 5-20%.
  • step 3 the ammonium persulfate described in step 3 is freshly prepared.
  • step 3 the etherified modified starch and ammonium persulfate are reacted for 10-30 minutes, so that the initiator ammonium persulfate and the etherified modified starch are fully reacted.
  • the molar ratio of the ammonium persulfate described in step 3 to the etherified modified starch is 1: (5-50); the molar ratio of the white product to acrylamide is (1-6): (1-6) .
  • the dropping rate of the white product and acrylamide described in step 3 is 2 drops/s.
  • step 3 is a stirring reaction at 25-55° C. for 2-10 h. Ensure that the entire reaction is carried out under anaerobic conditions.
  • the precipitating agent in step 3 is acetone or ethanol; the volume ratio of the precipitating agent and the hydrophobically modified cationic starch flocculant reaction system is 2:1.
  • the flocculant reaction system includes a flocculant and solvent water in the reaction system.
  • step 3 is Soxhlet extraction in an acetone solution at 80-105° C. for 2 days.
  • the invention also provides the application of the hydrophobically modified cationic starch flocculant in sludge dewatering.
  • Natural polymer flocculants (such as starch, cellulose, chitin, etc.) have the characteristics of low cost, green environmental protection, and a wide range of sources. Their molecular structure usually contains a large number of active groups such as hydroxyl and amine groups, which can be obtained by etherification. , amination, esterification, oxidation, graft copolymerization and other modification methods, introduce monomers with different functions into natural polymers, improve their own shortcomings such as poor solubility, low charge and low molecular weight, and obtain a wide variety of high-efficiency water treatment agent. The structure of the flocculant determines its application performance.
  • the hydrophobic group can form a hydrophobic area, further forming a rough and porous mud cake, and the rigid hydrophobic structure can act as an aggregate to improve the compressibility of the mud cake and facilitate the discharge of internal water.
  • flocculants with hydrophilic and hydrophobic amphiphilic structures in sludge dewatering in domestic and foreign literatures.
  • the present invention adopts the method of graft modification to obtain a hydrophobically modified cationic starch flocculant, which can regulate and control the hydrophobicity; at the same time, the amounts of binary comonomers, initiators and starch can be adjusted, and then the graft chains can be controlled.
  • the chain length and distribution of the flocculant greatly increase the molecular weight and the number of functional groups of the flocculant, and enhance the effect of electric neutralization and bonding and bridging.
  • the rigid hydrophobic chains can also act as aggregates to improve the filterability and dehydration of the mud cake; through the synergistic effect of the above-mentioned electric neutralization, bonding bridging and hydrophobic association effects , effectively improve the sludge disposal performance.
  • the raw material used in the present invention is a kind of natural polymer: starch, which has a wide range of sources, is non-toxic, biodegradable, and has no secondary pollution risk. Because the starch structure is rich in functional groups such as a large number of hydroxyl groups, it can not only be used as a base The material plays the role of grafting hydrophobic chains, and can also assist in the synergistic adsorption of pollutants in the water body, effectively enhancing the application range of natural polymer flocculants.
  • hydrophilicity and hydrophobicity of hydrophobically modified cationic starch flocculants can be adjusted and controlled by selecting different monomers (DMRs), modified starch flocculants with appropriate hydrophobicity can be selected according to different types and characteristics of sludge.
  • the hydrophobically modified cationic starch flocculant of the present invention not only has efficient sludge dewatering performance, but can reduce the sludge moisture content to below 80% under the action of 0.05MPa, and can also reduce the hydrophobic organic matter and COD in the water body. It also has antibacterial and deodorizing effects.
  • the preparation method and operation process of the product of the present invention are simple, the synthesis time is short, the source of raw materials is wide, the cost is low, and the product is widely used.
  • This product is an economical, green and environmentally friendly water treatment agent, which provides new ideas and useful references for the development and design of green, low-cost, high-performance natural polymer flocculants.
  • Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the monomer DMRs prepared in Example 1 and Comparative Example 1;
  • Fig. 2 is the Fourier transform infrared spectrogram of the monomer DMRs prepared in Example 1 and Comparative Example 1;
  • Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the flocculants prepared in Example 1 and Comparative Example 1;
  • Fig. 4 is the Fourier transform infrared spectrogram of the flocculants prepared in Example 1 and Comparative Example 1;
  • Fig. 5 is the contact angle diagram of the flocculants prepared in Example 1 and Comparative Example 1;
  • Fig. 6 is a graph of the relationship between the dosage of flocculant and the moisture content of mud cake prepared in Example 1 and Comparative Example 1;
  • Example 7 is a graph showing the relationship between the flocculants prepared in Example 1 and Comparative Example 1 and the specific resistance of sludge.
  • Step 1 Synthesis of active functional monomer DMRs: monomer methacryloyloxyethyl dimethyl ammonium bromide and 1-bromoalkyl compounds (including: 1-bromopropane, 1-bromopentane or 1-bromopentane) Bromoheptane) was dissolved in the organic solvent acetone (wherein the molar ratio of acetone, the monomer methacryloyloxyethyldimethylammonium bromide and the 1-bromoalkyl compound was 2:1:1), stirring at 60 °C 24h, when the reactants were completely reacted, the solvent was volatilized, and white product DMRs (including DMR3, DMR5 and DMR7) were obtained after elution;
  • Step 2 Preparation of etherified modified starch: Add 5g of starch and 2g of NaOH into water, alkalize and gelatinize at 90°C for 1h, and dropwise add 3g of 3-chloro-2-hydroxypropyltrimethylammonium chloride After continuing to react for 5 hours, 0.1 mol/L sodium hydroxide aqueous solution was added dropwise to adjust the pH to 10 to obtain etherified modified starch;
  • Step 3 Preparation of hydrophobically modified cationic starch flocculant: fully dissolve the obtained etherified modified starch in 100 mL of aqueous solution, so that the mass fraction of etherified modified starch is 20%, stir at 60 ° C for 1 hour, and pass Enter nitrogen, add freshly prepared ammonium persulfate solution, and react for 30 minutes, so that the ammonium persulfate solution and the etherified modified starch are fully reacted, wherein the molar ratio of ammonium persulfate to the etherified modified starch is 1:5; Add DMRs and acrylamide comonomer dropwise to the system at a speed of /s, the molar ratio of which is 1:6, and stir the reaction at 55 ° C for 10 h to ensure that the whole reaction is carried out under anaerobic conditions.
  • CS-DMR1 hydrophilic modified cationic starch flocculant
  • DMR1 methacryloyloxyethyltrimethylammonium chloride
  • Figure 1 shows the H NMR spectra of the monomeric DMRs prepared in Example 1 and Comparative Example 1.
  • FIG. 3 is the hydrogen nuclear magnetic resonance spectrum of the CS-DMRs prepared in Example 1 and Comparative Example 1
  • FIG. 4 is the Fourier infrared spectrum of the CS-DMRs prepared in Example 1 and Comparative Example 1.
  • the chemical shifts of its methylene and methyl protons in the 1 HNMR spectrum are 2.10 ppm and 1.55 ppm, respectively.
  • the characteristic infrared peaks at 1720, 1477 and 952 cm -1 correspond to the stretching vibrations of carbonyl groups.
  • the chemical shift of the quaternary ammonium salt methyl proton vibration is 3.20 ppm.
  • FIG. 5 shows the contact angles of CS-DMRs prepared in Example 1 and Comparative Example 1.
  • FIG. 5 shows the contact angles of CS-DMRs prepared in Example 1 and Comparative Example 1.
  • the contact angle of the sample is positively correlated with the hydrophobicity.
  • the CS-DMRs with the same charge density and different hydrophobicity were obtained by adjusting the ratio of the reaction monomer DMRs to AM and the total molar weight of the AM.
  • the hydrophilicity and hydrophobicity of the flocculant CS-DMRs were characterized.
  • CS-DMR7 contains the longest hydrophobic alkane chain structure, and its maximum contact angle is 61.32°, and the contact angles of CS-DMRs are all less than 90°, indicating that their solubility is also relatively good.
  • Figures 6-7 are graphs showing the relationship between the dosage of CS-DMRs prepared in Example 1 and Comparative Example 1, the moisture content of the mud cake and the specific resistance of the sludge.
  • both FCMC and SRF decreased rapidly at first, and after continuing to increase the dosage to the optimal dosage, The values of FCMC and SRF did not change much and tended to be stable.
  • CS-DMR7 with the highest hydrophobicity has the most excellent dehydration performance, which can reduce the FCMC from 95.47% to 79.26%.
  • Step 1 Synthesis of active functional monomer DMRs: monomer methacryloyloxyethyldimethylammonium bromide and 1-bromoalkyl compounds (including: 1-bromopropane, 1-bromopentane and 1-bromopentane) Bromoheptane) was dissolved in the organic solvent acetone (wherein the molar ratio of acetone, the monomer methacryloyloxyethyldimethylammonium bromide and the 1-bromoalkyl compound was 2:1:0.5), stirring at 45 °C 48h, when the reactants were completely reacted, the solvent was volatilized, and white product DMRs (including DMR3, DMR5 and DMR7) were obtained after elution;
  • Step 2 Preparation of etherified modified starch: Disperse 5g of starch in an aqueous solution, then add 0.5g of NaOH, alkalize and gelatinize at 80°C for 3h, and dropwise add 2g of 3-chloro-2-hydroxypropyltris The methyl ammonium chloride aqueous solution was continuously reacted for 4 hours, and then 0.1 mol/L sodium hydroxide aqueous solution was added dropwise to adjust the pH to 5 to obtain the etherified modified starch.
  • Step 3 Preparation of hydrophobically modified cationic starch flocculant: fully dissolve the obtained etherified modified starch in 100 mL of aqueous solution to make the mass fraction of the etherified modified starch to be 15%, and introduce nitrogen into the water bath at 40°C. Stir to make it fully dissolved, add freshly prepared ammonium persulfate solution, and react for 30 minutes, so that the ammonium persulfate solution and the etherified modified starch are fully reacted, wherein the molar ratio of ammonium persulfate to the etherified modified starch is 1:20.
  • DMRs and acrylamide comonomer were added dropwise to the system at a rate of 2 drops/s, the molar ratio of which was 5:2, and the reaction was stirred at 45 °C for 6 h to ensure that the entire reaction was carried out under nitrogen conditions.
  • a precipitant acetone was added, wherein the volume ratio of acetone to the product solution was 2:1, the product was precipitated, dried, pulverized, Soxhlet extracted in an acetone solution at 85°C for 2 days, and dried to obtain powdery hydrophobically modified cationic starch flocculation Agent CS-DMRs (including: CS-DMR3, CS-DMR5 and CS-DMR7).
  • the obtained DMRs had 1 H NMR and FTIR spectra similar to those in Figure 1, indicating that the DMRs were successfully prepared.
  • the prepared CS-DMRs have 1 H NMR and FTIR spectra and contact angles similar to those in Figure 2, indicating that CS-DMRs have been successfully prepared, and their sludge dewatering performance is similar to that of Example 1.
  • Step 1 Synthesis of active functional monomer DMRs: monomer methacryloyloxyethyl dimethyl ammonium bromide and 1-bromoalkyl compounds (including: 1-bromopropane, 1-bromopentane or 1-bromopentane) Bromoheptane) was dissolved in the organic solvent acetone (wherein the molar ratio of acetone, monomer methacryloyloxyethyldimethylammonium bromide and 1-bromoalkyl compound was 2:1:1), stirring at 30 °C 24h, when the reactants were completely reacted, the solvent was volatilized, and white product DMRs (including DMR3, DMR5 and DMR7) were obtained after elution;
  • Step 2 Preparation of etherified modified starch: add 5g of starch to 1.0g of NaOH and gelatinize for 1h under the alkaline condition of a 60°C water bath, add dropwise 1.5g of 3-chloro-2-hydroxypropyltrimethyl The ammonium chloride aqueous solution was kept at 60°C for 4 hours, and the solution was brown, and 0.1 mol/L sodium hydroxide aqueous solution was added dropwise to adjust the pH to 6 to obtain etherified modified starch;
  • Step 3 Preparation of hydrophobically modified cationic starch flocculant: fully dissolve the obtained etherified modified starch in 100 mL of aqueous solution, so that the mass fraction of etherified modified starch is 10%, stir at 60 ° C for 1 hour, and pass through Enter nitrogen, add freshly prepared ammonium persulfate solution, and react for 15 minutes, so that the ammonium persulfate solution and the etherified modified starch are fully reacted, wherein the molar ratio of ammonium persulfate to the etherified modified starch is 1:25.
  • the prepared active functional monomeric DMRs have 1 H NMR and FTIR spectra similar to those in Figure 1, indicating that DMRs were successfully prepared.
  • the prepared CS-DMRs have 1 H NMR and FTIR spectra and contact angles similar to those in Figure 2, indicating that CS-DMRs have been successfully prepared, and their sludge dewatering performance is similar to that of Example 1.
  • Step 1 Synthesis of active functional monomer DMRs: using monomer methacryloyloxyethyldimethylammonium bromide and 1-bromoalkyl compounds (including: 1-bromopropane, 1-bromopentane or 1-bromopentane) Bromoheptane) as the solute, using acetone as the solvent, the solute is dissolved in the solvent (wherein the molar ratio of acetone, the monomer methacryloyloxyethyldimethylammonium bromide and the 1-bromoalkyl compound is 2:0.5 : 0.5), stirred at 50°C for 72h, after the reactants were completely reacted, the solvent was volatilized, and white product DMRs (including DMR3, DMR5 and DMR7) were obtained after elution;
  • 1-bromoalkyl compounds including: 1-bromopropane, 1-bromopentane or 1-bromopentane
  • Step 2 Preparation of etherified modified starch: add 1.5g NaOH to the aqueous solution of 5g starch, alkalize and gelatinize at 40°C for 1.5h, and dropwise add 2g 3-chloro-2-hydroxypropyltrimethyl Aqueous ammonium chloride solution, after continuing to react for 2.5 hours, 0.1 mol/L aqueous sodium hydroxide solution was added dropwise to adjust pH to 8 to obtain etherified modified starch.
  • Step 3 Preparation of hydrophobically modified cationic starch flocculant: fully dissolving the obtained etherified modified starch in 100 mL of aqueous solution to make the mass fraction of etherified modified starch to be 10%, and introducing nitrogen gas into a water bath at 40°C Stir for 1 hour, add the freshly prepared ammonium persulfate solution, and react for 10 minutes, so that the ammonium persulfate solution and the etherified modified starch are fully reacted, wherein the molar ratio of ammonium persulfate to the etherified modified starch is 1:30.
  • DMRs and acrylamide comonomer were added dropwise to the system at a rate of 2 drops/s, the molar ratio of which was 4:3, and the reaction was stirred at 30 °C for 10 h to ensure that the entire reaction was carried out under anaerobic conditions.
  • precipitating agent ethanol wherein the volume ratio of ethanol and product solution is 2:1
  • the product is precipitated, dried, pulverized, Soxhlet extracted in 80 °C acetone solution for 2 days, dried to obtain powdery hydrophobically modified cationic starch Flocculants CS-DMRs (including: CS-DMR3, CS-DMR5 and CS-DMR7).
  • the prepared active functional monomeric DMRs have 1 H NMR and FTIR spectra similar to those in Fig. 1, indicating that the DMRs were successfully prepared.
  • the prepared CS-DMRs have 1 H NMR and FTIR spectra and contact angles similar to those in Figure 2, indicating that CS-DMRs have been successfully prepared, and their sludge dewatering performance is similar to that of Example 1.

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Abstract

本发明提供一种疏水改性阳离子淀粉絮凝剂及其制备方法和应用，主要是采用接枝共聚的方法，合成了一系列具有不同疏水程度的疏水改性阳离子淀粉絮凝剂。从分子结构来说，该方法不仅可以提高絮凝剂的分子量以及支链上阳离子官能团数目，增强电中和与粘结架桥作用，而且还可以引入大量疏水烷烃链，通过疏水缔合作用改善絮体和泥饼特性；通过上述电中和、粘结架桥及疏水缔合效应的协同作用，有效提高污泥处置性能。本发明疏水改性阳离子淀粉絮凝剂的制备方法简单、合成时间短、产率高、原材料来源广、成本低等优势，为开发和设计绿色环保、低成本、高性能天然高分子絮凝剂提供了新思路及有益的参考。

Description

一种疏水改性阳离子淀粉絮凝剂及其制备方法和应用 技术领域
本发明属于高分子化学合成及环境保护的交叉技术领域，具体涉及一种疏水改性阳离子淀粉絮凝剂及其制备方法和应用。
背景技术
近年来，生活污水和工业污水的排放量日益增加，截止到2014年，全国各市污水处理厂平均日处理能力比上年增长了3.5％，高达12896万m 3/天。巨量的废水经过各级工艺处理后，剩下了含水量较高的剩余污泥，含水率大于92％，加之污泥的处理处置费用昂贵，约占了整个水厂运作成本的一半左右，这使污泥的处理处置成为环境领域面临的巨大挑战。
目前，污泥的处理处置面临两方面的挑战，一方面，污泥作为污水处理的副产物，污泥中含有有毒有害物质，例如病原体，重金属，以及部分有机物，如果直接排放会对生态环境造成严重污染，需要对污泥进行适当处理处置降低其对环境带来的危害。另一方面，未经处理的污泥含水率一般在92％以上，需要对污泥进行脱水，减少污泥体积，降低其储存和运输成本。污泥含水率高是由于污泥颗粒表面会裹着水合层形成一种稳定的胶体悬浮液，这些颗粒带负电相互排斥导致沉降性能和脱水性能差，污泥固液分离比较困难。另外，污泥中的有机成分，尤其是胞外聚合物(EPS)会影响污泥脱水性能，增加污泥脱水难度。污泥脱水以机械脱水为主流工艺，受污泥组成特性的影响，若直接进行机械脱水难以实现良好的脱水效果。因此，机械脱水前，需要对污泥进行预处理便于后续高效脱水。
混凝/絮凝是常规污泥预处理技术之一，混凝/絮凝工艺为后续机械脱水减少污泥体积奠定重要基础。混凝/絮凝法由于操作简单、成本低、适用范围广和处理效果好等优点在废水处理中得到了广泛应用，而混凝/絮凝剂的选择成为了污水处理技术的关键和核心。目前，市场上广为使用的是合成有机高分子絮凝剂如聚丙烯酰胺(PAM)类和无机混凝剂铁盐和铝盐等。尽管无机混凝剂与有机高分子絮凝剂具有良好的混凝/絮凝效果，是目前市场主流的水处理药剂，但在其实际使用过程中由于不可避免的存在金属离子以及高毒性有机单体残留等问题，对水体安全带来了潜在的风险。因此，开发新型、高效、环保的混凝剂/絮凝剂一直是热门研究课题。
基于上述分析，本发明设计一种可控制疏水程度的疏水改性阳离子淀粉絮凝剂，能更为有效的降低泥饼含水率，提高污泥处置性能。
发明内容
本发明提供一种疏水改性阳离子淀粉絮凝剂及其制备方法和应用，该絮凝剂的亲疏水性易于调节，可以更好地与污泥胶体中两亲性EPS相互作用，并且通过接枝共聚的方法，提高絮凝剂的分子量和官能团数目，增强絮凝和污泥脱水性能。
为实现上述技术目的，本发明提供如下技术方案：
一种疏水改性阳离子淀粉絮凝剂，所述疏水改性阳离子淀粉絮凝剂的结构式如下：
Figure PCTCN2021108551-appb-000001
其中，n可为1-12中的任意整数。
本发明还提供一种疏水改性阳离子淀粉絮凝剂的制备方法，包括以下步骤：
步骤一：将有机溶剂、甲基丙烯酰氧乙基二甲基溴化铵和1-溴烷基化合物混合，搅拌，加入有机溶剂洗脱，得到白色产物；
步骤二：在淀粉中加入氢氧化钠进行碱化和糊化反应，然后加入3-氯-2-羟丙基三甲基氯化铵水溶液继续反应，调节pH，得到醚化改性淀粉；
步骤三：在氮气氛围下，在所述醚化改性淀粉中加入过硫酸铵，然后加入丙烯酰胺和所述白色产物，搅拌，反应完成后加入沉淀剂沉淀，过滤，干燥，粉碎，再用丙酮溶液索氏提取，烘干，即得疏水改性阳离子淀粉絮凝剂。
制备疏水改性阳离子淀粉絮凝剂的反应方程式如下：
Figure PCTCN2021108551-appb-000002
其中，CTA代表3-氯-2-羟丙基三甲基氯化铵；AM代表丙烯酰胺；DMRs代表具有不同烷烃链长度的阳离子单体；CS-DMRs代表接枝不同烷烃链长度单体后得到的改性阳离子淀粉絮凝剂；APS代表过硫酸铵。
进一步地，所述白色产物为DMRs，包括：DMR3、DMR5和DMR7。所述得到的疏水改性阳离子淀粉絮凝剂为CS-DMRs，包括：CS-DMR3、CS-DMR5和CS-DMR7。
进一步地，步骤一所述1-溴烷基化合物包括1-溴丙烷、1-溴戊烷和1-溴庚烷中的一种；所述有机溶剂为丙酮。
进一步地，步骤一所述搅拌是在温度为30-60℃条件下搅拌24-72h。
进一步地，步骤一所述有机溶剂与1-溴烷基化合物和甲基丙烯酰氧乙基二甲基溴化铵总摩尔比为2：(1-2)。所述有机溶剂为丙酮。
进一步地，步骤二反应时间为1-3h，反应温度为40-100℃；继续反应时间为2-5h；pH为5-10。
进一步地，步骤三所述醚化改性淀粉质量分数为5-20％。
进一步地，步骤三所述过硫酸铵为新鲜配制的。
进一步地，步骤三所述醚化改性淀粉和过硫酸铵反应10-30min，使得引发剂过硫酸铵与醚化改性淀粉充分反应。
进一步地，步骤三所述过硫酸铵与醚化改性淀粉的摩尔比为1：(5-50)；所述白色产物与丙烯酰胺的摩尔比为(1-6)：(1-6)。
进一步地，步骤三所述白色产物和丙烯酰胺的滴加速度为2滴/s。
进一步地，步骤三所述搅拌为在25-55℃条件下搅拌反应2-10h。保证整个反应在无氧条件下进行。
进一步地，步骤三所述沉淀剂为丙酮或乙醇；所述沉淀剂与疏水改性阳离子淀粉絮凝剂反应体系的体积比为2:1。絮凝剂反应体系包括絮凝剂以及反应体系中溶剂水等。
进一步地，步骤三所述提取为在80-105℃丙酮溶液中索氏提取2天。
本发明还提供疏水改性阳离子淀粉絮凝剂在污泥脱水中的应用。
天然高分子絮凝剂(如：淀粉，纤维素，甲壳素等)具有成本低、绿色环保、来源广泛等特点，其分子结构中通常含有大量的羟基、胺基等活性基团，可借助醚化、胺化、酯化、氧化、接枝共聚等改性方法，向天然高分子中引入不同功能的单体，改善其自身溶解性差、带电荷低、分子量低等缺点，制得种类繁多、高效的水处理剂。絮凝剂的结构决定了其应用性能，此前人们对高分子絮凝剂的开发，注重改性功能基团的选择，主要采用一些亲水性的阳离子单体增强水溶性的同时提高絮凝性能。但是面对亲/疏水性多变的有机污染物以及具有双亲性胞外聚合物包裹的污泥，则需要在絮凝剂分子中引入一些疏水成分，有利于疏水基团与疏水性污染物紧密结合，改善絮凝性能。在污泥脱水过程中，疏水基团可以形成疏水区域，进一步形成粗糙、多孔的泥饼，并且刚性的疏水结构可以充当骨料，改善泥饼的压缩性，有利于内部水分排出。目前，国内外文献中关于具有亲疏水两亲结构的絮凝剂在污泥脱水中应用的报道十分有限。
与现有技术相比，本发明的有益效果为：
(1)本发明采用接枝改性的方法，制得疏水改性的阳离子淀粉絮凝剂，可以调控疏水性；同时可以调节二元共聚单体、引发剂以及淀粉的量，进而控制接枝链的链长和分布，大大的提高了絮凝剂的分子量和官能团数目，增强电中和与粘结架桥作用；同时由于改性后絮凝剂具有疏水性，提高了与污泥表面疏水性物质的结合，有利于絮体的形成和聚集，并且刚性的疏水链还可以充当骨料，提高泥饼的过滤性和脱水性；通过上述电中和、粘结架桥及疏水缔合效应的协同作用，有效提高污泥处置性能。
(2)本发明采用的原料是一种天然高分子：淀粉，其来源广泛、无毒、可生物降解、无二次污染风险，由于淀粉结构中富含大量的羟基等官能团，不仅可以作为基材起到接枝疏水链的作用，还可以辅助协同吸附水体中污染物的作用，有效地增强了天然高分子絮凝剂的应用范围。
(3)由于疏水改性阳离子淀粉絮凝剂的亲疏水性可通过选择不同的单体(DMRs)调节并控制，因此，可根据污泥的不同种类和特点选择合适疏水程度的改性淀粉絮凝剂。
(4)本发明的疏水改性阳离子淀粉絮凝剂不仅具有高效的污泥脱水性能，可以在0.05MPa作用下将污泥含水率降至80％以下，同时还可以降低水体中疏水性有机物和COD值，还兼具有抑菌、除臭等功效。
(5)本发明产品的制备方法和操作工艺简单、合成时间短、原材料来源广、成本低廉、产品使用范围广。该产品是一种经济、绿色、环保的水处理剂，为开发和设计绿色环保、低成本、高性能天然高分子絮凝剂提供了新思路及有益的参考。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为实施例1和对比例1制备的单体DMRs的核磁共振氢谱图；
图2为实施例1和对比例1制备的单体DMRs的傅里叶红外光谱图；
图3为实施例1和对比例1制备的絮凝剂的核磁共振氢谱图；
图4为实施例1和对比例1制备的絮凝剂的傅里叶红外光谱图；
图5为实施例1和对比例1制备的絮凝剂的接触角图；
图6为实施例1和对比例1制备的絮凝剂投加量与泥饼含水率关系图；
图7为实施例1和对比例1制备的絮凝剂与污泥比阻关系图。
具体实施方式
现详细说明本发明的多种示例性实施方式，该详细说明不应认为是对本发明的限制，而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式，并非用于限制本发明。另外，对于本发明中的数值范围，应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小 范围的上限和下限可独立地包括或排除在范围内。
除非另有说明，否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料，但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入，用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时，以本说明书的内容为准。
在不背离本发明的范围或精神的情况下，可对本发明说明书的具体实施方式做多种改进和变化，这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见的。本申请说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等，均为开放性的用语，即意指包含但不限于。
实施例1
步骤一：活性功能单体DMRs的合成：将单体甲基丙烯酰氧乙基二甲基溴化铵和1-溴烷基化合物(包括：1-溴丙烷、1-溴戊烷或1-溴庚烷)溶解在有机溶剂丙酮中(其中丙酮、单体甲基丙烯酰氧乙基二甲基溴化铵和1-溴烷基化合物的摩尔比2:1:1)，60℃下搅拌24h，待反应物完全反应，溶剂挥发，洗脱后得到白色产物DMRs(包括DMR3、DMR5和DMR7)；
步骤二：醚化改性淀粉的制备：将5g淀粉和2g NaOH的加入水中，在90℃下碱化和糊化1h，滴加3g 3-氯-2-羟丙基三甲基氯化铵水溶液，继续反应5h后，滴加0.1mol/L的氢氧化钠水溶液调制pH至10，得到醚化改性淀粉；
步骤三：疏水改性阳离子淀粉絮凝剂的制备：充分溶解得到的醚化改性淀粉于100mL水溶液中，使醚化改性淀粉质量分数为20％，于60℃条件下搅拌1小时，并通入氮气，加入新鲜配制的过硫酸铵溶液，反应30min,使得过硫酸铵溶液与醚化改性淀粉充分反应，其中过硫酸铵与醚化改性淀粉的摩尔比为1:5；以2滴/s的速度向体系中滴加DMRs与丙烯酰胺共聚单体，其摩尔比为1:6，在55℃条件下搅拌反应10h，保证整个反应在无氧条件下进行，反应完成后，加入沉淀剂乙醇，其中乙醇与产物溶液的体积比为2:1，将产物沉淀、干燥、粉碎，在105℃丙酮溶液中索氏提取2天，烘干，得到粉末状疏水改性阳离子淀粉絮凝剂CS-DMRs (包括：CS-DMR3、CS-DMR5及CS-DMR7)。
对比例1
同实施例1，区别在于以甲基丙烯酰氧乙基三甲基氯化铵(DMR1)作为活性功能单体，制得一种亲水性改性阳离子淀粉絮凝剂(CS-DMR1)。
试验例：
1、图1为实施例1和对比例1制备的单体DMRs的核磁共振氢谱图，从图中可以看出，化学位移δ为6.09ppm(a)和5.71ppm(b)的峰被指定为H 2C＝C；化学位移δ＝1.87ppm(c)是＝C–CH 3；化学位移δ＝4.55ppm(d)是O–CH 2–；化学位移δ＝3.70ppm(e)，3.32ppm(f)，3.08ppm(g)是与季铵盐–N +(CH 3) n连接的碳氢C-H振动峰；长的烷烃链–(CH 2) 6CH 3碳氢振动峰的化学位移位于δ1.71ppm(h)，1.21ppm(i)，1.28ppm(j)，0.78ppm(k)。
图2为实施例1和对比例1制备的DMRs单体的FTIR光谱图，从图中可以看出，1720cm -1处的特征峰是由于DMRs上的C＝O伸缩振动引起的。1477和952cm -1峰对应于DMRs上N +(CH 3)上的C-H振动峰。
1HNMR和FTIR光谱结果表明，活性功能单体DMRs被成功制备。
2、图3为实施例1和对比例1制备的CS-DMRs的核磁共振氢谱图，图4为实施例1和对比例1制备的CS-DMRs的傅里叶红外光谱图。从图中可以看出，对于AM单体,在 1HNMR波谱中其亚甲基和甲基质子的化学位移分别为2.10ppm和1.55ppm。在FTIR光谱中，在1664cm -1处观察到AM上CONH 2基团的C＝O伸缩振动特征峰。对于单体DMRs，在FTIR波谱中，在1720、1477和952cm -1处的红外特征峰对应于羰基的伸缩振动。在 1HNMR波谱中，季铵盐甲基质子振动的化学位移为3.20ppm。
根据以上 1HNMR和FTIR信息表明：单体AM与DMRs被成功接枝到CS上。
图5为实施例1和对比例1制备的CS-DMRs的接触角。接触角作为衡量材料疏水性的一个重要参数，样品的接触角大小与疏水性呈正相关。合成过程中通过调节反应单体DMRs与AM的比例以及总的摩尔量不变，制得具有相同电荷密度不同疏水度的CS-DMRs。如图5所示，表征了絮凝剂CS-DMRs的亲疏水性。在这些絮凝剂CS-DMRs中，接触角的大小顺序为CS-DMR7>CS-DMR5>CS-DMR3>CS-DMR1，也表明它的疏水性的强弱顺序，这一结论与絮凝剂的结构相一致，CS-DMR7中含 有最长的疏水烷烃链结构，其接触角最大为61.32°，并且CS-DMRs的接触角均小于90°表明其溶解性也相对较好。
3、图6-7为实施例1和对比例1制备的CS-DMRs投加量与泥饼含水率和污泥比阻的关系图。从图中可以看出，随着CS-DMRs投加量从0.5mg/g TSS增加到3.5mg/g TSS，FCMC和SRF均先快速下降，继续增加投加量到最优投加量后，FCMC和SRF数值变化不大趋于稳定。在这4种CS-DMRs絮凝剂中，具有最高疏水性的CS-DMR7拥有最优异的脱水性能，能将FCMC从95.47％下降到79.26％。不仅FCMC和SRF数值较低，而且最优投加量也相对较低。CS-DMRs絮凝剂之间存在明显不同的脱水性能差异主要归因于其疏水程度不同，进一步说明絮凝剂的疏水结构有利于污泥的脱水。也就是说，具有亲疏水结构的有机高分子絮凝剂，由于疏水缔合与电中和及粘结架桥效应的协同作用，在提高污泥脱水性能方面优于亲水性有机高分子絮凝剂。
实施例2
步骤一：活性功能单体DMRs的合成：将单体甲基丙烯酰氧乙基二甲基溴化铵和1-溴烷基化合物(包括：1-溴丙烷、1-溴戊烷和1-溴庚烷)溶解在有机溶剂丙酮中(其中丙酮、单体甲基丙烯酰氧乙基二甲基溴化铵和1-溴烷基化合物的摩尔比2:1:0.5)，45℃下搅拌48h，待反应物完全反应，溶剂挥发，洗脱后得到白色产物DMRs(包括DMR3、DMR5和DMR7)；
步骤二：醚化改性淀粉的制备：将5g淀粉分散于水溶液中，然后加入0.5g NaOH，在80℃条件下碱化和糊化3h，滴加2g 3-氯-2-羟丙基三甲基氯化铵水溶液，继续反应4h后，滴加0.1mol/L的氢氧化钠水溶液调制pH至5，得到醚化改性淀粉。
步骤三：疏水改性阳离子淀粉絮凝剂的制备：充分溶解得到的醚化改性淀粉于100mL水溶液中，使醚化改性淀粉质量分数为15％，并通入氮气，于水浴40℃条件下搅拌使其充分溶解，加入新鲜配制的过硫酸铵溶液，反应30min,使得过硫酸铵溶液与醚化改性淀粉充分反应，其中过硫酸铵与醚化改性淀粉的摩尔比为1:20。以2滴/s的速度向体系中滴加DMRs与丙烯酰胺共聚单体，其摩尔比为5:2，在45℃条件下搅拌反应6h，保证整个反应在氮气条件下进行，反应完成后，加入沉淀剂丙酮，其中丙酮与产物溶液的体积比为2:1，将产物沉淀、干燥、粉 碎，在85℃丙酮溶液中索氏提取2天，烘干，得到粉末状疏水改性阳离子淀粉絮凝剂CS-DMRs(包括：CS-DMR3、CS-DMR5及CS-DMR7)。
经检测，得到的DMRs具有与图1相似的 1H NMR和FTIR光谱，表明DMRs被成功制备。制得的CS-DMRs具有与图2相似的 1H NMR和FTIR光谱以及接触角，表明CS-DMRs已被成功制备，其污泥脱水性能类同实施例1。
实施例3
步骤一：活性功能单体DMRs的合成：将单体甲基丙烯酰氧乙基二甲基溴化铵和1-溴烷基化合物(包括：1-溴丙烷、1-溴戊烷或1-溴庚烷)溶解在有机溶剂丙酮中(其中丙酮、单体甲基丙烯酰氧乙基二甲基溴化铵和1-溴烷基化合物的摩尔比2:1:1)，30℃下搅拌24h，待反应物完全反应，溶剂挥发，洗脱后得到白色产物DMRs(包括DMR3、DMR5和DMR7)；
步骤二：醚化改性淀粉的制备：将5g淀粉加入到1.0g NaOH中并在60℃水浴的碱性条件下糊化1h，滴加1.5g 3-氯-2-羟丙基三甲基氯化铵水溶液，继续保持60℃条件下反应4h后，此时溶液呈现咖啡色，滴加0.1mol/L的氢氧化钠水溶液调制pH至6，得到醚化改性淀粉；
步骤三：疏水改性阳离子淀粉絮凝剂的制备：充分溶解得到的醚化改性淀粉于100mL水溶液中，使醚化改性淀粉质量分数为10％，于60℃条件下搅拌1小时，并通入氮气，加入新鲜配制的过硫酸铵溶液，反应15min,使得过硫酸铵溶液与醚化改性淀粉充分反应，其中过硫酸铵与醚化改性淀粉的摩尔比为1:25。以2滴/s的速度向体系中滴加DMRs与丙烯酰胺共聚单体，其摩尔比为2:5，在25℃条件下搅拌反应3h，保证整个反应在无氧条件下进行，反应完成后，加入沉淀剂乙醇，其中乙醇与产物溶液的体积比为2:1，将产物沉淀、干燥、粉碎，在100℃丙酮溶液中索氏提取2天，烘干，得到粉末状疏水改性阳离子淀粉絮凝剂CS-DMRs(包括：CS-DMR3、CS-DMR5及CS-DMR7)。
制得的活性功能单体DMRs具有与图1相似的 1H NMR和FTIR光谱，表明DMRs被成功制备。制得的CS-DMRs具有与图2相似的 1H NMR和FTIR光谱以及接触角，表明CS-DMRs已被成功制备，其污泥脱水性能类同实施例1。
实施例4
步骤一：活性功能单体DMRs的合成：以单体甲基丙烯酰氧乙基二甲基溴化 铵和1-溴烷基化合物(包括：1-溴丙烷、1-溴戊烷或1-溴庚烷)为溶质，以丙酮为溶剂，将溶质溶解在溶剂中(其中丙酮、单体甲基丙烯酰氧乙基二甲基溴化铵和1-溴烷基化合物的摩尔比2:0.5:0.5)，50℃下搅拌72h，待反应物完全反应，溶剂挥发，洗脱后得到白色产物DMRs(包括DMR3、DMR5和DMR7)；
步骤二：醚化改性淀粉的制备：将1.5g NaOH加入到5g淀粉的水溶液中，在40℃下碱化和糊化1.5h，滴加2g 3-氯-2-羟丙基三甲基氯化铵水溶液，继续反应2.5h后，滴加0.1mol/L的氢氧化钠水溶液调制pH至8，得到醚化改性淀粉。
步骤三：疏水改性阳离子淀粉絮凝剂的制备：充分溶解得到的醚化改性淀粉于100mL水溶液中，使醚化改性淀粉质量分数为10％，并通入氮气，于40℃水浴条件下搅拌1小时，加入新鲜配制的过硫酸铵溶液，反应10min,使得过硫酸铵溶液与醚化改性淀粉充分反应，其中过硫酸铵与醚化改性淀粉的摩尔比为1:30。以2滴/s的速度向体系中滴加DMRs与丙烯酰胺共聚单体，其摩尔比为4:3，在30℃条件下搅拌反应10h，保证整个反应在无氧条件下进行，反应完成后，加入沉淀剂乙醇，其中乙醇与产物溶液的体积比为2:1，将产物沉淀、干燥、粉碎，在80℃丙酮溶液中索氏提取2天，烘干，得到粉末状疏水改性阳离子淀粉絮凝剂CS-DMRs(包括：CS-DMR3、CS-DMR5及CS-DMR7)。
制得的活性功能单体DMRs具有与图1相似的 1H NMR和FTIR光谱，表明DMRs被成功制备。制得的CS-DMRs具有与图2相似的 1H NMR和FTIR光谱以及接触角，表明CS-DMRs已被成功制备，其污泥脱水性能类同实施例1。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 一种疏水改性阳离子淀粉絮凝剂，其特征在于，所述疏水改性阳离子淀粉絮凝剂的结构式如下：
    Figure PCTCN2021108551-appb-100001
    其中，n可为1-12中的任意整数。
  2. 一种如权利要求1所述的疏水改性阳离子淀粉絮凝剂的制备方法，其特征在于，包括以下步骤：
    步骤一：将有机溶剂、甲基丙烯酰氧乙基二甲基溴化铵和1-溴烷基化合物混合，搅拌，加入有机溶剂洗脱，得到白色产物；
    步骤二：在淀粉中加入氢氧化钠进行碱化和糊化反应，然后加入3-氯-2-羟丙基三甲基氯化铵水溶液继续反应，调节pH，得到醚化改性淀粉；
    步骤三：在氮气氛围下，在所述醚化改性淀粉中加入过硫酸铵，然后加入丙烯酰胺和所述白色产物，搅拌，反应完成后加入沉淀剂沉淀，过滤，干燥，粉碎，再用丙酮溶液索氏提取，烘干，即得疏水改性阳离子淀粉絮凝剂。
  3. 根据权利要求2所述的制备方法，其特征在于，步骤一所述1-溴烷基化合物包括1-溴丙烷、1-溴戊烷和1-溴庚烷中的一种；所述有机溶剂为丙酮。
  4. 根据权利要求2所述的制备方法，其特征在于，步骤一所述搅拌是在温度为30-60℃条件下搅拌24-72h。
  5. 根据权利要求2所述的制备方法，其特征在于，步骤一所述有机溶剂与1-溴烷基化合物和甲基丙烯酰氧乙基二甲基溴化铵的总摩尔比为2：(1-2)。
  6. 根据权利要求2所述的制备方法，其特征在于，步骤二反应时间为1-3h，反应温度为40-100℃；继续反应时间为2-5h，pH为5-10。
  7. 根据权利要求2所述的制备方法，其特征在于，步骤三所述醚化改性淀粉质量分数为5-20％。
  8. 根据权利要求2所述的制备方法，其特征在于，步骤三所述过硫酸铵与所述醚化改性淀粉的摩尔比为1：(5-50)；所述白色产物与所述丙烯酰胺的摩尔比为(1-6)：(1-6)。
  9. 一种如权利要求2-8任一项所述的制备方法制备的疏水改性阳离子淀粉絮凝剂在污泥脱水中的应用。
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