CN114604963A - Functional biological carrier, preparation method and application thereof - Google Patents
Functional biological carrier, preparation method and application thereof Download PDFInfo
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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
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
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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
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
- C02F3/106—Carbonaceous materials
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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
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
- C02F3/108—Immobilising gels, polymers or the like
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- 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
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Abstract
The invention relates to the technical field of wastewater treatment, in particular to a functional biological carrier, and a preparation method and application thereof. The functional biological carrier comprises: a polyethylene bio-carrier; and a loading layer compounded on the surface of the polyethylene biological carrier; the components of the load layer comprise polyglycidyl methacrylate and carbon materials. The method comprises the steps of grafting the poly glycidyl methacrylate on the surface of a polyethylene biological carrier by an irradiation method, and combining the poly glycidyl methacrylate grafted on the surface of the polyethylene biological carrier with a carbon material by a chemical combination method to prepare the functional biological carrier. Compared with the traditional polyethylene biological carrier, the carrier has higher specific surface area and surface potential, has good biocompatibility and conductivity, promotes the attachment growth of a biological film and enhances the electron transfer effect among microbial species. The carrier can be used as a suspended filler of a moving bed biofilm reactor, and the biological treatment efficiency of wastewater and the system stability are improved.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a functional biological carrier, and a preparation method and application thereof.
Background
The activated sludge method is the most common biological wastewater treatment process, but in the process, because the activated sludge exists in a floc form, the sludge floc is easy to run off along with effluent in practical application, so that a great deal of microorganism loss is caused. Novel reactors such as a moving bed membrane bioreactor (MBBR) and a deep bed filter are filled with biological carriers such as filler or filter materials, and the surfaces of the novel reactors can be enriched with microorganisms, so that the microorganisms are prevented from being lost along with effluent, and the biological treatment effect is further enhanced.
The commonly used MBBR filler is made of high polymer materials and has the advantages of large specific surface area, long service life and the like. Although the biofilm attached to the MBBR filler can enhance the biological treatment efficiency and reduce the loss of microorganisms, most of polymer materials lack reactive groups on the surface and have poor biocompatibility, and the biofilm attached to the filler is easy to fall off due to collision or water flow impact. In addition, researches show that an inter-species electron transfer phenomenon exists among part of microorganisms, and the performance of anaerobic methanogenesis and denitrification can be improved by adding materials with a conductive function such as biochar and the like into a reactor. However, in the conventional MBBR filler, the interaction between microorganisms attached to the filler itself is not significant due to the insulating properties of the polymer material used for the filler itself, and there is no promotion effect on the inter-species electron transfer between microorganisms. Therefore, there is room for further improvement in the biological wastewater treatment efficiency.
In recent years, the conductive functional carrier is prepared by combining a conductive functional material such as biochar and the like and MBBR filler in a heating melting, bonding, extrusion blending and other modes, so as to achieve the purposes of promoting biological adhesion and enhancing the electron transfer among microorganism species. However, these methods still have some disadvantages, on one hand, the part of the conductive functional carrier is easy to fall off due to the physical action between the material and the filler in long-term operation; on the other hand, the modes of extrusion blending and the like consume more conductive functional materials, and the economic cost is high. Therefore, there is a lack of a conductive functional carrier that operates stably and is economical and friendly.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a functional biological carrier, a preparation method and an application thereof, and the functional biological carrier provided by the present invention can be used as a suspended filler of a moving bed biofilm reactor, so as to improve the biological treatment efficiency of wastewater.
The invention provides a functional biological carrier, which comprises:
a polyethylene bio-carrier;
and a loading layer compounded on the surface of the polyethylene biological carrier;
the components of the load layer comprise polyglycidyl methacrylate and a carbon material.
Preferably, the carbon material includes at least one of biochar and graphite.
Preferably, the biochar is prepared according to the following method:
a) soaking sawdust in hydrochloric acid solution, washing with distilled water, drying, and pulverizing;
b) and pyrolyzing the crushed sawdust in a nitrogen atmosphere to obtain the biochar.
The invention also provides a preparation method of the functional biological carrier, which comprises the following steps:
A) uniformly mixing a dichloromethane solution containing glycidyl methacrylate with a polyethylene biological carrier, removing oxygen in the system and sealing;
B) placing the sealed system in a radiation field for irradiation;
C) and mixing the irradiated polyethylene biological carrier with a dichloromethane solution containing a carbon material, reacting, and curing to obtain the functional biological carrier.
Preferably, the mass ratio of the glycidyl methacrylate to the polyethylene biological carrier is 2-3: 0.5 to 1.5;
the mass concentration of the dichloromethane solution containing glycidyl methacrylate is 20-25%;
oxygen in the system was removed by introducing nitrogen into the system.
Preferably, the radiation field adopts 7.4 x 1014Bq 60A source of Co gamma-rays;
the irradiation dose rate is 10-50 Gy/min, and the absorbed dose is 10-500 KGy;
after the irradiation, the method further comprises the following steps: washed with dichloromethane.
Preferably, the mass ratio of the carbon material to the polyethylene biological carrier in the step A) is 0.04-4: 2 to 5.
Preferably, in the step C), the reaction temperature is room temperature, and the reaction time is 0.5-4 h.
Preferably, the curing temperature is 60-70 ℃;
the curing mode is water bath curing, and the curing is carried out in a sealed environment.
The invention also provides the application of the functional biological carrier in wastewater treatment;
the functional biological carrier is the functional biological carrier described above or the functional biological carrier prepared by the preparation method described above.
The invention provides a functional biological carrier, which comprises: a polyethylene bio-carrier; and a loading layer compounded on the surface of the polyethylene biological carrier; the components of the load layer comprise polyglycidyl methacrylate and a carbon material. The method comprises the steps of grafting the poly glycidyl methacrylate to the surface of a polyethylene biological carrier by an irradiation method, and combining the poly glycidyl methacrylate grafted to the surface of the polyethylene biological carrier with a carbon material by a chemical combination method, thereby preparing the functional biological carrier. Compared with the traditional polyethylene biological carrier, the functional biological carrier has higher specific surface area and surface potential, has good biocompatibility and conductivity, and can promote the attachment growth of a biological film and enhance the electron transfer effect among microbial species. The carrier can be used as a suspended filler of a Moving Bed Biofilm Reactor (MBBR), improves the biological treatment efficiency of wastewater and the stability of a system, and reduces the economic cost.
Drawings
FIG. 1 is a schematic structural diagram of a functional bio-carrier according to an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a functional biological carrier, which comprises:
a polyethylene bio-carrier;
and a loading layer compounded on the surface of the polyethylene biological carrier;
the components of the load layer comprise polyglycidyl methacrylate and a carbon material.
FIG. 1 is a schematic structural diagram of a functional bio-carrier according to an embodiment of the present invention. Wherein, 1 is a polyethylene biological carrier, 2 is polyglycidyl methacrylate, and 3 is a carbon material.
The functional biological carrier provided by the invention comprises a polyethylene biological carrier 1. In certain embodiments of the invention, the polyethylene bio-carrier is MBBR filler with specifications K1, K2, or K3. In certain embodiments, the polyethylene bio-carrier specification is K1. The invention has no special limitation on the type and source of the polyethylene biological carrier, can be generally sold in the market, and particularly can be the polyethylene biological carrier produced by Nopont environmental protection science and technology Limited in Henan.
The functional biological carrier provided by the invention also comprises a loading layer compounded on the surface of the polyethylene biological carrier. The components of the supporting layer comprise poly glycidyl methacrylate 2 and a carbon material 3.
In some embodiments of the present invention, the thickness of the load layer is 0.05 to 0.5 mm. In some embodiments, the thickness of the load layer is 0.05-0.3 mm.
In certain embodiments of the present invention, the carbon material comprises at least one of biochar and graphite. In certain embodiments, the carbon material comprises biochar and graphite, and the mass ratio of the biochar to the graphite is 0.5-1: 0.5 to 1. In certain embodiments, the mass ratio of biochar to graphite is 1: 1. in some embodiments of the present invention, the graphite has a particle size of 200 to 500 mesh, preferably 325 mesh.
In certain embodiments of the invention, the biochar is prepared according to the following method:
a) soaking sawdust in hydrochloric acid solution, washing with distilled water, drying, and pulverizing;
b) and pyrolyzing the crushed sawdust in a nitrogen atmosphere to obtain the biochar.
In step a):
in certain embodiments of the present invention, the hydrochloric acid solution has a mass concentration of 10% to 15%, preferably 10%.
In some embodiments of the present invention, the wood chips have a particle size of 1 to 10 mm.
In some embodiments of the present invention, the soaking time is 0.5 to 2 hours. In certain embodiments, the soaking time is 0.5 h.
In some embodiments of the present invention, the drying temperature is 60 to 80 ℃, preferably 60 ℃.
In some embodiments of the present invention, the particle size of the crushed wood chips is 40 to 200 mesh. The comminution is carried out in a universal mill.
In step b):
in certain embodiments of the invention, the pyrolysis temperature is 400 to 600 ℃; the pyrolysis time is 2-4 h, preferably 3 h. In certain embodiments, the temperature of the pyrolysis is 400 ℃, 500 ℃ or 600 ℃, preferably 400 ℃.
The pyrolysis is carried out in an alumina crucible of a tube furnace.
The invention also provides a preparation method of the functional biological carrier, which comprises the following steps:
A) uniformly mixing dichloromethane solution containing glycidyl methacrylate with polyethylene biological carrier, removing oxygen in the system and sealing;
B) placing the sealed system in a radiation field for irradiation;
C) and mixing the irradiated polyethylene biological carrier with a dichloromethane solution containing a carbon material, reacting, and curing to obtain the functional biological carrier.
The raw material components used in the preparation method of the functional biological carrier are the same as above, and are not described in detail herein.
The method comprises the steps of mixing a dichloromethane solution containing Glycidyl Methacrylate (GMA) with a polyethylene biological carrier uniformly, removing oxygen in the system and sealing.
In certain embodiments of the present invention, the mass ratio of the glycidyl methacrylate to the polyethylene bio-carrier is 2-3: 0.5 to 1.5, preferably 2.5: 1.
in certain embodiments of the present invention, the concentration of the glycidyl methacrylate-containing methylene chloride solution is 20% to 25%, preferably 25%, by mass.
In certain embodiments of the invention, the blending is performed in an irradiation vial.
In certain embodiments of the invention, oxygen is removed from the system by passing nitrogen through the system. Specifically, the method comprises the following steps: and introducing nitrogen into the irradiation bottle to remove oxygen in the irradiation bottle. The time for introducing the nitrogen gas may be 5-10 min, and in some embodiments, the time for introducing the nitrogen gas is 5 min.
After removing oxygen from the irradiation bottle, sealing was performed.
And then, the sealed system is placed in a radiation field for irradiation. Specifically, the sealed irradiation bottle is placed in a radiation field for irradiation.
In some embodiments of the invention, the radiation field is 7.4 × 1014Bq 60A source of Co gamma-rays;
the irradiation dose rate is 10-50 Gy/min, and the absorbed dose is 10-500 KGy.
In certain embodiments of the invention, the irradiation is at a dose rate of 20Gy/min and an absorbed dose of 30 KGy.
After irradiation, glycidyl methacrylate is grafted to a polyethylene biological carrier, and meanwhile, glycidyl methacrylate reacts to obtain the polyglycidyl methacrylate.
In some embodiments of the present invention, after the irradiating, further comprising: washed with dichloromethane. To remove unreacted monomer and homopolymer.
And after cleaning, mixing the cleaned polyethylene biological carrier with a dichloromethane solution containing a carbon material, reacting, and solidifying to obtain the functional biological carrier.
In certain embodiments of the present invention, the mass ratio of the carbon material to the polyethylene bio-carrier in step a) is 0.04 to 4: 2-5, preferably 0.4: 3.
in some embodiments of the present invention, the concentration of the carbon material-containing methylene chloride solution is 1 to 100 g/L. In certain embodiments, the concentration of the carbon material-containing methylene chloride solution is 10 g/L.
In certain embodiments of the invention, the mixing is homogenisation.
In some embodiments of the present invention, the reaction temperature is room temperature and the reaction time is 0.5 to 4 hours. In certain embodiments, the reaction time is 2 hours.
In certain embodiments of the present invention, the curing temperature is 60 to 70 ℃. In certain embodiments, the temperature of the curing is 65 ℃.
In certain embodiments of the present invention, the curing is by water bath curing, which is performed in a sealed environment.
In certain embodiments of the invention, the above-mentioned dichloromethane is 99.5% pure.
The invention also provides an application of the functional biological carrier in wastewater treatment;
the functional biological carrier is the functional biological carrier described above or the functional biological carrier prepared by the preparation method described above.
Specifically, the invention provides the application of the functional biological carrier as a suspended filler for wastewater treatment, such as: the functional biological carrier is applied as a suspended filler of a moving bed biofilm reactor.
The source of the raw materials used in the present invention is not particularly limited, and the raw materials may be those generally commercially available.
Has the advantages that:
the functional biological carrier provided by the invention has the advantages that all substances are combined by chemical action, the combination is firm, and the functional carbon material is not easy to fall off and can be used for a long time.
The functional biological carrier provided by the invention only has a layer of functional carbon material combined on the surface, reduces the adding cost of the conductive functional material, and is economical and friendly.
The functional biological carrier provided by the invention can be used for providing microorganism adhesion and enhancing the inter-species electron transfer of the microorganism, thereby further improving the biological treatment efficiency of the wastewater.
In order to further illustrate the present invention, the following examples are provided to describe a functional bio-carrier, its preparation method and application in detail, but should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all commercially available.
Example 1
Preparing biochar:
1) soaking wood chips with the particle size of 1-10 mm in 10% hydrochloric acid solution for 0.5h, washing with distilled water, drying at 60 ℃, and crushing the dried wood chips with a universal crusher, wherein the particle size of the crushed wood chips is 40-200 meshes;
2) and putting the crushed wood chips into an alumina crucible, putting the alumina crucible into a tubular furnace, and pyrolyzing the wood chips at 400 ℃ for 3 hours under the nitrogen atmosphere to obtain the biochar.
Preparation of functional biological carrier:
1) uniformly mixing a polyethylene biological carrier with the specification of K1 and 25% of dichloromethane solution containing glycidyl methacrylate in mass concentration in an irradiation bottle, introducing nitrogen into the irradiation bottle for 5min to remove oxygen in the irradiation bottle, and sealing;
the mass ratio of the glycidyl methacrylate to the polyethylene biological carrier is 2.5: 1;
2) placing the sealed irradiation bottle in a radiation field for irradiation;
the radiation field adopts 7.4 multiplied by 1014Bq 60A source of Co gamma-rays; the irradiation dose rate is 20Gy/min, and the absorbed dose is 30 KGy;
after irradiation, taking out the polyethylene biological carrier, and cleaning the polyethylene biological carrier by using dichloromethane to remove unreacted monomers and homopolymers;
3) after cleaning, uniformly mixing the cleaned polyethylene biological carrier with a dichloromethane solution containing a carbon material with the concentration of 10g/L, reacting for 2 hours at room temperature, sealing the system, and performing water bath solidification at 65 ℃ to obtain a functional biological carrier;
the carbon material is the biochar prepared above;
the mass ratio of the carbon material to the polyethylene biological carrier in the step 1) is 0.4: 3.
the obtained functional biological carrier comprises:
a polyethylene bio-carrier;
and a loading layer compounded on the surface of the polyethylene biological carrier; the thickness of the load layer is 0.05-0.3 mm;
the components of the load layer comprise polyglycidyl methacrylate and a carbon material.
The obtained functional biological carrier is added into a heterotrophic denitrification moving bed biological membrane reactor, the volume of the functional biological carrier accounts for 40% of the volume of the moving bed biological membrane reactor, the COD of the inlet water of the reactor is 300mg/L, the nitrate is 50mg/L, the hydraulic retention time in the reactor is 8h, the nitrate removal rate of the reactor is measured, and the result is shown in Table 1.
Example 2
The temperature of pyrolysis in example 1 was changed to 500 deg.c, and the remaining steps were performed as in example 1, to obtain a functional bio-carrier. The nitrate removal rate of the reactor was measured according to the test method of example 1, and the results are shown in table 1.
Example 3
The temperature of pyrolysis in example 1 was changed to 600 ℃, and the remaining steps were performed as in example 1, to obtain a functional bio-carrier. The nitrate removal rate of the reactor was measured according to the test method of example 1, and the results are shown in table 1.
Example 4
The carbon material in example 1 was changed to graphite, and the remaining steps were performed as in example 1 to prepare a functional bio-carrier. The nitrate removal rate of the reactor was measured according to the test method of example 1, and the results are shown in table 1.
Example 5
Changing the carbon material in example 1 into biochar and graphite, wherein the mass ratio of the biochar to the graphite is 1: 1, the rest of the steps are carried out according to the example 1, and the functional biological carrier is prepared. The nitrate removal rate of the reactor was measured according to the test method of example 1, and the results are shown in table 1.
Comparative example 1
Preparation of functional biological carrier:
1) uniformly mixing a polyethylene biological carrier with the specification of K1 and 25% of dichloromethane solution containing glycidyl methacrylate in mass concentration in an irradiation bottle, introducing nitrogen into the irradiation bottle for 5min to remove oxygen in the irradiation bottle, and sealing;
the mass ratio of the glycidyl methacrylate to the polyethylene biological carrier is 2.5: 1;
2) placing the sealed irradiation bottle in a radiation field for irradiation;
the radiation field adopts 7.4 multiplied by 1014Bq 60A source of Co gamma-rays; the irradiation dose rate is 20Gy/min, and the absorbed dose is 30 KGy;
after irradiation, taking out the polyethylene biological carrier, and cleaning the polyethylene biological carrier by using dichloromethane to remove unreacted monomers and homopolymers;
3) after cleaning, sealing the cleaned polyethylene biological carrier, and curing the polyethylene biological carrier in water bath at 65 ℃ to obtain a functional biological carrier;
the obtained functional biological carrier is added into a heterotrophic denitrification moving bed biological membrane reactor, the volume of the functional biological carrier accounts for 40% of the volume of the moving bed biological membrane reactor, the COD of the inlet water of the reactor is 300mg/L, the nitrate is 50mg/L, the hydraulic retention time in the reactor is 8h, the nitrate removal rate of the reactor is measured, and the result is shown in Table 1.
TABLE 1 nitrate removal rates for reactors of examples 1-5 and comparative example 1
As can be seen from table 1, compared to comparative example 1, the functional bio-carrier of examples 1 to 5 significantly improves the removal rate of nitrate in the moving bed biofilm reactor, wherein the removal rate of nitrate in examples 1 and 5 exceeds 95%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A functional biovector comprising:
a polyethylene bio-carrier;
and a loading layer compounded on the surface of the polyethylene biological carrier;
the components of the load layer comprise polyglycidyl methacrylate and a carbon material.
2. The functional biovector of claim 1 wherein said carbon material comprises at least one of biochar and graphite.
3. The functional biovector of claim 2, wherein the biochar is prepared according to the following method:
a) soaking sawdust in hydrochloric acid solution, washing with distilled water, drying, and pulverizing;
b) and pyrolyzing the crushed sawdust in a nitrogen atmosphere to obtain the biochar.
4. A preparation method of a functional biological carrier comprises the following steps:
A) uniformly mixing dichloromethane solution containing glycidyl methacrylate with polyethylene biological carrier, removing oxygen in the system and sealing;
B) placing the sealed system in a radiation field for irradiation;
C) and mixing the irradiated polyethylene biological carrier with a dichloromethane solution containing a carbon material, reacting, and curing to obtain the functional biological carrier.
5. The preparation method according to claim 4, wherein the mass ratio of the glycidyl methacrylate to the polyethylene bio-carrier is 2-3: 0.5 to 1.5;
the mass concentration of the dichloromethane solution containing glycidyl methacrylate is 20-25%;
oxygen in the system was removed by introducing nitrogen into the system.
6. The method of claim 4, wherein the radiation field is 7.4 x 1014Bq60A source of Co gamma-rays;
the irradiation dose rate is 10-50 Gy/min, and the absorbed dose is 10-500 KGy;
after the irradiation, the method further comprises the following steps: washed with dichloromethane.
7. The preparation method according to claim 4, wherein the mass ratio of the carbon material to the polyethylene bio-carrier in the step A) is 0.04-4: 2 to 5.
8. The preparation method according to claim 4, wherein in the step C), the reaction temperature is room temperature and the reaction time is 0.5-4 h.
9. The preparation method according to claim 4, wherein the curing temperature is 60-70 ℃;
the curing mode is water bath curing, and the curing is carried out in a sealed environment.
10. The application of a functional biological carrier in wastewater treatment;
the functional biological carrier is the functional biological carrier of any one of claims 1 to 4, or the functional biological carrier prepared by the preparation method of any one of claims 5 to 9.
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