CN114229992A - Preparation of composite modified carrier and sewage treatment method - Google Patents

Preparation of composite modified carrier and sewage treatment method Download PDF

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CN114229992A
CN114229992A CN202111545627.1A CN202111545627A CN114229992A CN 114229992 A CN114229992 A CN 114229992A CN 202111545627 A CN202111545627 A CN 202111545627A CN 114229992 A CN114229992 A CN 114229992A
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carrier
composite modified
polylactic acid
water
solution
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CN114229992B (en
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李立欣
何征明
蒋本超
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Liuzhou Xike Automotive Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20—Bacteria; Culture media therefor
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/16—Total nitrogen (tkN-N)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/18—PO4-P
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/06—Nutrients for stimulating the growth of microorganisms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

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Abstract

The invention belongs to the technical field of sewage treatment, and discloses a composite modified carrier, a preparation method and a sewage treatment method, wherein the preparation method comprises the following steps: preparing a culture medium; inoculating common flocculent producing bacteria on a culture medium under an aseptic condition, and culturing for 72h at the temperature of 30 ℃; preparing a composite material: adding polylactic acid into trichloromethane, stirring in water bath, and fully dissolving; adding a biological flocculant solution dissolved with supersaturated sodium chloride into a dissolving beaker, and fully stirring and uniformly mixing; adding a proper amount of polyethylene common plastic carrier into the trichloromethane solution in which the polylactic acid, the supersaturated sodium chloride and the biological flocculant are fully dissolved to ensure that the carrier is completely soaked by the trichloromethane, taking out the soaked carrier, and naturally ventilating and drying. The polylactic acid provided by the invention is stable in acid-base solution, the thermal decomposition temperature is high, and the biological flocculant-doped modified polylactic acid three-dimensional porous material has good affinity with organisms.

Description

Preparation of composite modified carrier and sewage treatment method
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a preparation method of a composite modified carrier and a sewage treatment method.
Background
At present, the typical filler system in the existing market is made of Polyethylene (PE), the bulk density is high, and the suitability of biofilm growth is relatively poor. The unique structure and composition of the original PE material determines its good stability but is accompanied by poor bioaffinity and hydrophilicity. Polylactic acid does not exist in nature and is generally produced by artificial synthesis. Polylactic acid, also called polylactide, is a biodegradable high molecular polyester material, belongs to the synthesis of linear aliphatic polyesters, and can be obtained by chemical polymerization of cyclic dimer of lactic acid or direct polymerization of lactic acid. Polylactic acid is non-toxic to a human body, non-irritating, good in biocompatibility, and bioabsorbable, and does not leave any environmental problem after being degraded, and has been considered as the most promising degradable high polymer material in the medical field, so that research and development on the polylactic acid are extremely active. Since the hydrophobicity of PLA hinders cell adhesion and proliferation, polylactic acid must be modified to increase its number of hydrophilic functional groups. However, the prior art disclosures fail to take into account the properties of the filler: good biological affinity (suitable for biofilm formation growth), good hydrophilicity, larger specific surface area and porosity and better adsorbability, and the existing filler can not realize quick start of the biofilm while purifying sewage.
Through the above analysis, the problems and defects of the prior art are as follows: the filler used in the sewage treatment plant at present has the advantages of economy, environmental protection, difficult blockage and the like. However, the carrier produced by the prior art has poor biofilm formation effect, slow biofilm formation and little adhered biomass. The fundamental reason for this may be that the existing carriers have a great disadvantage in their performance, so that the carriers exhibit the disadvantage of poor biofilm formation performance during the application in waterworks.
The difficulty in solving the above problems and defects is: the priming effect of conventional biofilms is very slow. The materials used in common sewage treatment plants are polyethylene, and the hydrophilicity of the materials is poor. In addition, the material has poor biocompatibility, and has the advantage of durability, but the comprehensive performance of the material is poor. Other types of materials have various disadvantages. For example, polyurethane foam is easily blocked, fibrous materials have a low amount of bioadhesion, and the materials are not durable enough.
The general carrier modification does not meet the requirements of the town sewage plant carrier use standard (CJ/T461-. The modification of the method is only carried out by taking a common polyethylene carrier as a framework. In addition to this type of material, other types of materials are not easily modified as a backbone.
The modified carrier is usually prepared by thermoplastic method and mixed recasting, and the method does not need recasting the polyethylene material skeleton. Although the technology is mature, the method has high energy consumption and high economic cost.
The significance of solving the problems and the defects is as follows: the official standard for the contact angle of PE material is 87.5 deg., and is less hydrophilic. After the modification of the biological flocculant doped with the PLA flocculant, the contact angle of the surface of the material can be reduced to 52 degrees. The hydrophilic performance of the material is greatly improved.
The smaller contact angle means that the water-soluble carrier is more hydrophilic, and microorganisms floating in the water film near the carrier can be better close to the modified carrier and can be better planted on the surface of the modified carrier, so that the reversible adhesion of the initial stage of the biological film is provided with the greatest possibility. In addition, the PLA is doped with the biological flocculant, so that the biocompatibility of the material is improved, and the material can be used as a slow-release carbon source. The method fundamentally solves the problems of poor hydrophilicity and poor biocompatibility, is different from the common method for doping the modified carrier (most of the substances required by the thermoplastic method), not only fundamentally reduces the material modification cost, but also shortens the preparation time of the modified carrier, and is more economically improved. The technology can not only rapidly prepare the composite modified carrier, but also is beneficial to the development of the sewage treatment industry.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for treating sewage by using a composite modified carrier and application thereof. In particular to a method for preparing a composite modified carrier of a PLA doped biological flocculant and treating sewage.
The invention is realized in such a way that a preparation method of a composite modified carrier comprises the following steps:
the preparation method of the biological flocculant solution comprises the following steps:
(1) preparing a culture medium, and adjusting the pH value;
(2) inoculating flocculogenic bacteria (mainly used for secreting flocculant) under aseptic condition, and culturing at 30 deg.C for 72 h.
Preparing a composite modified carrier;
(1) adding polylactic acid powder into trichloromethane, stirring in a water bath, and fully dissolving;
(2) adding a supersaturated sodium chloride biological flocculant solution into a trichloromethane solution in which polylactic acid is dissolved, fully stirring and dissolving;
(3) adding a proper amount of polyethylene common plastic carrier into the trichloromethane solution in which the polylactic acid and the supersaturated sodium chloride bioflocculant are fully dissolved to ensure that the trichloromethane solution is completely soaked by the trichloromethane;
(4) and taking out the soaked carrier, and naturally ventilating and drying.
Further, in the initial preparation stage of the three-dimensional porous material, physical reversible adsorption of microorganisms is realized by utilizing the characteristic of large specific surface area; in the later preparation stage, polysaccharide and protein of the carrier residue are utilized to realize irreversible adsorption of microorganisms.
Further, after the three-dimensional porous material is prepared, the three-dimensional porous material is applied to the field planting adhesion of a carrier biological membrane, and a phospholipid method is adopted to detect biomass.
Further, common flocculogens were inoculated: bacillus sphaericus (Bacillus sphaeicus), Klebsiella sp (Klebsiella sp.), and the like.
The invention also aims to provide a composite modified carrier prepared by the preparation method.
The invention also aims to provide a sewage treatment method by using the composite modified carrier, which comprises the following steps: the prepared three-dimensional porous material is applied to the field planting adhesion of a carrier biological membrane, a phospholipid method is adopted to detect biomass, and a spectrophotometry method is adopted to detect COD, total nitrogen and total phosphorus.
Further, the permanent planting adhesion of the carrier biofilm comprises:
the prepared carrier is put into a reactor to operate for two months, the operation period of the reactor is 3 hours of aeration, 1 hour of standing is carried out, and water and sludge are discharged in the later period of standing for 5 min.
Further, the specific process of putting the prepared carrier into the reactor is as follows: before sampling, the reactor is emptied, and then a self-made sampler is used for taking out a proper amount of filler from different heights of the reactor;
placing the object to be tested in a 2500mL triangular flask with a plug, adding 47.5mL of extraction mixed solution of chloroform, methanol and water, shaking for 10min with force, standing for 12h, and adding 12.5mL of chloroform and water into the triangular flask respectively to ensure that the final chloroform: methanol: water is 1: 2: 0.8, and standing is carried out for 12 hours;
taking out 12.5mL of the lower chloroform phase containing lipid components, transferring to a 50mL test tube with a plug scale, and evaporating in a water bath;
adding 4mL of 5% potassium persulfate solution into the test tube, adding water to 25mL scale, digesting in an autoclave at 121 ℃ for 30min, and determining the phosphate concentration in the digestion solution according to a method for preparing a standard curve;
putting the composite modified carrier into a reactor and operating for two months; taking 4 carriers every ten days, and determining biomass adhered to the carriers by a phospholipid method; detecting the removal rate of COD, total nitrogen and total phosphorus in the sewage every two or three days during the biofilm formation; the COD concentration of the inlet water is kept at 400mg/L, TN 40mg/L and TP10 mg/L.
Further, the volume ratio of the chloroform to the methanol to the water is 1: 2: 0.8;
further, as a result of measuring the phosphate concentration in the digestion solution by the method for preparing the calibration curve, nmol P filler or nmol P/cm is used3Filler representation, 1nmol P approximately corresponds to Escherichia coli size of cells 108And putting the prepared carrier into the reactor for two months.
According to the invention, the biological flocculant is added into the polylactic acid, so that a large amount of polysaccharide and protein are doped in the porous polylactic acid, and the porous polylactic acid is used as a slow-release carbon source and is applied to industrial wastewater with insufficient carbon source.
By combining all the technical schemes, the invention has the advantages and positive effects that:
(1) under a certain temperature conditionThe chloroform is volatilized, and the polylactic acid can form a three-dimensional porous material in a saturated sodium chloride solution. The formed porous material has a larger specific surface (7.64-47.41 m) compared with the common PE carrier2(g) and pore diameter (2.11-6.20 μm).
(2) In the process of compounding polylactic acid and polysaccharide-protein scaffold forming the bioflocculant, polysaccharide has positive charges and is combined with protein molecules through electrostatic action to form a polyelectrolyte compound; the protein contains a large number of hydrophilic groups such as amino and carboxyl, so that the hydrophilic performance of the carrier is increased along with the introduction of the bioflocculant, and the permeability and oxygen permeability of the solute are improved.
(3) Compared with the common PLA adhesion modified carrier, the PLA + bioflocculant composite modified carrier can see a light yellow bioflocculant wrapped inside in addition to a three-dimensional porous structure under an optical microscope (see figure 7). On the carrier loaded with the biological membrane after the experiment is finished, the sample of the composite modified carrier material loaded with the biological membrane prepared by the method for preparing the sample of the scanning electron microscope can effectively observe the structure and the biological community aggregate of the biological flocculant in the sample.
The material of the invention has extremely large surface area and porosity, can realize the rapid biofilm formation of the carrier in the initial stage due to the physical property through the composite modified carrier, and has obvious technical advantages. The invention takes into account the properties of the filler: bioaffinity (adhesion of cell groups to the carrier, suitable for biofilm growth). Meanwhile, the microorganism adsorbed by the physical property generates extracellular polymer and other groups which are easy to adhere to the surface of the material on the surface of the carrier, so that the microorganism is adsorbed from simple reversible physics, and stable irreversible adhesion is gradually formed. According to the invention, the biological flocculant is added into the polylactic acid, so that a large amount of polysaccharide and protein are doped in the porous polylactic acid, and the porous polylactic acid can also be used as a slow-release carbon source and applied to sewage treatment of low carbon sources.
Meanwhile, the composite three-dimensional porous scaffold is prepared by the method of graft copolymerization and physical blending-chemical crosslinking, the connectivity among scaffold pores is good, and the porosity is more than 75%. The polysaccharide can be chemically modified by sulfuric acid acylation, carboxymethylation, hydroxylation and the like, for example, an N-acetylated chitin film has higher tensile strength, permeability and blood compatibility, is more stable in acid-base solution, has higher thermal decomposition temperature and has better affinity with organisms. In the initial preparation stage, the physical reversible adsorption of microorganisms is realized by utilizing the advantage of large specific surface area; and in the later stage, polysaccharide and protein doped with the carrier are utilized to realize irreversible adsorption of microorganisms.
Drawings
FIG. 1 is a flow chart of a sewage treatment method using a composite modified carrier according to an embodiment of the present invention.
FIG. 2 is a flow chart of the preparation of a bioflocculant provided in an embodiment of the present invention.
FIG. 3 is a comparative graph of unmodified polyethylene carriers provided by the examples of the present invention, and complex modification of pure PLA modified carriers and PLA + bioflocculant engineering bacteria. (firstly, PLA + biological flocculant composite modified carrier; secondly, PLA modified carrier; thirdly blank carrier)
FIG. 4 is a diagram of COD removal rate data provided by the example of the present invention.
FIG. 5 is a graph of total nitrogen removal data provided by an embodiment of the present invention.
Fig. 6 is a diagram of TP removal rate data provided by an embodiment of the present invention.
FIG. 7 is a graph of biomass data provided by an embodiment of the invention.
FIG. 8 is a diagram of a modified support under a microscope provided by an embodiment of the invention. (PLA doped biological flocculant composite modified carrier; PLA modified carrier; biomembrane; partial enlarged view of biomembrane)
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a method for treating sewage by using a composite modified carrier, which is described in detail below by combining with the attached drawings.
The method for treating sewage by using the composite modified carrier provided by the invention can also be implemented by adopting other steps by persons of ordinary skill in the art, and the method for treating sewage by using the composite modified carrier provided by the invention in figures 1 and 2 is only a specific example.
The sewage treatment method with the composite modified carrier provided by the embodiment of the invention comprises the preparation of the composite modified carrier and the preparation of a biological flocculant solution.
As shown in fig. 1, the preparation method of the composite modified carrier provided by the embodiment of the present invention includes the following steps:
s101, adding polylactic acid powder into a trichloromethane solution, stirring in a water bath, and fully dissolving;
s102, adding supersaturated sodium chloride and a biological flocculant solution into a trichloromethane solution in which polylactic acid is dissolved, and fully stirring and dissolving;
s103, adding a proper amount of polyethylene common plastic carrier into the trichloromethane solution in which the polylactic acid, the supersaturated sodium chloride and the biological flocculant are fully dissolved to ensure that the trichloromethane solution is completely soaked by the trichloromethane;
s104, taking out the soaked carrier, and naturally ventilating and drying;
s105, the modified material is applied to quick start of a biological membrane, and a phospholipid method is used for detecting biomass in the application process, so that the removal effect is good.
In S101 provided by the embodiment of the present invention, the specific process is: pouring 20-40 mL of levorotatory 300-mesh polylactic acid powder into a 5L beaker, adding 2L of analytically pure trichloromethane, and putting the beaker into a 65 ℃ water bath kettle, heating at a constant temperature and fully stirring to fully dissolve the polylactic acid in the trichloromethane.
In S102 provided by the embodiment of the present invention, the specific process is: and pouring 0.5-1L of supersaturated sodium chloride biological flocculant solution into the beaker in the polylactic acid dissolving process. Stirring is continuously carried out during the pouring process.
In S103 provided by the embodiment of the present invention, the specific process is: adding a proper amount of polyethylene common plastic carrier into the trichloromethane solution in which the polylactic acid, the supersaturated sodium chloride and the biological flocculant are fully dissolved so as to ensure that the trichloromethane is completely soaked.
In S103 provided by the embodiment of the present invention, the specific process is: and taking out the soaked carrier, and naturally ventilating and drying.
As shown in fig. 2, the preparation method of the bioflocculant solution provided by the embodiment of the present invention includes the following steps:
s201, preparing a culture medium, and adjusting the pH value;
s202, inoculating common flocculogenic bacteria such as Bacillus sphaericus (Bacillus sphaeicus) and Klebsiella sp under aseptic conditions, and culturing at 30 ℃ for 72 h.
In S201 provided in the embodiment of the present invention, the specific process is: the production medium (per liter) consists of 10 g glucose, 2 g KH2PO4, 5 g K2HPO40.2 g MgSO4·7H2O, 0.1 g sodium chloride, 0.5 g urea and 0.5 g yeast extract. The initial pH value is adjusted to 7.2-7.5. All medium solutions were prepared with distilled water and sterilized at 121 ℃ for 30 min.
S202 provided by the embodiment of the invention is inoculated with flocculent bacteria under the aseptic condition and cultivated for 72h at the temperature of 30 ℃.
The biological flocculant is added into the polylactic acid, so that a large amount of polysaccharide and protein are doped in the porous polylactic acid, and the porous polylactic acid is used as a slow-release carbon source and is applied to industrial wastewater with insufficient carbon source.
In the process of compounding the polylactic acid and the polysaccharide-protein scaffold of the engineering bacteria, polysaccharide has positive charges and is combined with protein molecules through electrostatic action to form a polyelectrolyte compound; the protein contains a large number of hydrophilic groups such as amino and carboxyl, so that the hydrophilic performance of the carrier is increased along with the introduction of the bioflocculant, and the permeability and oxygen permeability of the solute are improved.
In S105 provided by the embodiment of the invention, the modified material is applied to a microbial community for rapid field planting and adhesion on a carrier, and a phospholipid method is used for detecting biomass in the application process, and the specific process is as follows:
the prepared carrier is put into a reactor to operate for two months, the operation period of the reactor is 3 hours of aeration, 1 hour of standing is carried out, water and sludge are discharged at the later stage of standing for 5min, and the measurement methods of COD, total nitrogen and total phosphorus are carried out according to the national standard.
The specific process of putting the prepared carrier into the reactor is as follows: before sampling, the reactor was vented and then a self-made sampler was used to take appropriate amounts of the packing from different heights in the reactor.
Placing the substance to be tested in a 2500mL triangular flask with a plug, adding 47.5mL of extraction mixed solution of chloroform, methanol and water (the volume ratio is 1: 2: 0.8), shaking for 10min, standing for 12h, adding 12.5mL of chloroform and water into the triangular flask respectively to obtain a final chloroform: methanol: water is 1: 2: 0.8, and standing is carried out for 12 hours;
taking out 12.5mL of the lower chloroform phase containing lipid components, transferring to a 50mL test tube with a plug scale, and evaporating in a water bath;
adding 4mL of 5% potassium persulfate solution into the test tube, adding water to 25mL scale, digesting in an autoclave at 121 ℃ for 30min, and determining the phosphate concentration in the digestion solution according to a method for preparing a standard curve; as a result, the filler is filled with nmol P or nmol P/cm3Filler means 1nmol of P approximately corresponding to cell 10 of e.coli (e.coli) size8Putting the prepared carrier into a reactor and operating for two months;
putting the composite modified carrier into a reactor and operating for two months; taking 4 carriers every ten days, and determining biomass adhered to the carriers by a phospholipid method; detecting the removal rate of COD, total nitrogen and total phosphorus in the sewage every two or three days during the biofilm formation; the COD concentration of the inlet water is kept at 400mg/L, TN 40mg/L and TP10 mg/L.
The technical solution of the present invention will be described in detail with reference to the following specific examples.
(1) Pouring 20-40 mL of levorotatory 300-mesh polylactic acid powder into a 5L beaker, adding 2L of analytically pure trichloromethane, and putting the beaker into a 65 ℃ water bath kettle, heating at a constant temperature and fully stirring to fully dissolve the polylactic acid in the trichloromethane. And pouring 0.5-1L of biological flocculant solution in which supersaturated sodium chloride is dissolved into the beaker in the polylactic acid dissolving process. Stirring is continuously carried out during the pouring process. Adding a proper amount of polyethylene common plastic carrier into the trichloromethane solution in which the polylactic acid, the supersaturated sodium chloride and the biological flocculant are fully dissolved so as to ensure that the trichloromethane is completely soaked. And taking out the soaked carrier, and naturally ventilating and drying.
The preparation method of the biological flocculant comprises the following steps:
the production medium (per liter) consists of 10 g glucose, 2 g KH2PO4, 5 g K2HPO40.2 g MgSO4·7H2O, 0.1 g sodium chloride, 0.5 g urea and 0.5 g yeast extract. The initial pH value is adjusted to 7.2-7.5. All medium solutions were prepared with distilled water and sterilized at 121 ℃ for 30 min. Then inoculating flocculogenous bacteria under aseptic condition, and culturing at 30 ℃ for 72 h.
(2) Before sampling, the reactor was vented and then a self-made sampler was used to take appropriate amounts of the packing from different heights in the reactor. Placing the substance to be tested in a 2500mL triangular flask with a plug, adding 47.5mL of extraction mixed solution of chloroform, methanol and water (the volume ratio is 1: 2: 0.8), shaking for 10min, standing for 12h, adding 12.5mL of chloroform and water into the triangular flask respectively to obtain a final chloroform: methanol: the water is 1: 2: 0.8, and the mixture is kept stand for 12 hours. The lower chloroform phase 12.5mL containing the lipid fraction was removed and transferred to a 50mL graduated tube and evaporated in a water bath. Adding 4mL of 5% potassium persulfate solution into the test tube, adding water to 25mL scale, digesting in an autoclave at 121 ℃ for 30min, and determining the phosphate concentration in the digestion solution according to the method for preparing a standard curve. As a result, the filler is filled with nmol P or nmol P/cm3Filler means 1nmol of P approximately corresponding to cell 10 of e.coli (e.coli) size8And putting the prepared carrier into the reactor for two months.
The composite modified carrier is put into a reactor to run for two months. Every ten days, 4 carriers were taken and biomass adhered to the carriers was measured by the phospholipid method. And during the biofilm formation, the removal rate of COD, total nitrogen and total phosphorus in the sewage is detected every two or three days. The COD concentration of the inlet water is kept at 400mg/L, TN 40mg/L and TP10 mg/L.
Fig. 3 is a comparison graph of an unmodified polyethylene carrier provided by an example of the present invention, and a pure PLA-modified carrier and a composite modified carrier of PLA + bioflocculants.
In fig. 3: the method comprises the following steps: PLA + biological flocculant composite modified carrier; secondly, the step of: a PLA modified carrier;
③: a blank vector.
Example 2
(1) Pouring 20-40 mL of levorotatory 300-mesh polylactic acid powder into a 5L beaker, adding 2L of analytically pure trichloromethane, putting the beaker into a 65 ℃ water bath kettle, heating at a constant temperature and fully stirring to fully dissolve the polylactic acid in the trichloromethane, and adding a proper amount of polyethylene common plastic carrier to fully soak the polylactic acid in the trichloromethane. And taking out the soaked carrier, and naturally ventilating and drying.
(2) Before sampling, the reactor was vented and then a self-made sampler was used to take appropriate amounts of the packing from different heights in the reactor. Placing the substance to be tested in a 2500mL triangular flask with a plug, adding 47.5mL of chloroform, methanol and water extraction mixed solution (the volume ratio is 1: 2: 0.8), shaking for 10min, standing for 12h, adding 12.5mL of chloroform and water into the triangular flask respectively to obtain a final chloroform: methanol: 1 part of water: 1: 0.9, standing for 12 h. The lower chloroform phase 12.5mL containing the lipid fraction was removed and transferred to a 50mL graduated tube and evaporated in a water bath. Adding 4mL of 5% potassium persulfate solution into the test tube, adding water to 25mL scale, digesting in an autoclave at 121 ℃ for 30min, and determining the phosphate concentration in the digestion solution according to the method for preparing a standard curve. As a result, the filler is filled with nmol P or nmol P/cm3Filler means 1nmol of P approximately corresponding to cell 10 of e.coli (e.coli) size8And (4) respectively.
(3) The single PLA modified carrier is put into a reactor to run for two months. Every ten days, 4 carriers were taken and biomass adhered to the carriers was measured by the phospholipid method. And during the biofilm formation, the removal rate of COD, total nitrogen and total phosphorus in the sewage is detected every two or three days. The COD concentration of the influent water is maintained at 400mg/L, TN 40mg/L and TP10 mg/L.
Example 3
(1) The support without any modification was put into the reactor and run for two months. The operation period of the reactor is 3 hours of aeration, 1 hour of standing, 5 minutes of water and sludge discharging in the later stage of standing, and the measurement methods of COD, total nitrogen and total phosphorus are carried out according to the national standard.
(2) Before sampling, the reactor was vented and then a self-made sampler was used to take appropriate amounts of the packing from different heights in the reactor. Placing the substance to be tested in a 2500mL triangular flask with a plug, adding 47.5mL of chloroform, methanol and water extraction mixed solution (volume ratio is 1: 2: 0.8), shaking for 10min, standing for 12h, adding 12.5mL of chloroform and water into the triangular flask respectively to obtain a final chloroform: methanol: 1 part of water: 1: 0.9, standing for 12 h. The lower chloroform phase 12.5mL containing the lipid fraction was removed and transferred to a 50mL graduated tube and evaporated in a water bath. Adding 4mL of 5% potassium persulfate solution into the test tube, adding water to 25mL scale, digesting in an autoclave at 121 ℃ for 30min, and determining the phosphate concentration in the digestion solution according to the method for preparing a standard curve. As a result, the filler is filled with nmol P or nmol P/cm3Filler means 1nmol of P approximately corresponding to cell 10 of e.coli (e.coli) size8And (4) respectively.
(3) The polyethylene support without any modification was put into the reactor and run for two months. Every ten days, 4 carriers were taken and biomass adhered to the carriers was measured by the phospholipid method. And during the biofilm formation, the removal rate of COD, total nitrogen and total phosphorus in the sewage is detected every two or three days. The COD concentration of the influent water is maintained at 400mg/L, TN 40mg/L and TP10 mg/L.
Through the three examples and the operation of the composite modified carrier for two months, the removal rate of COD or total nitrogen is higher than that of the blank group and the pure PLA modified carrier, as shown in FIG. 4, FIG. 5, FIG. 6 and FIG. 7. The biomass of the composite modified carrier is greatly improved compared with the blank group and the PLA modified group as a result of measuring the biomass by a phospholipid method (the biomass is detected by the phospholipid method).
In the invention, the saturated sodium chloride is dispersed in the solution so as to ensure that the polylactic acid which is not fixed is pore-formed, and the polylactic acid can be mixed with protein or polysaccharide to be mutually soluble and doped. The polylactic acid can be dissolved in an organic solvent, and when the organic solvent is volatilized, the polylactic acid is attached to the surface of the carrier and is doped with polysaccharide and protein to form a layer of porous material film. In the PLA-bioflocculant blending bracket system, water exists in the pores of the bracket material and can permeate into the bioflocculant to slowly swell to form certain gel, so that the balance water absorption rate of the bracket is increased. The bioflocculant is a secretion product of bioflocculant engineering bacteria, is a mixture of water-soluble polysaccharide and protein, has carboxyl and amino on a molecular chain at the same time, is protonated by the amino in an acidic medium and is protonated by the carboxyl in an alkaline medium, and the two processes influence the intermolecular action of polymers, so that the dissociation of hydrogen bonds of the polymers is caused, and a large amount of water is absorbed.
Compared with the common PLA loaded modified carrier, the PLA + bioflocculant composite modified carrier can see a light yellow bioflocculant wrapped inside in addition to a three-dimensional porous structure under an optical microscope (see figure 8). On the carrier loaded with the biological membrane after the experiment is finished, the sample of the composite modified carrier material loaded with the biological membrane prepared by the method for preparing the sample of the scanning electron microscope can effectively observe the structure and the biological community aggregate of the biological flocculant in the sample.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.

Claims (9)

1. The preparation method of the composite modified carrier is characterized by comprising the following steps of:
the preparation method of the biological flocculant solution comprises the following steps:
(1) preparing a culture medium, and adjusting the pH value;
(2) inoculating flocculogenic bacteria secreting biological flocculant under aseptic condition, and culturing at 30 deg.C for 72 h;
preparing a composite modified carrier:
(1) adding trichloromethane into the polylactic acid powder, stirring in a water bath, and dissolving;
(2) adding a supersaturated sodium chloride biological flocculant solution into a trichloromethane solution in which polylactic acid is dissolved, stirring and dissolving;
(3) adding a common polyethylene plastic carrier into a trichloromethane solution in which polylactic acid and a supersaturated sodium chloride bioflocculant are dissolved to ensure that the common polyethylene plastic carrier is completely soaked by trichloromethane;
(4) and taking out the soaked carrier, and naturally ventilating and drying.
2. The method for preparing the composite modified carrier of claim 1, wherein the carrier comprises 10 g glucose and 2 g KH per liter of biological medium2PO45 g of K2HPO40.2 g MgSO4·7H2O, 0.1 g sodium chloride, 0.5 g urea and 0.5 g yeast extract.
3. The method for preparing the composite modified vector according to claim 1, wherein common flocculants including Bacillus sphaericus (Bacillus sphaeicus), Klebsiella sp, and the like are inoculated.
4. The method for preparing the composite modified carrier according to claim 1, wherein the three-dimensional porous material is prepared and then applied to the field planting adhesion of carrier biological membranes, and a phospholipid method is adopted to detect biomass.
5. A composite modified carrier prepared by the preparation method of any one of claims 1 to 4.
6. The method for treating sewage by using the composite modified carrier as claimed in claim 5, wherein the method for treating sewage by using the composite modified carrier comprises the following steps: the prepared three-dimensional porous material is applied to the field planting adhesion of a carrier biological membrane, and COD, total nitrogen and total phosphorus biomass are detected by adopting a phospholipid method.
7. The method of claim 6, wherein the permanent planting adhesion of the carrier biofilm comprises:
the prepared carrier is put into a reactor to operate for two months, the operation period of the reactor is 3 hours of aeration, 1 hour of standing is carried out, and water and sludge are discharged in the later period of standing for 5 min.
8. The method for treating sewage by using the composite modified carrier as claimed in claim 7, wherein the specific process of putting the prepared carrier into the reactor is as follows: before sampling, the reactor is emptied, and then a proper amount of filler is taken out from different heights of the reactor;
placing the object to be tested in a 2500mL triangular flask with a plug, adding 47.5mL of extraction mixed solution of chloroform, methanol and water, shaking for 10min with force, standing for 12h, and adding 12.5mL of chloroform and water into the triangular flask respectively to ensure that the final chloroform: methanol: 1 part of water: 2: 0.8, standing for 12 hours;
taking out 12.5mL of the lower chloroform phase containing lipid components, transferring to a 50mL test tube with a plug scale, and evaporating in a water bath;
to the tube was added 4mL of 5% potassium persulfate solution and water to 25mL mark. Digesting in a high-pressure steam sterilizing pot at 121 ℃ for 30min, and determining the concentration of phosphate in the digestion solution according to a method for making a standard curve;
putting the composite modified carrier into a reactor and operating for two months; taking 4 carriers every ten days, and determining biomass adhered to the carriers by a phospholipid method; detecting the removal rate of COD, total nitrogen and total phosphorus in the sewage every two or three days during the biofilm formation; the COD concentration of the influent water is maintained at 400mg/L, TN 40mg/L and TP10 mg/L.
9. The method for treating sewage by using the composite modified carrier as claimed in claim 8, wherein the volume ratio of the chloroform to the methanol to the water is 1: 2: 0.8;
the phosphate concentration in the digestion solution is measured by the method for preparing the standard curve, and the result is nmol P filler or nmol P/cm3Filler representation, 1nmol P corresponding to Escherichia coli size of cells 108And putting the prepared carrier into the reactor for two months.
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CN109231433A (en) * 2018-10-22 2019-01-18 成都新柯力化工科技有限公司 A kind of sewage treatment biomembrane composite carrier and preparation method
CN111995026A (en) * 2020-06-28 2020-11-27 嘉兴市爵拓科技有限公司 Environment-friendly efficient composite biological flocculant and preparation method thereof

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CN104961227A (en) * 2015-06-26 2015-10-07 合肥济坤环保科技有限责任公司 Modified polyurethane suspended filler and preparation method and application thereof
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