CN113213617B - Preparation method of modified magnetic suspension biological carrier for nitrosation process - Google Patents
Preparation method of modified magnetic suspension biological carrier for nitrosation process 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
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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
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
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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
- C02F3/28—Anaerobic digestion processes
- C02F3/2813—Anaerobic digestion processes using anaerobic contact processes
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- 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
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
Abstract
The invention relates to the technical field of wastewater treatment, in particular to a preparation method of a modified magnetic suspended biological carrier for a nitrosation process.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a preparation method of a modified magnetic suspension biological carrier for a nitrosation process.
Background
The anaerobic biofilm and activated sludge composite process (An-IFFAS) and the anaerobic moving bed biofilm process (AMBBR) based on the suspended biological carriers combine the advantages of An anaerobic activated sludge process and a biofilm process, and show unique potential in the anaerobic treatment of organic sewage. The carrier is used as the core of the process, and the physical and chemical properties of the carrier play an important role in the water treatment efficiency of the process. The current commercial High Density Polyethylene (HDPE) has a problem of poor biocompatibility.
Disclosure of Invention
In order to achieve the purpose, the invention provides a preparation method of a modified magnetic suspended biological carrier for a nitrosation process, which improves the hydrophilicity and the conductivity of an HDPE (high-density polyethylene) base material, promotes the direct inter-inoculation electron transfer of anaerobic ammonium oxidation bacteria, improves the removal rate of flora on ammonia nitrogen, and increases the functional design of the traditional suspended biological carrier. The specific technical scheme is as follows:
s1, material preparation and pretreatment
Preparing HDPE base materials, modified functional materials and magnetic powder required by carrier preparation, and drying the raw materials at 115 ℃ for 5h to remove moisture;
s2 preparation of modified functional material
S2-1, preparing Cr-MIL-101-NH by one-step method2MOF system of CQD configuration;
s2-2, preparing a CNT sponge by using a template sacrifice method;
s2-3, preparation of Fe/graphene @ MOF composite system
S2-3-1, sealing ethanol and heating the MOF system prepared in the step S2-1 at 80 ℃ for 8h, and completely activating and opening pore channels;
s2-3-2, adding zero-valent iron and graphene into the MOF system subjected to activation treatment in the step S2-3-1, and violently stirring for 2h at 70 ℃; then, vacuum drying the mixture product at 80 ℃ for 24h to obtain a Fe/graphene @ MOF composite system;
s2-4, preparation of Fe/graphene @ MOF/CNT composite system
S2-4-1, sealing ethanol and heating the CNT sponge prepared in the step S2-2 at 80 ℃ for 8 hours, and completely activating and opening the pore channel;
s2-4-2, adding the Fe/graphene @ MOF composite system prepared in the step S2-3-2 into ethanol in the step S2-4-1 according to the proportion that 1-2 parts of the Fe/graphene @ MOF composite system are matched with 1 part of CNT sponge, and stirring vigorously for 2 hours; then, vacuum drying the mixture product at 80 ℃ for 24 hours to obtain a Fe/graphene @ MOF/CNT composite system;
s2-5, mixing and uniformly stirring 2-4 parts of the Fe/graphene @ MOF/CNT composite carrier prepared in the step S2-4-2, 3 parts of diatomite and 1 part of talcum powder together to obtain a modified functional material;
s3, granulating
Weighing HDPE base materials, modified functional materials and magnetic powder required by preparation of the carrier according to a proportion, and completely and uniformly stirring; then, extruding the mixture by a single screw extruder, cooling by water and cutting by a granulator to obtain carrier particles;
s4, extrusion Molding
Carrying out extrusion molding, shaping, cooling and cutting on the carrier particles prepared in the step S3 to obtain a cylindrical carrier;
s5 magnetization
And (4) magnetizing the cylindrical carrier prepared in the step (S4) by a magnetizer to obtain the modified magnetic suspension biological carrier.
Further, the specific steps of preparing the MOF system in step S2-1 are as follows:
s2-1-1 reaction of H2BDC-NH2，Cr(NO3)3·9H2Dissolving O and NaOH in deionized water, and vigorously stirring at 25 deg.C for 30 min;
s2-1-2, after the mixture solution prepared in the step S2-1-2 is cooled to room temperature, centrifugally separating the mixture solution to obtain a solid product;
s2-1-3, washing the solid product prepared in the step S2-1-2 with N-N dimethylformamide, methanol and deionized water respectively for 8-10 times, and then drying for 24 hours at 100 ℃ to obtain an MOF system.
Further, in the step S2-1-1, H2BDC-NH2：1.44g，8.0mmol； Cr(NO3)3·9H2O: 3.20g, 8.0 mmol; NaOH: 0.80g, 20 mmol; deionized water: 60 mL.
Further, the specific steps of preparing the CNT sponge in the step S2-2 are as follows:
s2-2-1, mixing PVDF, NaCl and CNT, and ball-milling into uniform powder;
s2-2-2, heating the mixed powder prepared in the step S2-2-1 at 200 ℃ for 3 hours, and cooling the mixed powder to room temperature to obtain a block sample;
s2-2-3, polishing to remove the outermost layer of the block sample prepared in the step S2-2-2, and then washing the polished block sample for multiple times in a water bath condition at 85 ℃ until NaCl is completely dissolved;
s2-2-4, drying the block sample treated by the step S2-2-3 at-70 ℃ for 24h to obtain the porous CNT sponge.
Further, in the step S2-2-1, PVDF, NaCl, and CNT are mixed in a mass ratio of 3: 5: 4.
Further, in the step 2-3-2, zero-valent iron and graphene are added into the MOF system after the activation treatment in the step S2-3-1, wherein the addition amount of the zero-valent iron is as follows: 1-2 wt%, and the addition amount of graphene is as follows: 3 to 5 wt%.
Further, in the step S3, the mass ratio of the HDPE base material, the modified functional material, and the magnetic powder in the carrier is 100: 9: 7.
further, in step S3, the specific parameters of the granulation process are as follows: the temperature range of the feed hopper is 180-195 ℃, and the rotating speed of the screw is 25 rpm.
Further, in step S4, the specific parameters of the extrusion molding process are as follows: the temperature of the feeding stage is 135 ℃, the temperature of the melting stage is 150 ℃, the temperature of the mixing stage is 160 ℃, and the temperature of the forming stage is 140 ℃; the screw speed was 25 rpm.
Compared with the existing suspended biological carrier, the invention has the beneficial effects that:
the invention provides a preparation method of a modified magnetic suspended biological carrier for a nitrosation process, which improves the hydrophilicity and the conductivity of an HDPE (high-density polyethylene) substrate, promotes the direct inter-inoculation electron transfer of anaerobic ammonium oxidation bacteria, improves the removal rate of flora on ammonia nitrogen, and increases the functional design of the traditional suspended biological carrier.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is an SEM image of a MOF system made by the present invention;
fig. 3 is an SEM image of the CNT sponge prepared according to the present invention.
Detailed Description
In order to further illustrate the adopted modes and the obtained effects of the invention, the technical scheme of the invention is clearly and completely described by combining the embodiment and the experimental example.
Example 1
Example 1 mainly describes a specific method for preparing a modified magnetic suspension biological carrier, which comprises the following steps:
the equipment used to prepare the modified magnetically suspended biological carriers is shown in Table 1.
TABLE 1 apparatus for the production of the vectors
The specific preparation method of the modified magnetic suspension biological carrier comprises the following specific steps:
s1, preparing and pretreating materials
Preparing HDPE base materials, modified functional materials and magnetic powder required by the preparation of a carrier, and drying the raw materials at 115 ℃ for 5 hours to remove moisture;
s2 preparation of modified functional material
S2-1, preparing Cr-MIL-101-NH by one-step method2MOF system of CQD configuration;
s2-2, preparing CNT sponge by using a template sacrifice method;
s2-3, preparation of Fe/graphene @ MOF composite system
S2-3-1, sealing ethanol and heating the MOF system prepared in the step S2-1 at 80 ℃ for 8h, and completely activating and opening pore channels;
s2-3-2, adding 1 wt% of zero-valent iron and 3 wt% of graphene into the MOF system subjected to activation treatment in the step S2-3-1, and violently stirring for 2h at 70 ℃; then, vacuum drying the mixture product at 80 ℃ for 24h to obtain a Fe/graphene @ MOF composite system;
s2-4, preparation of Fe/graphene @ MOF/CNT composite system
S2-4-1, sealing ethanol and heating the CNT sponge prepared in the step S2-2 at 80 ℃ for 8 hours, and completely activating and opening the pore channel;
s2-4-2, adding the Fe/graphene @ MOF composite system prepared in the step S2-3-2 into ethanol obtained in the step S2-4-1 according to the proportion that 1 part of the Fe/graphene @ MOF composite system is matched with 1 part of CNT sponge, and stirring vigorously for 2 hours; then, vacuum drying the mixture product at 80 ℃ for 24h to obtain a Fe/graphene @ MOF/CNT composite system;
s2-5, mixing and stirring 2 parts of the Fe/graphene @ MOF/CNT composite carrier prepared in the step S2-4-2, 3 parts of diatomite and 1 part of talcum powder uniformly to obtain a modified functional material;
s3, granulating
According to the following steps of 100: 9: 7, weighing the HDPE base material, the modified functional material and the neodymium iron boron required by the preparation of the carrier according to the mass ratio, and completely and uniformly stirring; extruding the uniformly mixed raw materials by an SJ-30 type single screw extruder, wherein the simple temperature of each extruder is 180 ℃, 185 ℃, 195 ℃ and 180 ℃, and the screw rotating speed is 50 rpm; cooling the extruded strip material by cooling water, and cutting the strip material into carrier particles by using a granulator for later use;
s4, extrusion Molding
Adding the carrier particles prepared in the step S3 into an SJ-30 type single-screw extruder for extrusion molding; the extrusion molding process of the extruder can be divided into a feeding stage, a melting stage, a uniformly mixing stage and a molding stage, wherein the temperatures of the stages are 135 ℃, 150 ℃, 160 ℃ and 140 ℃; the screw speed was 25 rpm;
shaping and cooling the extruded material by a vacuum shaping device after the shaping action of the die; in the production process of the carrier, continuous automatic production can be realized due to the continuous traction of the traction machine; the shaped carrier is cut into a Kl type carrier under the cutting of special scissors. The prepared carrier had a cylindrical shape with a diameter of l 0mm, a height of 10mm and a specific surface area of 590m2/m3. The middle part of the cylindrical carrier is provided with a strong cross grid support of a simply supported beam for reinforcing the carrier, and the outer part of the cylindrical carrier is provided with fins for increasing the surface area of the carrier;
s5 magnetization
And (4) magnetizing the cylindrical carrier prepared in the step (S4) by a magnetizer to obtain the modified magnetic suspension biological carrier.
Specifically, the specific steps for preparing the MOF system in step S2-1 are as follows:
s2-1-1, mixing H2BDC-NH2(1.44g，8.0mmol)，Cr(NO3)3·9H2O (3.20g, 8.0mmol) and NaOH (0.80g, 20mmol) were dissolved in 60mL deionized water and stirred vigorously at 25 ℃ for 30 min;
s2-1-2, after the mixture solution prepared in the step S2-1-2 is cooled to room temperature, centrifugally separating the mixture solution to obtain a solid product;
s2-1-3, washing the solid product prepared in the step S2-1-2 respectively with N-N dimethylformamide, methanol and deionized water for 10 times, and then drying at 100 ℃ for 24 hours to obtain an MOF system.
Specifically, the specific steps of preparing the CNT sponge in the step S2-2 are as follows:
s2-2-1, and mixing the components in a mass ratio of 3: 5: 4, mixing PVDF, NaCl and CNT and ball-milling into uniform powder;
s2-2-2, heating the mixed powder prepared in the step S2-2-1 at 200 ℃ for 3 hours, and cooling the mixed powder to room temperature to obtain a block sample;
s2-2-3, polishing to remove the outermost layer of the block sample prepared in the step S2-2-2, and then washing the polished block sample for multiple times in a water bath condition at 85 ℃ until NaCl is completely dissolved;
s2-2-4, drying the block sample treated by the step S2-2-3 at-70 ℃ for 24h to obtain the porous CNT sponge.
Example 2
Example 2 is based on the solution described in example 1, and is intended to illustrate the design of the solution under another parameter, which is the same except for the following:
s2-3-2, adding 2 wt% of zero-valent iron and 5 wt% of graphene into the MOF system subjected to activation treatment in the step S2-3-1, and violently stirring for 2h at 70 ℃; and then, vacuum drying the mixture product at 80 ℃ for 24h to obtain a Fe/graphene @ MOF composite system.
S2-4-2, adding the Fe/graphene @ MOF composite system prepared in the step S2-3-2 into ethanol obtained in the step S2-4-1 according to the proportion that 2 parts of the Fe/graphene @ MOF composite system are matched with 1 part of CNT sponge, and stirring vigorously for 2 hours; and then vacuum-drying the mixture product at 80 ℃ for 24h to obtain a Fe/graphene @ MOF/CNT composite system.
S2-5, mixing and stirring 4 parts of the Fe/graphene @ MOF/CNT composite carrier prepared in the step S2-4-2, 3 parts of diatomite and 1 part of talcum powder uniformly to obtain the modified functional material.
Experimental example 1
Experimental example 1 is described based on the preparation method described in the above example 1, and is intended to illustrate the physical properties of the carrier prepared according to the present invention.
1. Hydrophilicity of the support
The hydrophilicity of the common HDPE carrier and the modified carrier is detected by adopting a method for testing the contact angle between the surface of the carrier and a water drop.
Firstly, a flaky sample with a flat surface is cut off from a carrier, and then the flaky sample is placed in a forced air drying oven and dried for 2 hours at the temperature of 80 ℃. The contact angle of the sample with the water drop was measured using a static contact angle tester. When the instrument is operated, a certain amount of water is slowly dropped on the surface of the carrier sample, the size of the contact angle of the surface of the carrier is obtained by processing through software equipped in the instrument, the modified carrier sample is measured for 3 times, and the test result is shown in table 2.
TABLE 2 Carrier hydrophilicity
The data in table 2 show that the surface contact angle of the conventional HDPE carrier is 92 °, while the surface contact angle of the modified carrier designed according to the present invention is 95 ± 3 °, which indicates that the modified carrier designed according to the present invention has slightly better hydrophilic performance than the conventional HDPE carrier.
2. Conductivity of carrier
And detecting the conductivity of the common HDPE carrier and the modified carrier by using a four-probe conductivity testing instrument.
The carrier was first cut out into flat sheet samples, after which the surface of the carrier was wiped with a lens-wiping paper. The sample was carefully placed in the test stand with the gold electrode in good contact with the sample. And operating software equipped in the instrument, and processing the obtained sample to obtain the conductivity of the sample.
Modified support the sample support measurement set was: group 1 is MOF/CNT composite system; group 2 is a Fe @ MOF/CNT composite system; and the group 3 is a Fe/graphene @ MOF/CNT composite system.
Experimental group 3: the carrier is Fe/graphene @ MOF/CNT composite system, the measurement is carried out for 3 times, and the test result is shown in Table 3.
TABLE 3 Carrier conductivity
The data in Table 3 show that ordinary HDPE carriersThe conductivity of the body was 1.69X 10-5S/cm, and the conductivity obtained by testing is increased by increasing the doping amount of the conductive component of the modified carrier designed by the invention. This demonstrates that the idea of the improved conductivity of the carrier of the present invention is correct: the modified support has better conductivity than a conventional HDPE support.
Experimental example 2
Experimental example 2 is based on the preparation method described in example 1 above, and is intended to clarify the effect of the carrier of the present invention in practice.
1. Inoculated sludge and simulated wastewater
The inoculated sludge is the return sludge of an anaerobic digestion reaction tank of a certain sludge treatment plant of Sichuan, and the total suspended solid concentration (TSS) is 11892 +/-212 mg/L. The ratio of volatile suspended solids concentration (VSS) to total suspended solids concentration was 0.52. Prior to inoculation, the inoculated sludge was filtered using a filter screen. The amount of seeded sludge per reactor was 600mL.
The artificial simulation of high-concentration organic wastewater comprises the following components: the organic carbon source consisted of 2.6mL/L ethanol, 1.079g/L sodium acetate, and 0.72g/L sodium propionate, contributing to a COD ratio of about 4: l: 1, 0.22g/L of urea, 0.12g/L of monopotassium phosphate, 0.19g/L of dipotassium phosphate, 0.05g/L of anhydrous sodium sulfate, 0.06g/L of calcium chloride dihydrate and 0.lgL of magnesium chloride hexahydrate.
The trace element lmL/L comprises the following components: 5g/L of hydrated manganese sulfate, 0.5g/L of nickel chloride hexahydrate, lg/L of ferrous sulfate heptahydrate, 1.4g/L of zinc chloride, 0.51g/L of chlorodiamond hexahydrate, 0.L g/L of anhydrous copper sulfate, 0.2g/L of boric acid, 24g/L of sodium molybdate Ol and 0.1g/L of aluminum potassium sulfate dodecahydrate.
By adding a proper amount of sodium bicarbonate into water, the pH of the inlet water is maintained within the range of 7.5-7.9, and a proper growth environment is provided for producing anaerobic ammonium oxidation bacteria. The aeration amount is adjusted through a rotameter to control the concentration of Dissolved Oxygen (DO) to be 5-7 mg/.
2. Experiment grouping
Two control groups:
control group 1: anaerobic activated sludge reaction;
control group 2: and adding HDPE carrier for reaction.
Three experimental groups:
experimental group 1: the carrier is an MOF/CNT composite system;
experimental group 2: the carrier is a Fe/graphene @ MOF composite system;
experimental group 3: the carrier is a Fe/graphene @ MOF/CNT composite system.
The reactor operating mode was continuous flow operation according to An-IFFAS operating mode, with a peristaltic pump being used to adjust the sludge reflux ratio to 80%. The temperature of the five reaction groups was thermostated at 25 ℃. In order to ensure that the carrier-sludge-sewage can be fully mixed, five mechanical stirrers are arranged, the stirring frequency is controlled to be l h by using a time relay, the stirring is stopped for 5 hours, and a biological membrane is formed by intermittent stirring. L is
2. Experimental operation
At the initial stage of startup, the COD concentration of inlet water is about 300 +/-20 mg/L and NH4+When the-N concentration is 50mg/L, the parallel operation is carried out for 10 days without adding carriers, and the treatment effect is ensured to have no obvious difference among reactors. After 10 days, HDPE carrier and modified carrier were added to the reactor at 30% of the reactor volume in the corresponding experimental group.
The first phase was the biofilm formation initiation phase (day 1 to day 33). And when the operation is carried out to the 41 th day, the second stage is entered: day 34 to day 45. The specific results are shown in Table 4.
TABLE 4 Ammonia nitrogen removal Performance of five experimental groups
The data in Table 4 show the NH of the plain support in the first stage4+The highest N removal rate was 83.3%, while in the control group of modified carriers, H was increased with the improvement in the conductivity of the carrier4+The N removal rate is increased to 88.6%, and NH is improved along with improvement of the hydrophilicity of the carrier4+The N removal increased to 93.7%; second stage, generalSupported NH4+The highest N removal rate was 84.5%, while in the control group of modified carriers, H was increased with the improvement in the conductivity of the carrier4+The N removal rate increased to 89.9%, NH with improved hydrophilicity of the support4+the-N removal rate rose to 94.1%. The above data indicate that the present invention is successful in modifying suspended biological carriers.
Claims (9)
1. A preparation method of a modified magnetic suspension biological carrier for a nitrosation process is characterized by mainly comprising the following steps:
s1, material preparation and pretreatment
Preparing HDPE base materials, modified functional materials and magnetic powder required by the preparation of a carrier, and drying the raw materials at 115 ℃ for 5 hours to remove moisture;
s2 preparation of modified functional material
S2-1, preparing Cr-MIL-101-NH by one-step method2MOF system of CQD configuration;
s2-2, preparing a CNT sponge by using a template sacrifice method;
s2-3, preparation of Fe/graphene @ MOF composite system
S2-3-1, sealing ethanol and heating the MOF system prepared in the step S2-1 at 80 ℃ for 8h, and completely activating and opening pore channels;
s2-3-2, adding zero-valent iron and graphene into the MOF system subjected to activation treatment in the step S2-3-1, and violently stirring for 2h at 70 ℃; then, vacuum drying the mixture product at 80 ℃ for 24h to obtain a Fe/graphene @ MOF composite system;
s2-4, preparation of Fe/graphene @ MOF/CNT composite system
S2-4-1, sealing ethanol and heating the CNT sponge prepared in the step S2-2 at 80 ℃ for 8 hours, and completely activating and opening the pore channel;
s2-4-2, adding the Fe/graphene @ MOF composite system prepared in the step S2-3-2 into ethanol obtained in the step S2-4-1 according to the proportion that 1-2 parts of the Fe/graphene @ MOF composite system are matched with 1 part of CNT sponge in parts by weight, and stirring vigorously for 2 hours; then, vacuum drying the mixture product at 80 ℃ for 24h to obtain a Fe/graphene @ MOF/CNT composite system;
s2-5, mixing and uniformly stirring 2-4 parts by mass of the Fe/graphene @ MOF/CNT composite carrier prepared in the step S2-4-2, 3 parts by mass of diatomite and 1 part by mass of talcum powder to obtain a modified functional material;
s3, granulating
Weighing HDPE base materials, modified functional materials and magnetic powder required by preparation of the carrier according to a proportion, and completely and uniformly stirring; then, extruding the mixture by a single screw extruder, cooling by water and cutting by a granulator to obtain carrier particles;
s4, extrusion Molding
Carrying out extrusion molding, shaping, cooling and cutting on the carrier particles prepared in the step S3 to obtain a cylindrical carrier;
s5 magnetization
And (5) magnetizing the cylindrical carrier prepared in the step (S4) by a magnetizing machine to obtain the modified magnetic suspension biological carrier.
2. The method for preparing a modified magnetic levitation biological carrier for nitrosation process as claimed in claim 1, wherein said step S2-1 is to prepare MOF system of Cr-MIL-101-NH2/CQD configuration by the following steps:
s2-1-1, mixing H2BDC-NH2，Cr(NO3)3·9H2Dissolving O and NaOH in deionized water, and vigorously stirring at 25 deg.C for 30 min;
s2-1-2, after the mixture solution prepared in the step S2-1-2 is cooled to room temperature, centrifugally separating the mixture solution to obtain a solid product;
s2-1-3, washing the solid product prepared in the step S2-1-2 with N-N dimethylformamide, methanol and deionized water for multiple times, and drying at 100 ℃ for 24 hours to obtain the MOF system with Cr-MIL-101-NH2/CQD configuration.
3. The method for preparing a modified magnetic levitation biological carrier for nitrosation process as claimed in claim 2, wherein in said step S2-1-1, H2BDC-NH2：1.44g，8.0mmol；Cr(NO3)3·9H2O：3.20g，8.0mmol; NaOH: 0.80g, 20 mmol; deionized water: 60 mL.
4. The method for preparing a modified magnetic suspension biological carrier for a nitrosation process of claim 1, wherein said step S2-2 comprises the following steps:
s2-2-1, mixing PVDF, NaCl and CNT, and ball-milling into uniform powder;
s2-2-2, heating the mixed powder prepared in the step S2-2-1 at 200 ℃ for 3 hours, and cooling the mixed powder to room temperature to obtain a block sample;
s2-2-3, polishing to remove the outermost layer of the block sample prepared in the step S2-2-2, and then washing the polished block sample for multiple times in a water bath condition at 85 ℃ until NaCl is completely dissolved;
s2-2-4, drying the block sample treated by the step S2-2-3 at-70 ℃ for 24h to obtain the porous CNT sponge.
5. The method for preparing a modified magnetic levitation biological carrier for nitrosation process as claimed in claim 4, wherein in said step S2-2-1, PVDF, NaCl and CNT are mixed in a mass ratio of 3: 5: 4.
6. the method for preparing a modified magnetic suspended biological carrier for a nitrosation process of claim 1, wherein in step S2-3-2, zero-valent iron and graphene are added to the MOF system after activation treatment in step S2-3-1, wherein the addition amount of zero-valent iron is: 1-2 wt%, and the addition amount of graphene is as follows: 3 to 5 wt%.
7. The method for preparing a modified magnetic suspension biological carrier for nitrosation process as claimed in claim 1, wherein in said step S3, the mass ratio of HDPE substrate, modified functional material and magnetic powder in the carrier is 100: 9: 7.
8. the method for preparing a modified magnetic suspension biological carrier for nitrosation process as claimed in claim 1, wherein in said step S3, the specific parameters of the granulation process are as follows: the temperature range of the feed hopper is 180-195 ℃, and the rotating speed of the screw is 25 rpm.
9. The method for preparing a modified magnetic levitation biological carrier for nitrosation process as claimed in claim 1, wherein in said step S4, the specific parameters of extrusion molding process are as follows: the temperature of the feeding stage is 135 ℃, the temperature of the melting stage is 150 ℃, the temperature of the mixing stage is 160 ℃, and the temperature of the forming stage is 140 ℃; the screw speed was 25 rpm.
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