CN113621092B - Microbubble surface function modifier and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of sewage treatment, and provides a preparation method of a microbubble surface function modifier, which comprises the following steps: mixing hydroxypropyl trimethyl ammonium chloride chitosan aqueous solution and n-butyl aldehyde or/and 1-octyl aldehyde ethanol solution, heating for reaction, then adding sodium cyanoborohydride aqueous solution for reaction, separating and purifying to obtain the amphiphilic chitosan, namely the microbubble surface function modifier. The amphiphilic chitosan has the quaternary ammonium salt substitution degree of 85-120 percent and the alkyl substitution degree of 80-120 percent; can be applied to sewage treatment, in particular to the treatment of high algae-containing wastewater by microbubble modified air flotation. The amphiphilic chitosan is simple to prepare, high in substitution degree and good in stability, has the effects of neutralizing and adsorbing electronegative pollutants, and ensures that modified microbubbles are not easy to break; has the characteristics of wide application range, good water outlet quality and the like.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and relates to a microbubble surface function modifier and a preparation method thereof.
Background
At present, the problem of lake and reservoir water source pollution is increasingly prominent, wherein the algae pollution is particularly serious. Eutrophication of water in lake and reservoir water causes mass propagation of algae, which causes water quality problems such as odor, algal toxins, disinfection by-products and the like. As the algae cells have the characteristics of small specific gravity, high negative charge, strong stability and the like, the algae cells are difficult to sink in water, the traditional coagulating sedimentation process is difficult to effectively remove, and a series of problems of filter chamber blockage, short backwashing period, increased dosage and the like are caused. A traditional Dissolved Air Flotation (DAF) process generates micro bubbles with the diameter of 0.1-100 mu m, does not damage algal cells in the air flotation process, can effectively avoid the release risk of algal toxins, odor substances and algae-derived organic matters, and is widely applied to an algae removal process. But the micro-bubble gas-liquid interface is easy to adsorb OH - And the algae cells and the algae-derived organic matters have electronegativity (-7 to-17 mV) at the same time when the algae cells and the algae-derived organic matters are negatively charged (-50 to-20 mV), so that electrostatic repulsion between the microbubbles and the algae influences the adhesion effect and the stability. In addition, van der waals force is lacked between microbubbles and algae, the common microbubble sweeping area is small, the trapping effect between microbubbles and algae is poor, and adhesion is unstable and easy to desorb. It can be seen that the surface properties (surface charge, surface force, etc.) of the microbubbles are key influencing factors for dissolved air flotation.
The microbubble surface function modification air floatation technology not only ensures that microbubbles are not easy to break, but also overcomes the electrostatic repulsion between the microbubbles and algae cells to ensure that the microbubbles are easier to contact and adhere with the algae cells by adding a surface modifier into an air dissolving system and simultaneously ensuring that the surface of the microbubbles generates positive charges, bridges and other functional characteristics while generating bubbles, thereby improving the treatment capacity of air dissolving air floatation and improving the quality of outlet water.
Chitosan (CTS) is a cationic polysaccharide polymer existing in nature, contains abundant free amino, N-acetamido and hydroxyl in molecules, and has strong adsorption and electric neutralization capacity; meanwhile, the chitosan has a complex spiral linear molecular structure, the long-chain characteristic of the polymer can form an interception network, the surface contact area of microbubbles is increased, and a large amount of algae cells can be adsorbed to form a floc structure of 'microbubble-macromolecule-algae cells', so that the adhesion efficiency is enhanced, and the adsorption and bridging effects are exerted. Meanwhile, the chitosan has the characteristics of no toxicity, no harm, easy biodegradation and environmental friendliness, and is approved by the United states environmental protection agency as a purifying agent for drinking water. However, chitosan has the defects of large influence by pH, poor solubility, no hydrophilic and hydrophobic structures and the like, is attached to the surface of micro bubbles only by electrostatic force, is easy to desorb under poor hydraulic conditions, has large influence on the quality of effluent water, and limits the application of the chitosan. The chitosan can be used for modifying, activating and coupling amino and hydroxyl with stronger activity on a chitosan molecular chain, and recent researches show that the chitosan serving as a microbubble surface modifier has larger optimization space and wide application prospect.
Disclosure of Invention
The invention aims to provide safe, efficient, environment-friendly and green amphiphilic chitosan and a preparation method thereof aiming at the problems in the conventional microbubble surface function modification air floatation technology, and the amphiphilic chitosan can be used as a bubble modifier for the high algae water enhanced modification air floatation algae removal technology.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of amphiphilic chitosan comprises the following steps:
(1) Mixing a hydroxypropyl trimethyl ammonium chloride chitosan aqueous solution and an ethanol solution of n-butyl aldehyde or/and 1-octyl aldehyde, and heating for complete reaction to obtain a reaction mixture;
(2) And adding a sodium cyanoborohydride aqueous solution into the reaction mixture to react completely, and separating and purifying the reaction liquid to obtain a product, namely the amphiphilic chitosan.
Preferably, the substitution degree of the quaternary ammonium salt of the hydroxypropyl trimethyl ammonium chloride chitosan is 85% -120%.
Preferably, the molar ratio of the hydroxypropyl trimethyl ammonium chloride chitosan to aldehyde is 1 (0.5-2).
Preferably, the reaction temperature in step (1) is 40-80 ℃.
Preferably, the molar ratio of sodium cyanoborohydride to aldehyde in step (2) is 1.
Preferably, the separation and purification steps in the step (2) are as follows: adding acetone into the reaction solution, separating to obtain a precipitate, washing the precipitate with acetone, and drying the precipitate to obtain the catalyst.
Preferably, the hydroxypropyl trimethyl ammonium chloride chitosan is prepared by the following method:
(i) Dissolving chitosan in an acetic acid solution, then alkalifying with NaOH, separating to obtain a precipitate, and washing to be neutral to obtain the alkalified chitosan;
(ii) Dispersing the alkalized chitosan into isopropanol, dropwise adding an isopropanol solution of 2, 3-epoxypropyltrimethylammonium chloride under the heating condition to react until the reaction is finished, and then separating and purifying to obtain the hydroxypropyl trimethyl ammonium chloride chitosan.
Preferably, the deacetylation degree of the chitosan is more than or equal to 95%.
Preferably, the pH after basification is 9.
Preferably, the mass ratio of the chitosan to the 2, 3-epoxypropyltrimethylammonium chloride is 1: (1-3).
Preferably, the reaction temperature in step (ii) is 65-85 ℃; the reaction time is 8-10h.
Preferably, the separation and purification step in step (ii) is: adding absolute ethyl alcohol into the reaction solution, separating to obtain a precipitate, washing the precipitate with absolute ethyl alcohol, and drying.
Preferably, the concentration of the acetic acid solution is 1-2%.
The amphiphilic chitosan obtained by the preparation method has the quaternary ammonium salt substitution degree of 85-120% and the alkyl substitution degree of 80-120%.
An application of the amphiphilic chitosan in sewage treatment.
Preferably, the sewage is algae-containing wastewater.
Preferably, the treatment method is microbubble modified air flotation.
The invention has the following advantages:
the amphiphilic chitosan is prepared by taking chitosan as a raw material and respectively carrying out hydrophilic group association with 2, 3-epoxypropyltrimethylammonium chloride (GTMAC), so that the amphiphilic chitosan has a quaternary ammonium group with a hydrophilic structure and the water solubility of the chitosan is enhanced; and grafting with n-butyl aldehyde and 1-octyl aldehyde respectively to connect two alkyl groups with different carbon chain lengths on a chitosan molecular chain, so that the chitosan molecular chain has a hydrophobic structure, the chitosan is firmly attached to the surface of the micro-bubble and is not easy to desorb, the micro-particle in the sewage is destabilized, and the collision adhesion efficiency of the micro-bubble and algae cells or other solid small particles is improved.
The amphiphilic chitosan takes 2, 3-epoxypropyltrimethylammonium chloride as a hydrophilic group to be associated with chitosan, on one hand, the amphiphilic chitosan can generate a hydrophilic acting force with the hydrophilic group of soluble organic matters in water, the adsorption effect of the hydrophilic group and the soluble organic matters in water is enhanced, the decontamination efficiency of air floatation is improved, on the other hand, the water solubility and the oxidation resistance of chitosan are enhanced, the pH range of use is wide, the using amount is small, and the cost is low. The chitosan is grafted with chitosan by taking n-butyl and n-octyl as hydrophobic groups, the functionality of the chitosan is expanded, the long-chain hydrophobic side group strengthens the adhesion effect of the chitosan and the surfaces of micro-bubbles, and the long-chain hydrophobic side group can be firmly adhered to the surfaces of the micro-bubbles under the action of hydrophobic force and electrostatic attraction to generate a region with positive charges, so that the electrostatic repulsion between the micro-bubbles and algae cells is overcome, the formed air-borne algae flocs are stable and difficult to desorb, the algae cells and the chitosan can conveniently enter a scum layer along with the micro-bubbles, and the algae removal process is completed. The introduction of the long-chain hydrophobic groups also increases the contact area of chitosan with microbubbles and algae cells, plays a role in bridging, and is easier to capture pollutants in water to strengthen collision adhesion efficiency, thereby realizing the surface function modification of the microbubbles and further strengthening the air floatation performance.
The amphiphilic chitosan and the algae-derived organic matter in the raw water both have long-chain structures, the amphiphilic chitosan and the microbubbles and the algae cells can form a microbubble-amphiphilic chitosan-algae-derived organic matter-algae cell network structure to enhance the pollution removal effect, intermolecular hydrogen bonds formed by the chitosan, the algae cells and the algae-derived organic matter enhance the stability of the network structure, and the amphiphilic chitosan and the algae-derived organic matter have strong cohesive force and capture capacity on pollutants in water.
The amphiphilic chitosan is simple to prepare, high in substitution degree and good in stability, has the effects of neutralizing and adsorbing electronegative pollutants, and ensures that modified microbubbles are not easy to break; has the characteristics of wide application range, good water outlet quality and the like.
Drawings
FIG. 1 is a Fourier transform Infrared Spectroscopy (FTIR) plot of Chitosan (CTS) and the amphiphilic chitosans obtained in examples 1-4;
FIG. 2 is a scanning electron micrograph of Chitosan (CTS) and the amphiphilic chitosan obtained in examples 1-4.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited to the following examples.
Example 1 Synthesis of amphiphilic Chitosan
(1) Weighing 3g of chitosan (the deacetylation degree is 95 percent) and dissolving in 150mL of 2 percent acetic acid solution, then dropwise adding 1mol/L NaOH solution until the pH value is 9, and stirring for 12h at room temperature for alkalization; then carrying out centrifugal separation to obtain a precipitate, and washing the precipitate to be neutral by using water to obtain the alkalized chitosan;
(2) Weighing 3g of 2, 3-epoxypropyltrimethylammonium chloride, adding a small amount of isopropanol, and dissolving to obtain about 20mL of solution;
(3) Adding 100mL of isopropanol into the alkalized chitosan, violently stirring for 1h at 50 ℃ to uniformly disperse the chitosan in the isopropanol, slowly heating to 85 ℃, dropwise adding the isopropanol solution of 2, 3-epoxypropyltrimethylammonium chloride within 1h, continuously heating and stirring for reaction for 8h, cooling the reaction solution to room temperature, adding 150mL of absolute ethanol, centrifuging to obtain a precipitate, washing the precipitate with the absolute ethanol, drying at 80 ℃ to constant weight to obtain 2.7g of hydroxypropyltrimethylammonium chloride chitosan with the quaternary ammonium salt substitution degree of about 89%, and grinding to 100 meshes for later use;
(4) Weighing 0.5g of hydroxypropyl trimethyl ammonium chloride chitosan, dissolving in 50mL of distilled water, mixing 0.2mL of 1-octanal, dissolving in 50mL of absolute ethyl alcohol, mixing the two, heating and stirring at 40 ℃, and reacting for 8 hours to obtain a reaction mixture;
(5) Weighing 0.09g of sodium cyanoborohydride, dissolving in water, adding into the reaction mixture obtained in the step (4), stirring for reaction for 12h, adding 100mL of acetone into the reaction solution, performing centrifugal separation to obtain a precipitate, washing the precipitate with acetone for 3 times, and performing vacuum drying on the precipitate at 50 ℃ for 12h to obtain 0.41g of amphiphilic chitosan, wherein an infrared spectrogram and a scanning electron microscope picture are shown in the figure 1 and 2 respectively.
The amphiphilic chitosan was determined to have a degree of quaternized substitution of 88.64% and a degree of alkylated substitution of 93.58%.
Example 2 Synthesis of amphiphilic Chitosan
(1) Weighing 3g of chitosan (the deacetylation degree is 95 percent) and dissolving in 150mL of 2 percent acetic acid solution, then dropwise adding 1mol/L NaOH solution until the pH value is 9, and stirring for 10h at room temperature for alkalization; then, carrying out centrifugal separation to obtain a precipitate, and washing the precipitate to be neutral by using water to obtain the alkalized chitosan;
(2) Weighing 3g of 2, 3-epoxypropyltrimethylammonium chloride, adding a small amount of isopropanol, and dissolving to obtain about 20mL of solution;
(3) Adding 100mL of isopropanol into the alkalized chitosan, violently stirring for 1h at 50 ℃ to uniformly disperse the chitosan in the isopropanol, slowly heating to 75 ℃, dropwise adding an isopropanol solution of 2, 3-epoxypropyltrimethylammonium chloride within 1h, continuously heating and stirring for reaction for 9h, cooling the reaction solution to room temperature, adding 150mL of absolute ethyl alcohol, centrifuging to obtain a precipitate, washing the precipitate with the absolute ethyl alcohol, drying at 80 ℃ to constant weight to obtain 2.7g of hydroxypropyl trimethylammonium chloride chitosan with the quaternary ammonium salt substitution degree of about 93%, and grinding to 100 meshes for later use;
(4) Weighing 0.5g of hydroxypropyl trimethyl ammonium chloride chitosan, dissolving in 50mL of distilled water, mixing 0.2mL of 1-octanal, dissolving in 50mL of absolute ethyl alcohol, mixing the two, and heating and stirring at 80 ℃ for reacting for 6 hours to obtain a reaction mixture;
(5) Weighing 0.09g of sodium cyanoborohydride, dissolving in water, adding into the reaction mixture obtained in the step (4), stirring for reaction for 12h, adding 100mL of acetone into the reaction solution, performing centrifugal separation to obtain a precipitate, washing the precipitate with acetone for 3 times, and performing vacuum drying on the precipitate at 50 ℃ for 12h to obtain 0.43g of amphiphilic chitosan, wherein an infrared spectrogram and a scanning electron microscope picture are shown in the figure 1 and 2 respectively.
The quaternary ammonium substitution degree of the amphiphilic chitosan is 92.38 percent and the alkylation substitution degree is 95.06 percent.
Example 3 Synthesis of amphiphilic Chitosan
(1) Weighing 3g of chitosan (the deacetylation degree is 99%) and dissolving the chitosan in 150mL of 1% acetic acid solution, then dropwise adding 1mol/L NaOH solution until the pH value is 9, and stirring for 8h at room temperature for alkalization; then, carrying out centrifugal separation to obtain a precipitate, and washing the precipitate to be neutral by using water to obtain the alkalized chitosan;
(2) 6g of 2, 3-epoxypropyltrimethylammonium chloride is weighed and dissolved by adding a small amount of isopropanol to obtain about 20mL of solution;
(3) Adding 100mL of isopropanol into the alkalized chitosan, violently stirring for 1h at 50 ℃ to uniformly disperse the chitosan in the isopropanol, slowly heating to 65 ℃, dropwise adding the isopropanol solution of 2, 3-epoxypropyltrimethylammonium chloride within 1h, continuously heating and stirring for reaction for 9h, cooling the reaction solution to room temperature, adding 150mL of absolute ethanol, centrifuging to obtain a precipitate, washing the precipitate with the absolute ethanol, drying at 80 ℃ to constant weight to obtain 3.1g of hydroxypropyltrimethylammonium chloride chitosan with the quaternary ammonium salt substitution degree of 103%, and grinding to 100 meshes for later use;
(4) Weighing 0.5g of hydroxypropyl trimethyl ammonium chloride chitosan, dissolving in 50mL of distilled water, mixing and dissolving 0.23mL of n-butyl aldehyde in 50mL of absolute ethyl alcohol, mixing the two, and heating and stirring at 80 ℃ for reaction for 6 hours to obtain a reaction mixture;
(5) Weighing 0.18g of sodium cyanoborohydride, dissolving in water, adding into the reaction mixture obtained in the step (4), stirring for reaction for 10 hours, adding 100mL of acetone into the reaction solution, performing centrifugal separation to obtain a precipitate, washing the precipitate with acetone for 3 times, and performing vacuum drying on the precipitate at 50 ℃ for 12 hours to obtain 0.4g of amphiphilic chitosan, wherein the infrared spectrogram of the amphiphilic chitosan is shown in figure 1, and the scanning electron micrograph is shown in figure 2.
The amphiphilic chitosan is measured to have the quaternization substitution degree of 103.37 percent and the alkylation substitution degree of 118.34 percent.
Example 4 Synthesis of amphiphilic Chitosan
(1) Weighing 3g of chitosan (deacetylation degree is 99%) and dissolving the chitosan in 150mL of 2% acetic acid solution, then dropwise adding 1mol/L NaOH solution until the pH value is 9, and stirring for 10h at room temperature for alkalization; then carrying out centrifugal separation to obtain a precipitate, and washing the precipitate to be neutral by using water to obtain the alkalized chitosan;
(2) Weighing 9g of 2, 3-epoxypropyltrimethylammonium chloride, adding a small amount of isopropanol to dissolve the chloride to obtain about 20mL of solution;
(3) Adding 100mL of isopropanol into the alkalized chitosan, violently stirring for 1h at 50 ℃ to uniformly disperse the chitosan in the isopropanol, slowly heating to 75 ℃, dropwise adding an isopropanol solution of 2, 3-epoxypropyltrimethylammonium chloride within 1h, continuously heating and stirring for reaction for 8h, cooling the reaction solution to room temperature, adding 150mL of absolute ethyl alcohol, centrifuging to obtain a precipitate, washing the precipitate with the absolute ethyl alcohol, drying at 80 ℃ to constant weight to obtain 3.3g of hydroxypropyl trimethylammonium chloride chitosan with the quaternary ammonium salt substitution degree of about 105%, and grinding to 100 meshes for later use;
(4) Weighing 0.5g of hydroxypropyl trimethyl ammonium chloride chitosan, dissolving in 50mL of distilled water, mixing and dissolving 0.45mL of n-butyl aldehyde in 50mL of absolute ethyl alcohol, mixing the two, and heating and stirring at 80 ℃ for reaction for 4 hours to obtain a reaction mixture;
(5) Weighing 0.36g of sodium cyanoborohydride, dissolving in water, adding into the reaction mixture obtained in the step (4), stirring for reaction for 12h, adding 100mL of acetone into the reaction solution, performing centrifugal separation to obtain a precipitate, washing the precipitate with acetone for 3 times, and performing vacuum drying on the precipitate at 50 ℃ for 12h to obtain 0.39g of amphiphilic chitosan, wherein the infrared spectrogram of the amphiphilic chitosan is shown in figure 1, and the scanning electron micrograph is shown in figure 2.
The amphiphilic chitosan is measured to have 104.45 percent of quaternization substitution degree and 112.08 percent of alkylation substitution degree.
As can be seen from FIG. 1, examples 1 to 4 obtained an IR spectrum of 3481cm in the sample -1 Is the stretching vibration peak of CTS hydroxyl (-OH) at 1600cm -1 In the form of CTS free amino (-NH) 2 ) Characteristic absorption peak of 2928 cm -1 And 2857 cm -1 Is methyl (-CH) on CTS 3 ) And methylene (-CH) 2 -) peak of stretching vibration. After the CTS is modified by quaternization, the absorption peak of free amino groups is weakened, a characteristic absorption peak representing imine (-NH-) appears at 1669cm-1, and the absorption peak at 1480cm -1 In which-CH in a quaternary ammonium group is present 3 Characteristic absorption peak of (2), indicating 2, 3-ring-NH of oxypropyltrimethylammonium chloride with chitosan 2 The reaction produced hydroxypropyl trimethyl ammonium chloride chitosan (HTCC). The HTCC is 2928 cm after being subjected to alkylation modification -1 And 2857 cm -1 Has an increased peak intensity of 1669cm -1 The absorption peak at-NH-is further enhanced compared with HTCC, which shows that aldehyde compounds with different carbon chain lengths and-NH of CTS 2 The reaction takes place and amphiphilic chitosan is formed.
As can be seen from fig. 2, in the scanning electron micrographs of the samples obtained in examples 1 to 4, the CTS is in a sheet structure before modification, and the surface is smoother, more uniform in morphology and small in porosity compared to the surface after modification, and the CTS has higher crystallinity at this time. The surface appearance after modification is relatively close, after quaternization and alkylation modification, the surface of the modified material has a dense pore structure, becomes rough and has dense pores, probably because the crystallinity of the modified material is damaged by introducing quaternary ammonium groups and alkyl groups, the structure is loose, an obvious layered structure appears, and a plurality of aggregate particles appear on the surface, because the crystal structure of the modified material is seriously weakened compared with that of unmodified CTS.
Example 5 Synthesis of amphiphilic Chitosan
(1) Weighing 0.5g of hydroxypropyl trimethyl ammonium chloride chitosan obtained in example 2, dissolving in 50mL of distilled water, mixing 0.2mL of 1-octanal and dissolving in 50mL of absolute ethyl alcohol, mixing the two, and heating and stirring at 60 ℃ for reacting for 4 hours to obtain a reaction mixture;
(2) Weighing 0.09g of sodium cyanoborohydride, dissolving in water, adding into the reaction mixture obtained in the step (4), stirring for reaction for 12h, adding 100mL of acetone into the reaction solution, performing centrifugal separation to obtain a precipitate, washing the precipitate with acetone for 3 times, and performing vacuum drying on the precipitate at 50 ℃ for 12h to obtain 0.42g of amphiphilic chitosan.
The quaternary ammonium substitution degree of the amphiphilic chitosan is determined to be 92.38%, and the alkylation substitution degree is determined to be 113.59%.
Application example 1 treatment of algae-containing wastewater with different modifiers
Taking a plurality of parts of high algae sewage, wherein the initial algae density is 6 multiplied by 10 5 The amphiphilic chitosan in the embodiment 1 to 5 is respectively added into the chitosan solution per mL according to the dosage of 1.0mg/L, and the adding amount is the sameThe chitosan (degree of deacetylation: 95%), the hydroxypropyl trimethyl ammonium chloride chitosan, polydimethyl diallyl ammonium chloride, and hexadecyl trimethyl ammonium bromide of example 2 were compared, and the removal rate of algal cells and UV were determined by 10-minute microbubble air flotation 254 The removal rate and turbidity removal rate are shown in Table 1.
TABLE 1 treatment effect of different modifiers on algae-containing wastewater
As can be seen from the data in Table 1: the pollution removal effect of the modified chitosan is greatly improved, which is related to alkylation modification, the degree of substitution of alkylation reaches more than 90%, and the pollution removal effect is not obviously improved. The water solubility of the modifier is significantly improved with higher quaternization substitution. The amphiphilic chitosan prepared by the invention can more firmly act on the surface of the micro-bubble, thereby having better pollution removal efficiency.
Claims (8)
1. The preparation method of the amphiphilic chitosan is characterized by comprising the following steps:
(1) Mixing a hydroxypropyl trimethyl ammonium chloride chitosan aqueous solution with an ethanol solution of n-butyl aldehyde and 1-octyl aldehyde, and heating to react completely to obtain a reaction mixture;
(2) Adding a sodium cyanoborohydride aqueous solution into the reaction mixture to react completely, and separating and purifying the reaction solution to obtain a product, namely the amphiphilic chitosan;
the quaternary ammonium salt substitution degree of the hydroxypropyl trimethyl ammonium chloride chitosan is 85-120 percent; the molar ratio of the hydroxypropyl trimethyl ammonium chloride chitosan to the aldehyde is 1 (0.5-2);
the reaction temperature in the step (1) is 40-80 ℃;
in the step (2), the molar ratio of the sodium cyanoborohydride to the aldehyde is 1.1.
2. The preparation method according to claim 1, wherein the separation and purification step in the step (2) is: adding acetone into the reaction solution, separating to obtain a precipitate, washing the precipitate with acetone, and drying the precipitate to obtain the catalyst.
3. The preparation method according to claim 1, wherein the hydroxypropyl trimethyl ammonium chloride chitosan is prepared by the following method:
(i) Dissolving chitosan in an acetic acid solution, then alkalifying with NaOH, separating to obtain a precipitate, and washing to be neutral to obtain the alkalified chitosan;
(ii) Dispersing the alkalized chitosan into isopropanol, dropwise adding an isopropanol solution of 2, 3-epoxypropyltrimethylammonium chloride under the heating condition to react until the reaction is finished, and then separating and purifying to obtain the hydroxypropyl trimethyl ammonium chloride chitosan.
4. The method according to claim 3, wherein the degree of deacetylation of chitosan is 95% or more; the pH after alkalization is 9;
the mass ratio of the chitosan to the 2, 3-epoxypropyl trimethyl ammonium chloride is 1 (1-3);
the concentration of the acetic acid solution is 1-2%;
the reaction temperature in the step (ii) is 65-85 ℃; the reaction time is 8-10h.
5. The method according to claim 3, wherein the separation and purification step in step (ii) is: adding absolute ethyl alcohol into the reaction solution, separating to obtain a precipitate, washing the precipitate with absolute ethyl alcohol, and drying.
6. An amphiphilic chitosan obtained by the preparation method of any one of claims 1-5, characterized in that its quaternary ammonium salt substitution degree is 85% -120%, and alkyl substitution degree is 80% -120%.
7. Use of the amphiphilic chitosan of claim 6 in the treatment of wastewater.
8. The use of claim 7, wherein the wastewater is an algae-containing wastewater; the treatment method is microbubble modified air flotation.
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