CN113087312B - Chemical wastewater treatment process based on PSF-g-CS polymer microfiltration membrane - Google Patents
Chemical wastewater treatment process based on PSF-g-CS polymer microfiltration membrane Download PDFInfo
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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Abstract
The invention provides a PSF-g-CS polymer microfiltration membrane, which is prepared by taking polysulfone as a raw material, sequentially preparing chloromethylated polysulfone, hydroxy cycloenone polysulfone alkylated product and PSF-g-CS polymer, and finally preparing the PSF-g-CS polymer microfiltration membrane through electrostatic spinning, wherein the microfiltration membrane has good hydrophilic property, high membrane flux, strong pollution resistance, simple synthesis process and easy industrial production; the invention also provides a sewage treatment method based on the PSF-g-CS polymer microfiltration membrane, which combines the membrane technology, the flocculation precipitation technology and the microorganism technology, has high sewage treatment efficiency, and leads the effluent to completely reach the discharge standard.
Description
Technical Field
The invention belongs to the technical field of chemical sewage treatment, and particularly relates to a sewage treatment process based on a PSF-g-CS polymer microfiltration membrane.
Background
With the continuous development of social economy, the industrial value in production is continuously improved, however, while the industrial development is obtained, the problem of water pollution is also increasingly severe, wherein the problem of treatment of chemical sewage is widely concerned by society, the chemical sewage is toxic and irritant, the organic matter concentration is high, the pH is unstable, the nutritive substances are more, and the polluted water area is difficult to recover to the original state of the water area.
The pollutant components in the chemical wastewater are complex, and the optimal treatment effect can be achieved only by matching treatment of a plurality of methods in treatment. The sewage treatment of chemical plants at present is mainly divided into four major categories, namely physical treatment, chemical treatment, physicochemical treatment and biological treatment. The biological treatment mode is the main mode of chemical sewage treatment in China at present, and is mainly realized by degrading and converting organic matters in sewage through microorganisms, but valuable substances in the sewage can be wasted in the process, and in order to effectively recover valuable resources in the sewage and recycle the resources in the sewage, novel sewage treatment technologies need to be developed.
The development of the membrane technology can well solve the problems, and the advantages of low energy consumption, high efficiency and no pollution enable the membrane technology to be widely developed and utilized, but the membrane technology in China starts late, and problems still exist in the application process, such as the serious problem of membrane pollution, short service life of the membrane, low use efficiency when being matched with other sewage treatment methods, and the like.
Therefore, the invention provides a novel treatment method by preparing the PSF-g-CS polymer through modifying the polysulfone material to obtain the microfiltration membrane with good pollution resistance, and treating chemical sewage by combining the membrane technology with the flocculation precipitation technology and the microbial technology.
Disclosure of Invention
The invention aims to provide a PSF-g-CS polymer microfiltration membrane and a sewage treatment process based on the PSF-g-CS polymer microfiltration membrane, aiming at various problems in the existing chemical sewage treatment technology.
In order to solve the technical problems, the invention adopts the technical scheme that:
a sewage treatment process based on a PSF-g-CS polymer microfiltration membrane comprises a sewage storage tank, a filter tank, a regulating/settling tank, a membrane biological reaction tank and a clean water tank; the adjusting/settling tank is also connected with a sludge concentration tank, the membrane biological reaction tank is divided into an anoxic tank and a microfiltration biomembrane tank, and a microfiltration membrane used by the microfiltration biomembrane tank is a PSF-g-CS polymer microfiltration membrane; the membrane biological reaction tank is connected with a sludge concentration tank on one hand and is connected with an adjusting tank through a membrane regeneration waste liquid pipe on the other hand, the clean water tank is divided into a tank I and a tank II, and the tank I is connected with the adjusting tank; the sewage treatment method based on the PSF-g-CS polymer microfiltration membrane comprises the following steps:
firstly, introducing sewage accumulated in a sewage storage tank into a filtering tank, wherein the filtering tank contains a grid and a grid, and large-volume impurities are filtered out from the sewage passing through the filtering tank;
secondly, the effluent of the filter tank enters an adjusting/settling tank, the pH of the sewage is adjusted, the suspended solid SS of the sewage is preliminarily detected, if the SS is less than or equal to 300mg/L, the effluent can be directly introduced into a membrane biological reaction tank, and if the SS is more than 300mg/L, a coagulant is added to polymerize and settle large granular substances and suspended substances in the sewage, so that the chroma, the SS and the BOD are reduced 5 、COD Cr ；
Thirdly, the sludge generated by the adjusting/settling tank can be introduced into a sludge concentration tank, the sewage is introduced into a membrane biological reaction tank, and then passes through an anoxic tank and a microfiltration biological membrane tank in sequence, a sludge accumulation zone is arranged at the bottom of the membrane biological reaction tank, the generated sludge can be temporarily accumulated in the sludge accumulation zone and is periodically discharged into the sludge concentration tank, and the regenerated waste liquid of the biological membrane of the membrane biological reaction tank is discharged into the adjusting tank again through a membrane regenerated waste liquid pipe;
fourthly, introducing the sewage subjected to further biochemical treatment and physical filtration into a clean water tank I, detecting whether the sewage meets the standard, and introducing the sewage into the regulating tank again if the sewage does not meet the standard; and if the standard is reached, introducing into a clean water tank II, and discharging or recycling.
Preferably, the anoxic tank in the third step is an anoxic environment, the anoxic tank contains suspended fillers, and facultative anaerobic microorganisms such as yeasts, nitrifying bacteria or denitrifying bacteria are attached to the suspended fillers.
Preferably, the microfiltration biomembrane pool in the third step is in an aerobic environment and comprises an aeration device, a suspension filler and a micro-tubular membrane component, wherein aerobic microorganisms such as bacteria, fungi or aerobic nitrifying bacteria and the like are attached to the suspension filler, and a microfiltration membrane used by the micro-tubular membrane component is a PSF-g-CS polymer microfiltration membrane.
Preferably, the preparation method of the PSF-g-CS polymer microfiltration membrane comprises the following steps:
s1, chloromethylation of polysulfone: dissolving polysulfone in dichloromethane, stirring to completely dissolve the polysulfone, adding paraformaldehyde and trimethylchlorosilane, stirring uniformly, slowly adding a stannic chloride solution under a stirring state, and reacting to obtain chloromethylated polysulfone;
s2, preparation of hydroxycycloalkenone polysulfone: dissolving the cyclic diketone compound in 1M sodium hydroxide aqueous solution, adding chloromethylated polysulfone into the mixed solution, and heating the mixture for reaction to obtain hydroxycycloenone polysulfone;
s3, alkylation reaction of hydroxy cycloenone polysulfone: dissolving hydroxy cycloenone polysulfone in N, N-dimethylformamide, adding beta-halogenated acid ester and potassium carbonate, and heating to react to obtain an alkylation product;
s4, preparation of PSF-g-CS Polymer: dissolving the alkylated product and chitosan in absolute ethyl alcohol, adding an ethanol solution of titanium tetrachloride, controlling the temperature to react for 8-10 hours, then adding trifluoroacetic acid, and reacting for 2-3 hours at room temperature to obtain a PSF-g-CS polymer;
s5, preparation of PSF-g-CS polymer microfiltration membrane: dissolving the prepared PSF-g-CS polymer in N, N-dimethylformamide to prepare a solution with the concentration of 15-18 wt%, preparing a PSF-g-CS nano fibrous membrane by an electrostatic spinning technology, soaking the prepared fibrous membrane in deionized water, and drying in a vacuum drying oven to obtain the PSF-g-CS polymer microfiltration membrane capable of being used for a membrane bioreactor.
Preferably, in the step S1, the mass-to-volume ratio of the polysulfone to the paraformaldehyde, the trimethylchlorosilane to the stannic chloride is 40-50 g: 30-40 g: 90-100 mL: 2-3 mL, and the reaction temperature and the reaction time are respectively 35 ℃ and 60-70 h.
Preferably, the mass ratio of the cyclic dione compound to the chloromethylated polysulfone in the step S2 is 3-5: 10; the reaction condition is that the reaction is carried out for 8 to 10 hours at the temperature of 75 to 90 ℃; the cyclic diketone compound is one of 1, 3-cyclopentanedione, 1, 3-cyclohexanedione, 5-methylcyclohexane-1, 3-dione, 5-dimethyl-1, 3-cyclohexanedione, 5-isopropylcyclohexane-1, 3-dione, 5- (2-furyl) -1, 3-cyclohexanedione and 5- (2-thienyl) cyclohexane-1, 3-dione.
Preferably, the mass ratio of the hydroxycycloalkenone polysulfone to the beta-haloacid ester to the potassium carbonate in the step S3 is 10: 5-7: 4-5; the reaction condition is that the reaction is carried out for 3-4 h at the temperature of 60-70 ℃; the beta-haloacid ester is one of tert-butyl bromoacetate, tert-butyl chloroacetate, tert-butyl 2-bromobutyrate and tert-butyl 2-chloropropionate.
Preferably, the mass-to-volume ratio of the alkylated product, the chitosan and the titanium tetrachloride in the step S4 is 10g: 8-10 g: 1.5-2.0 mL; the control temperature is 15-20 ℃; the amount of the trifluoroacetic acid is 1/5-1/3 of the total volume of the mixed solution.
Preferably, the electrostatic spinning conditions in step S5 are that the spinning voltage is 20kv, the spinning speed is 0.8mL/h to 1.0mL/h, and the receiving distance is 15 cm; the temperature of the vacuum drying oven is 40-45 ℃.
In the invention, sewage is firstly filtered through a grid and a grid in sequence, then is discharged into a membrane biological reaction tank through pH regulation and precipitation treatment, the sewage firstly passes through an anoxic tank in the membrane biological reaction tank, the anoxic condition can inhibit the propagation of filamentous bacteria, the expansion of sludge is effectively inhibited, the biodegradability of the sewage is improved, meanwhile, the sewage is denitrified under the action of denitrifying bacteria, then passes through an aerobic microfiltration biomembrane tank, macromolecular organic compounds are degraded by aerobic microorganisms to generate micromolecular substances and stable and harmless inorganic substances, the organic substances in the sewage are completely removed through the adsorption of the microfiltration biomembrane, and the anoxic tank is arranged in front of a membrane component to prevent the membrane from being polluted and blocked due to the expansion of the sludge; the sewage passing through the membrane biological reaction tank firstly enters a clean water tank I, and if the sewage is detected to reach the discharge standard, the sewage is discharged into a clean water tank II for standby or discharge; if the sewage is detected to be incapable of meeting the discharge standard, the sewage enters the regulating tank again for treatment, and the discharged sewage is fully ensured to reach the standard.
The PSF-g-CS polymer microfiltration membrane prepared by the invention takes polysulfone as an initial raw material, reacts with a cyclic diketone compound to generate hydroxycycloketene polysulfone after undergoing a chloromethylation reaction, then reacts with beta-haloester to generate an alkylated product, finally reacts with amino of chitosan through Schiff base, removes Boc protective groups through trifluoroacetic acid to obtain a PSF-g-CS polymer, and is prepared by an electrostatic spinning technology.
The PSF-g-CS polymer microfiltration membrane prepared by taking polysulfone and chitosan with good biocompatibility as raw materials contains a large amount of carboxyl, hydroxyl, imine groups and ether groups, so that the microfiltration membrane has good hydrophilicity, the increase of the hydrophilicity improves the membrane flux and the anti-pollution performance of the membrane, the membrane hanging rate of microorganisms is increased, and the adhesion performance is enhanced; the PSF-g-CS polymer microfiltration membrane improves the adsorption performance of the polysulfone membrane on heavy metal ions and also improves the mechanical performance of the chitosan membrane, bonds such as hydroxyl groups and carboxyl groups dispersed in the membrane form hydrogen bond interaction, the crosslinking action between the polysulfone and the chitosan is enhanced, the tensile strength of the PSF-g-CS polymer microfiltration membrane is improved, a conjugated system formed by carbon-carbon double bonds-carbon-oxygen double bonds in structural unit molecules is further eliminated by reaction with Schiff base of the chitosan, the aging process of the membrane under the action of ultraviolet rays is reduced, and the aging resistance and the ultraviolet resistance of the polymer material are improved.
Compared with the prior art, the invention has the following advantages:
1. in the preparation process of the PSF-g-CS polymer microfiltration membrane, all the small molecular compounds, namely the cyclic diketone compound, the beta-haloacid ester and the trifluoroacetic acid, are simple and easily obtained, the price is low, and the synthesis process is simple and easy for industrial production.
2. The PSF-g-CS polymer microfiltration membrane prepared by the invention has good hydrophilic property, high membrane flux and strong dirt resistance, and has long service cycle and high sewage treatment efficiency when being applied to a membrane bioreactor.
3. The PSF-g-CS polymer microfiltration membrane has good adsorption performance on various metal ions, has strong hydrophilicity, is beneficial to microbial biofilm formation, and increases the biochemical reaction rate of sewage.
4. The invention combines the membrane technology, the flocculation precipitation technology and the microorganism technology based on the sewage treatment technology of the PSF-g-CS polymer microfiltration membrane, has high sewage treatment efficiency, and leads the effluent to completely reach the discharge standard.
Drawings
FIG. 1 is a flow diagram of a wastewater treatment system;
FIG. 2 is a flow chart of the preparation of PSF-g-CS polymer.
Detailed Description
The technical solutions of the present invention are further described in detail with reference to the drawings and specific embodiments so that those skilled in the art can better understand the present invention and can implement the present invention, but the embodiments are not limited to the present invention.
The sewage treated by the embodiment of the invention is the sewage of a certain chemical plant, and the BOD of the sewage is preliminarily detected 5 、COD Cr 431mg/L and 1075mg/L respectively, the SS is 769mg/L, the pH is 8.4, and the chroma is 825; the chemical plant sewage is treated by the sewage treatment process based on the PSF-g-CS polymer microfiltration membrane, and the sewage treatment system comprises a sewage storage tank, a filter tank, a regulating/settling tank, a membrane biological reaction tank and a clean water tank; the adjusting/settling tank is also connected with a sludge concentration tank, the membrane biological reaction tank is divided into an anoxic tank and a microfiltration biomembrane tank, and a microfiltration membrane used by the microfiltration biomembrane tank is a PSF-g-CS polymer microfiltration membrane; the membrane biological reaction tank is connected with a sludge concentration tank on one hand and regenerated by a membrane on the other handThe waste liquid pipe is connected with the adjusting tank, the clean water tank is divided into a tank I and a tank II, and the tank I is connected with the adjusting tank.
A sewage treatment method based on a PSF-g-CS polymer microfiltration membrane comprises the following steps:
firstly, introducing sewage accumulated in a sewage storage tank into a filtering tank, wherein the filtering tank sequentially comprises 15mm grids and 3 x 10mm grids, the grid spacing of the grids is 0.5m, and large-volume impurities are filtered from the sewage passing through the filtering tank;
secondly, the effluent of the filtering tank enters an adjusting/settling tank, the pH of the sewage is adjusted for the first time to be 6.8, and as the SS of the sewage is more than 300mg/L, a flocculating agent cationic polyacrylamide is added to polymerize and settle large granular substances and suspended matters in the sewage, the adding amount is 170mg/L, and the chroma, the SS and the BOD of the sewage are reduced primarily 5 、COD Cr (ii) a Again detect BOD 5 、COD Cr 249mg/L and 685mg/L respectively, 287mg/L SS and 581 chroma;
thirdly, the sludge generated by the adjusting/settling tank can be introduced into a sludge concentration tank, the sewage is introduced into a membrane biological reaction tank, and then passes through an anoxic tank (the dissolved oxygen is controlled to be less than 0.5mg/L and the sludge concentration is controlled to be 6g/L) and a microfiltration biological membrane tank (the dissolved oxygen is controlled to be more than 2mg/L and the sludge concentration is controlled to be 8g/L), the sludge generated by the membrane biological reaction tank can be temporarily accumulated in a sludge accumulation area at the bottom of the membrane biological reaction tank and is periodically discharged into the sludge concentration tank, and the regenerated waste liquid of the biological membrane in the membrane biological reaction tank is discharged into the adjusting tank; the microfiltration membrane used by the membrane biological reaction tank is a PSF-g-CS polymer microfiltration membrane; wherein the anoxic tank is in an anoxic environment, the anoxic tank contains a suspended filler and an aeration device, and facultative anaerobic microorganisms such as saccharomycetes, nitrobacteria or denitrifying bacteria and the like are attached to the suspended filler of the anoxic tank; the micro-filtration biomembrane pool is in an aerobic environment and comprises an aeration device, a suspension filler and a micro-tube type membrane component, wherein the suspension filler of the micro-filtration biomembrane pool is attached with aerobic microorganisms such as bacteria, fungi or aerobic nitrifying bacteria, and the micro-filtration membrane used by the micro-tube type membrane component is a PSF-g-CS polymer micro-filtration membrane; the suspended fillers in the anoxic tank and the microfiltration biomembrane tank are commercially available suspended ball porous polyurethane sponge fillers; the filling amount of the suspended filler in the anoxic tank and the micro-filtration biomembrane tank is respectively 60 percent and 50 percent.
Fourthly, introducing the sewage subjected to the further biochemical treatment and the physical filtration in the third step into a clean water tank I, detecting whether the sewage meets the standard or not, (the pH value can be adjusted to 6-8 again), and introducing the sewage into an adjusting tank again if the sewage does not meet the standard; and if the standard is reached, introducing into a clean water tank II, and discharging or recycling.
Example 1
A preparation method of a PSF-g-CS polymer microfiltration membrane comprises the following steps:
s1, chloromethylation of polysulfone: dissolving polysulfone (Mw35000) in dichloromethane, stirring to completely dissolve, adding paraformaldehyde and trimethylchlorosilane, wherein the mass-volume ratio of the polysulfone to the paraformaldehyde to the trimethylchlorosilane to the stannic chloride is 40g to 30g to 90mL to 2mL, stirring uniformly, slowly adding a stannic chloride solution under the stirring state, and reacting for 60 hours at 35 ℃ to obtain chloromethylated polysulfone;
s2, preparation of hydroxycycloalkenone polysulfone: dissolving 1, 3-cyclopentanedione in 1M aqueous solution of sodium hydroxide, adding chloromethylated polysulfone into the mixed solution, wherein the mass ratio of the 1, 3-cyclopentanedione to the chloromethylated polysulfone is 3:10, heating the mixture to 75 ℃, and reacting for 8 hours to obtain hydroxycycloketene polysulfone;
s3, alkylation reaction of hydroxy cycloenone polysulfone: dissolving hydroxycycloalkone polysulfone in N, N-dimethylformamide, adding tert-butyl bromoacetate and potassium carbonate, wherein the mass ratio of the hydroxycycloalkone polysulfone to the tert-butyl bromoacetate to the potassium carbonate is 10:5:4, and heating to 60 ℃ for reaction for 3 hours to obtain an alkylation product;
s4, preparation of PSF-g-CS Polymer: dissolving an alkylation product and chitosan (Mw50000) in absolute ethyl alcohol, adding an ethanol solution of titanium tetrachloride, controlling the mass-volume ratio of the alkylation product to the chitosan to the titanium tetrachloride to be 10g:8g:1.5mL, controlling the temperature to be 15 ℃ to react for 8h, then adding trifluoroacetic acid with the total volume of 1/5 of a mixed solution, and reacting for 2h at room temperature to obtain a PSF-g-CS polymer;
s5, preparation of PSF-g-CS polymer microfiltration membrane: dissolving the prepared PSF-g-CS polymer in N, N-dimethylformamide to prepare a solution with the concentration of 18 wt%, controlling the spinning voltage to be 20kv, the spinning speed to be 0.8mL/h and the receiving distance to be 15cm, preparing a PSF-g-CS nano fibrous membrane by an electrostatic spinning technology, soaking the prepared fibrous membrane in deionized water, and drying in a vacuum drying oven at 40 ℃ to obtain the PSF-g-CS polymer microfiltration membrane for the membrane bioreactor.
The prepared polysulfone composite microfiltration membrane is used in the sewage treatment process, and the BOD of the sewage treated in the clean water tank I is detected after the sewage treatment 5 、COD Cr 34mg/L and 71mg/L respectively, the SS is 38mg/L, and the chroma is 26; and (4) reaching the standard, and introducing into a clean water tank II for discharge or recycling.
Example 2
A preparation method of a PSF-g-CS polymer microfiltration membrane comprises the following steps:
s1, chloromethylation of polysulfone: dissolving polysulfone (Mw35000) in dichloromethane, stirring to completely dissolve, adding paraformaldehyde and trimethylchlorosilane, wherein the mass-volume ratio of the polysulfone to the paraformaldehyde to the trimethylchlorosilane to the stannic chloride is 45g to 35g to 95mL to 2mL, stirring uniformly, slowly adding a stannic chloride solution under the stirring state, and reacting for 60 hours at 35 ℃ to obtain chloromethylated polysulfone;
s2, preparation of hydroxycycloalkenone polysulfone: dissolving 5-methylcyclohexane-1, 3-dione in 1M aqueous solution of sodium hydroxide, adding chloromethylated polysulfone into the mixed solution, wherein the mass ratio of the 5-methylcyclohexane-1, 3-dione to the chloromethylated polysulfone is 2:5, and heating the mixture to 80 ℃ for reacting for 9 hours to obtain hydroxycycloalkone polysulfone;
s3, alkylation reaction of hydroxy cycloenone polysulfone: dissolving hydroxycycloenone polysulfone in N, N-dimethylformamide, adding tert-butyl 2-bromobutyrate and potassium carbonate, wherein the mass ratio of the hydroxycycloenone polysulfone to the tert-butyl 2-bromobutyrate to the potassium carbonate is 10:6:4, and heating to 60 ℃ for reaction for 3 hours to obtain an alkylation product;
s4, preparation of PSF-g-CS Polymer: dissolving an alkylation product and chitosan (Mw50000) in absolute ethyl alcohol, adding an ethanol solution of titanium tetrachloride, controlling the mass-volume ratio of the alkylation product to the chitosan to the titanium tetrachloride to be 10g:9g:2mL, controlling the temperature to be 15 ℃ to react for 9h, then adding trifluoroacetic acid with the total volume of 1/4 of a mixed solution, and reacting for 2h at room temperature to obtain a PSF-g-CS polymer;
s5, preparation of a PSF-g-CS polymer microfiltration membrane: dissolving the prepared PSF-g-CS polymer in N, N-dimethylformamide to prepare a solution with the concentration of 17 wt%, controlling the spinning voltage to be 20kv, the spinning speed to be 0.9mL/h and the receiving distance to be 15cm, preparing a PSF-g-CS nano fibrous membrane by an electrostatic spinning technology, soaking the prepared fibrous membrane in deionized water, and drying in a vacuum drying oven at 45 ℃ to obtain the PSF-g-CS polymer microfiltration membrane for the membrane bioreactor.
The prepared polysulfone composite microfiltration membrane is used in the sewage treatment process, and the BOD of the sewage treated in the clean water tank I is detected after the treatment 5 、COD Cr 31mg/L and 65mg/L respectively, 33mg/L SS and 26 chroma; and (4) reaching the standard, and introducing into a clean water tank II for discharge or recycling.
Example 3
A preparation method of a PSF-g-CS polymer microfiltration membrane comprises the following steps:
s1, chloromethylation of polysulfone: dissolving polysulfone (Mw35000) in dichloromethane, stirring to completely dissolve, adding paraformaldehyde and trimethylchlorosilane, wherein the mass-volume ratio of the polysulfone to the paraformaldehyde to the trimethylchlorosilane to the stannic chloride is 50g to 40g to 100mL to 3mL, stirring uniformly, slowly adding a stannic chloride solution under the stirring state, and reacting at 35 ℃ for 70 hours to obtain chloromethylated polysulfone;
s2, preparation of hydroxycycloalkenone polysulfone: dissolving 5- (2-thienyl) cyclohexane-1, 3-dione in 1M aqueous solution of sodium hydroxide, adding chloromethylated polysulfone into the mixed solution, wherein the mass ratio of the 5- (2-thienyl) cyclohexane-1, 3-dione to the chloromethylated polysulfone is 1:2, and heating the mixture to 90 ℃ for reacting for 10 hours to obtain hydroxycycloalkone polysulfone; thienyl) one of cyclohexane-1, 3-dione;
s3, alkylation reaction of hydroxy cycloenone polysulfone: dissolving hydroxycycloenone polysulfone in N, N-dimethylformamide, adding tert-butyl 2-chloropropionate and potassium carbonate, wherein the mass ratio of the hydroxycycloenone polysulfone to the tert-butyl 2-chloropropionate to the potassium carbonate is 10:7:5, and heating to 70 ℃ for reacting for 4 hours to obtain an alkylation product;
s4, preparation of PSF-g-CS Polymer: dissolving an alkylated product and chitosan (Mw50000) in absolute ethyl alcohol, adding an ethanol solution of titanium tetrachloride, controlling the mass-volume ratio of the alkylated product to the chitosan to the titanium tetrachloride to be 10g:10g:2mL, controlling the temperature to be 20 ℃ to react for 10 hours, then adding trifluoroacetic acid with the total volume of 1/3 of a mixed solution, and reacting for 3 hours at room temperature to obtain a PSF-g-CS polymer;
s5, preparation of a PSF-g-CS polymer microfiltration membrane: dissolving the prepared PSF-g-CS polymer in N, N-dimethylformamide to prepare a solution with the concentration of 15 wt%, controlling the spinning voltage to be 20kv, the spinning speed to be 1.0mL/h and the receiving distance to be 15cm, preparing a PSF-g-CS nano fibrous membrane by an electrostatic spinning technology, soaking the prepared fibrous membrane in deionized water, and drying in a vacuum drying oven at 45 ℃ to obtain the PSF-g-CS polymer microfiltration membrane for the membrane bioreactor.
The prepared polysulfone composite microfiltration membrane is used in the sewage treatment process, and the BOD of the sewage treated in the clean water tank I is detected after the treatment 5 、COD Cr 26mg/L and 60mg/L respectively, SS 32mg/L and chroma 24; and (4) reaching the standard, and introducing into a clean water tank II for discharging or recycling.
Comparative example 1
Compared with the example 3, in the comparative example 1, the chitosan and the polysulfone are directly mixed and dissolved in the N, N-dimethylformamide in a mass ratio of 1:1 to prepare a solution with a concentration of 15% for spinning to prepare the PSF-g-CS microfiltration membrane, and the rest preparation method and application data are the same as those in the example 3.
Comparative example 2
Compared with the example 3, in the comparative example 2, the alkylation product of the hydroxycycloalkone polysulfone is directly decarboxylated by trifluoroacetic acid to obtain the modified polysulfone material, then the modified polysulfone material is dissolved in N, N-dimethylformamide to prepare a solution with the concentration of 15%, a microfiltration membrane is prepared by spinning, chitosan is not added, and the other preparation method and application data are the same as those in the example 3.
Comparative example 3
Compared with the embodiment 3, in the comparative example 3, the alkylation product of the hydroxycycloalkone polysulfone is directly decarboxylated by trifluoroacetic acid to obtain a modified polysulfone material, then the modified polysulfone material and the chitosan are mixed and dissolved in N, N-dimethylformamide in a mass ratio of 1:1 to prepare a solution with a concentration of 15%, and the solution is spun to prepare the PSF-g-CS microfiltration membrane, wherein the rest preparation method and application data are the same as the embodiment 3.
Comparative example 4
The microfiltration membrane prepared in example 3 is also adopted to treat sewage, the filling amount of the suspended filler in the anoxic tank and the suspended filler in the microfiltration biological membrane tank are respectively changed to be 70 percent and 40 percent only when the sewage treatment process is adopted, and the other preparation methods, application data and treatment processes are the same as those of the microfiltration membrane prepared in example 3.
And (3) performance testing:
1. static water contact angle characterization: after dropping water droplets on the surface of the prepared film for 10 seconds, the contact angle was measured using a contact angle measuring instrument (model JC 2003A), and 5 points were averaged; the single polysulfone membrane and the chitosan membrane are prepared by preparing 15 wt% polysulfone or chitosan N, N-dimethylformamide solution
2. Pure water flux measurement: pure water at normal temperature was supplied to one side surface of the prepared membrane at 0.1MPa by the closed end method, and the amount of permeated water was measured.
3. Measurement of tensile Strength Change Rate: the tensile strength of the microfiltration membranes prepared in examples 1 to 3 and comparative examples 1 to 3 was measured, and then the membranes were immersed in 50mg/L of ClO 2 After 12h in the solution, washing with pure water, drying at normal temperature for 24h, measuring the tensile strength of the membrane again, and comparing the tensile strength change rate (%) of each group of microfiltration membranes.
The properties of the PSF-g-CS polymeric microfiltration membrane of the invention are shown in Table 1:
as can be seen from the data in Table 1, the contact angles of the PSF-g-CS polymer microfiltration membranes prepared in the embodiments 1 to 3 are reduced and the water fluxes are increased compared with the polysulfone membranes, which shows that the PSF-g-CS polymer microfiltration membranes improve the hydrophilic performance of the polysulfone membranes, and the reduction rate of the tensile strength simultaneously shows that the aging resistance of the microfiltration membranes of the embodiments 1 to 3 is enhanced; the microfiltration membrane prepared in the comparative example 1 is prepared by directly mixing polysulfone and chitosan, the membrane contact angle is increased, and the water flux is reduced, which shows that the hydrophilic property of polysulfone is not improved and the anti-aging property is not improved by directly adding chitosan; the microfiltration membrane contains exposed carboxyl, compared with the polysulfone membrane, the microfiltration membrane has obviously increased hydrophilic performance, reduced membrane contact angle and increased water flux, but due to the existence of carbon-oxygen conjugated double bonds, the microfiltration membrane not only has weak ultraviolet resistance, but also is easy to oxidize to age the membrane, and the ageing resistance of the microfiltration membrane is inferior to that of the microfiltration membranes in the embodiments 1 to 3; compared with the microfiltration membrane prepared by mixing the modified polysulfone material obtained by decarboxylation and chitosan, the microfiltration membrane prepared by the comparative example 3 has the advantages of reduced contact angle, increased water flux and enhanced membrane hydrophilic performance, but has the advantages of weakened hydrophilic performance, increased tensile strength reduction rate and easy aging compared with the microfiltration membranes prepared in examples 1-3.
TABLE 2 COD of the sewage treated by the microfiltration membranes or the methods of comparative examples 1 to 4 Cr 、BOD 5 Chroma and SS
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| BOD 5 | 176 | 72 | 113 | 30 |
| COD Cr | 304 | 139 | 209 | 67 |
| SS | 191 | 86 | 128 | 33 |
| Color intensity | 283 | 135 | 195 | 29 |
(COD and BOD units are mg/L)
As can be seen from the data in Table 2 in combination with the data of the sewage treated by the microfiltration membranes of the embodiments 1 to 3, the sewage treated by the microfiltration membranes of the embodiments 1 to 3 in combination with the sewage treatment method of the invention all reach the discharge standard (DB 41/1135-2016 discharge standard); the sewage treated by the microfiltration membrane prepared in the comparative example 1 does not reach the standard, the sewage treated by the microfiltration membranes of the comparative examples 2 and 3 only does not reach the standard in chromaticity, the microfiltration membrane which is the same as that of the microfiltration membrane prepared in the example 3 is adopted in the comparative example 4, the filling amount of the suspended filler is changed, and the BOD of the treated sewage is changed 5 、COD Cr SS and color are still up to standard, and the data show that the change of the filling amount has certain influence on the sewage treatmentHowever, the critical role in the present invention is still that of microfiltration.
Table 3 examples 1 to 3 and comparative examples 1 to 4 show the adsorption degradation rate (%) of organic substances in wastewater and the adsorption removal rate (%) of heavy metal ions
As can be seen from the data in Table 3, when the microfiltration membranes of the embodiments 1 to 3 are applied to sewage treatment, the removal rate of several organic matters and heavy metal ions reaches more than 93%, and the observation and detection of the sewage treatment process find that the microfiltration membrane surfaces of the embodiments 1 to 3 are easier to form a biofilm than those of the microfiltration membranes of the proportions 1 to 4, so that the organic matters are easier to degrade and utilize by microorganisms on the biofilm after being adsorbed; the comparative example 1 is a microfiltration membrane prepared by directly mixing polysulfone and chitosan, the removal rate of the microfiltration membrane on several organic matters and heavy metal ions is increased when the method is used for treating sewage, but the removal rate is only about 50%, and the performance of the polysulfone membrane in the sewage treatment process is improved by adding the chitosan; compared with a single polysulfone membrane, the modified polysulfone material is obviously enhanced in the adsorption degradation rate of organic matters and the adsorption removal rate of heavy metal ions, but obviously weakened in the performance of the microfiltration membrane in comparison with the microfiltration membranes in examples 1-3, because a large amount of hydroxyl, amino and carboxyl are added in the microfiltration membrane prepared in the comparative example 2, the adsorption performance of the microfiltration membrane is enhanced, and the adsorption performance of the microfiltration membrane is weakened due to the property of easy aging; the comparative example 3 has a lower effect on sewage treatment than the microfiltration membrane prepared in the comparative example 2 because the microfiltration membrane of the comparative example 3 has a weaker hydrophilic property and is more easily polluted in sewage treatment, thereby affecting various properties of the sewage treatment; in comparative example 4, only the addition amount of the suspended filler was changed, but the removal rate of each organic matter and heavy metal ion was still more than 90%, indicating that the change in the filling amount of the suspended filler in a certain range had little effect on sewage treatment.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (9)
1. A preparation method of a PSF-g-CS polymer microfiltration membrane is characterized by comprising the following steps:
s1, chloromethylation of polysulfone: dissolving polysulfone in dichloromethane, stirring to completely dissolve the polysulfone, adding paraformaldehyde and trimethylchlorosilane, stirring uniformly, slowly adding a stannic chloride solution under a stirring state, and reacting to obtain chloromethylated polysulfone;
s2, preparation of hydroxycycloalkenone polysulfone: dissolving a cyclic diketone compound in an alkaline aqueous solution, adding chloromethylated polysulfone into the mixed solution, and heating the mixture for reaction to obtain hydroxycycloenone polysulfone;
s3, alkylation reaction of hydroxyl cyclic ketene polysulfone: dissolving hydroxy cycloenone polysulfone in a solvent, adding beta-halogenated acid ester and potassium carbonate, and heating to react to obtain an alkylation product;
s4, preparation of PSF-g-CS Polymer: dissolving the alkylated product and chitosan in absolute ethyl alcohol, adding an ethanol solution of titanium tetrachloride, adding trifluoroacetic acid after reaction, and reacting at room temperature to obtain a PSF-g-CS polymer;
s5, preparation of a PSF-g-CS polymer microfiltration membrane: dissolving the prepared PSF-g-CS polymer in N, N-dimethylformamide to prepare a spinning solution, preparing a PSF-g-CS nano fibrous membrane by an electrostatic spinning technology, soaking the prepared fibrous membrane in deionized water, and drying in a vacuum drying oven to obtain the PSF-g-CS polymer microfiltration membrane for the membrane bioreactor.
2. The preparation method of the PSF-g-CS polymeric microfiltration membrane according to claim 1, wherein the mass-to-volume ratio of the polysulfone to the paraformaldehyde, the trimethylchlorosilane to the stannic chloride in the step S1 is 40-50 g: 30-40 g: 90-100 mL: 2-3 mL, and the reaction temperature and the reaction time are 35 ℃ and 60-70 hours respectively.
3. The preparation method of the PSF-g-CS polymer microfiltration membrane according to claim 1, wherein the mass ratio of the cyclic dione compound to the chloromethylated polysulfone in step S2 is 3-5: 10; the reaction condition is that the reaction lasts for 8-10 h at 75-90 ℃; the cyclic diketone compound is one of 1, 3-cyclopentanedione, 1, 3-cyclohexanedione, 5-methylcyclohexane-1, 3-dione, 5-dimethyl-1, 3-cyclohexanedione, 5-isopropylcyclohexane-1, 3-dione, 5- (2-furyl) -1, 3-cyclohexanedione and 5- (2-thienyl) cyclohexane-1, 3-dione.
4. The preparation method of the PSF-g-CS polymer microfiltration membrane according to claim 1, wherein the mass ratio of the hydroxycycloalkone polysulfone to the beta-haloacid ester to the potassium carbonate in step S3 is 10: 5-7: 4-5; the reaction condition is that the reaction is carried out for 3-4 h at the temperature of 60-70 ℃; the beta-haloacid ester is one of tert-butyl bromoacetate, tert-butyl chloroacetate, tert-butyl 2-bromobutyrate and tert-butyl 2-chloropropionate.
5. The preparation method of the PSF-g-CS polymeric microfiltration membrane according to claim 1, wherein the mass-to-volume ratio of the alkylated product, the chitosan and the titanium tetrachloride in step S4 is 10g: 8-10 g: 1.5-2.0 mL; controlling the temperature to be 15-20 ℃; the amount of the trifluoroacetic acid is 1/5-1/3 of the total volume of the mixed solution.
6. The PSF-g-CS polymer microfiltration membrane preparation method according to claim 1, wherein the electrospinning in step S5 is performed under conditions of a spinning voltage of 20kv, a spinning speed of 0.8mL/h to 1.0mL/h, and a reception distance of 15 cm; the temperature of the vacuum drying oven is 40-45 ℃.
7. A sewage treatment method of the PSF-g-CS polymer microfiltration membrane obtained by the preparation method of the PSF-g-CS polymer microfiltration membrane according to any one of claims 1-6, which is characterized in that the sewage treatment process sequentially passes through a sewage storage tank, a filter tank, a regulating/settling tank, a membrane biological reaction tank and a clean water tank; the adjusting/settling tank is also connected with a sludge concentration tank, the membrane biological reaction tank is divided into an anoxic tank and a microfiltration biomembrane tank, and a microfiltration membrane used by the microfiltration biomembrane tank is a PSF-g-CS polymer microfiltration membrane; the membrane biological reaction tank is connected with a sludge concentration tank on one hand and is connected with an adjusting tank through a membrane regeneration waste liquid pipe on the other hand, the clean water tank is divided into a tank I and a tank II, and the tank I is connected with the adjusting/settling tank; the sewage treatment method based on the PSF-g-CS polymer microfiltration membrane comprises the following steps:
firstly, introducing sewage accumulated in a sewage storage tank into a filtering tank, wherein the filtering tank contains a grid and a grid, and large-volume impurities are filtered out from the sewage passing through the filtering tank;
secondly, the effluent of the filtering tank enters an adjusting/settling tank, the pH of the sewage is adjusted, suspended solids SS of the sewage are preliminarily detected, if the SS is less than or equal to 300mg/L, the effluent is directly introduced into a membrane biological reaction tank, and if the SS is more than 300mg/L, a coagulant is added to polymerize and settle large granular substances and suspended solids in the sewage, so that the chroma, the SS, BOD 5 and COD Cr are reduced;
thirdly, the sludge generated by the adjusting/settling tank is introduced into a sludge concentration tank, the sewage is introduced into a membrane biological reaction tank, the sewage passes through an anoxic tank and a microfiltration biological membrane tank in sequence, a sludge accumulation zone is arranged at the bottom of the membrane biological reaction tank, the generated sludge is temporarily accumulated in the sludge accumulation zone and is periodically discharged into the sludge concentration tank, and the regenerated waste liquid of the biological membrane of the membrane biological reaction tank is discharged into the adjusting tank again through a membrane regenerated waste liquid pipe;
fourthly, introducing the sewage subjected to further biochemical treatment and physical filtration into a clean water tank I, detecting whether the sewage meets the standard, and introducing the sewage into the regulating tank again if the sewage does not meet the standard; and if the standard is reached, introducing into a clean water tank II, and discharging or recycling.
8. The PSF-g-CS polymer microfiltration membrane-based sewage treatment method according to claim 7, wherein in the third step, the anoxic tank is in an anoxic environment, the anoxic tank contains suspended filler, and facultative anaerobic microorganisms are attached to the suspended filler in the anoxic tank.
9. The method for treating sewage based on PSF-g-CS polymeric microfiltration membrane according to claim 8, wherein the microfiltration biomembrane pool in the third step is aerobic environment and comprises an aeration device, suspended filler and a micro-tubular membrane component, wherein aerobic microorganisms are attached to the suspended filler in the microfiltration biomembrane pool, and the micro-tubular membrane component uses the PSF-g-CS polymeric microfiltration membrane as the microfiltration membrane.
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