CN116676301A - Magnetic microorganism immobilization material for removing ammonia nitrogen in water body and preparation method thereof - Google Patents
Magnetic microorganism immobilization material for removing ammonia nitrogen in water body and preparation method thereof Download PDFInfo
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- 244000005700 microbiome Species 0.000 title claims abstract description 69
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 32
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 26
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 24
- 238000004132 cross linking Methods 0.000 claims abstract description 24
- 239000000017 hydrogel Substances 0.000 claims abstract description 24
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 24
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000499 gel Substances 0.000 claims abstract description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007863 gel particle Substances 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000012546 transfer Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 claims 1
- 230000000813 microbial effect Effects 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 14
- 239000002351 wastewater Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- 239000000696 magnetic material Substances 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000004060 metabolic process Effects 0.000 description 5
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- 230000009471 action Effects 0.000 description 4
- 238000005273 aeration Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000000149 chemical water pollutant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 238000005303 weighing Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- 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
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- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
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Abstract
The invention provides a magnetic microorganism immobilization material for removing ammonia nitrogen in a water body and a preparation method thereof, belonging to the technical field of immobilized microorganism carrier wastewater treatment, and comprising the following steps: (1) Preparation of Fe under nitrogen atmosphere by chemical coprecipitation method 3 O 4 A nanoparticle; (2) Adding polyvinyl alcohol into water, stirring and dissolving for 120min at the temperature of 90-95 ℃ to obtain a polyvinyl alcohol gel solution; (3) The polyvinyl alcohol gel solution is heatedAdding sodium carboxymethylcellulose at 50-55deg.C, stirring for 120min to obtain uniform mixed hydrogel; (4) Cooling the mixed hydrogel to 20-25 ℃, and adding diatomite and Fe into the mixed hydrogel 3 O 4 The nano particles and the composite strains are uniformly stirred to form composite hydrogel; (5) Dripping the composite hydrogel into the gel containing Al by a syringe 2 (SO 4 ) 3 Stirring and crosslinking the mixture in the saturated boric acid solution to obtain gel particles; (6) Transfer of gel particles to Na 2 SO 4 Stirring and crosslinking again in the solution to obtain the magnetic microorganism immobilization material.
Description
Technical Field
The invention relates to the technical field of immobilized microorganism carrier wastewater treatment, in particular to a magnetic microorganism immobilization material for removing ammonia nitrogen in a water body and a preparation method thereof.
Background
With the rapid development of economy, the excessive discharge of industrial wastewater, domestic sewage, landfill leachate and the like causes the increase of ammonia nitrogen content in water, and the wastewater containing a large amount of ammonia nitrogen has great influence on the environment and human body. Excessive ammonia nitrogen is easy to cause mass propagation of algae and other microorganisms in water, and water eutrophication is caused. Ammonia nitrogen also increases water treatment cost and chlorine consumption, and has certain toxic effect on human beings and organisms. Control and prevention of ammonia nitrogen pollution is critical to environmental protection.
The treatment methods for ammonia nitrogen wastewater at home and abroad mainly comprise a physical method (a stripping method, an ion exchange method and a membrane absorption method), a chemical method (a break point chlorination method, a chemical precipitation method and a high-grade oxidation method), a biological method (a nitrification-denitrification process, a shortcut nitrification-denitrification process, a synchronous nitrification-denitrification process, an anaerobic ammonia oxidation process) and the like. The physical and chemical method has simple process and high denitrification efficiency, but has high running cost and is easy to cause secondary pollution; the biological denitrification method not only can remove ammonia nitrogen more effectively, but also is economical and has no secondary pollution.
The microorganism immobilization technology is a technical method for immobilizing microorganisms on a carrier by adopting a physical or chemical method to enable the microorganisms to grow and reproduce, improving the utilization rate of thalli and realizing the improvement of sewage treatment efficiency. The technology has the advantages of simple operation, strong toxicity resistance, easy solid-liquid separation, small sludge yield and extremely high application value. Common microorganism immobilization methods include adsorption methods, entrapment methods, covalent bonding methods, and crosslinking methods. Among them, the embedding method is the most studied and widely used immobilization method at present. The embedded microorganism has little loss and large microorganism loading capacity, and the microorganism can keep activity well. However, the embedding method also has some problems, such as: the embedded carrier material has poor physical properties and low mechanical strength, and the embedded microorganisms are easy to leach out of the carrier; the porous structure of the carrier influences the pollutant removal effect, the large pore size of the carrier can lead to the loss of embedded microorganisms from the carrier, and the small pore size can increase the mass transfer resistance of nutrients and metabolites, so that the metabolic activity of the microorganisms is reduced. Therefore, it is important to prepare an immobilized material with good physical and chemical properties and pore structure.
Disclosure of Invention
The invention aims to provide a magnetic microorganism immobilization material for removing ammonia nitrogen in a water body and a preparation method thereof, and solves the technical problems of poor physical properties and low mechanical strength of the existing carrier material. The magnetic microorganism immobilization material can effectively immobilize microorganisms, degrade ammonia nitrogen in water by enhancing the combined action of ammonia nitrogen adsorption by a carrier and microorganism metabolism, and has high removal efficiency.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a magnetic microorganism immobilization material for removing ammonia nitrogen in water body comprises polyvinyl alcohol, sodium carboxymethyl cellulose, diatomite and Fe 3 O 4 And (3) nanoparticles.
Further, polyvinyl alcohol, sodium carboxymethyl cellulose, diatomaceous earth, and Fe 3 O 4 The mass ratio of the nano particles is 10:1:1:1.
A preparation method of a magnetic microorganism immobilization material for removing ammonia nitrogen in a water body comprises the following steps:
(1) Preparation of Fe under nitrogen atmosphere by chemical coprecipitation method 3 O 4 A nanoparticle;
(2) Adding polyvinyl alcohol into water, stirring and dissolving for 120min at the temperature of 90-95 ℃ to obtain a polyvinyl alcohol gel solution;
(3) Adding sodium carboxymethylcellulose into the polyvinyl alcohol gel solution at the temperature of 50-55 ℃ and stirring for 120min to obtain uniform mixed hydrogel;
(4) Cooling the mixed hydrogel to 20-25 ℃, and adding diatomite and Fe into the mixed hydrogel 3 O 4 The nano particles and the composite strains are uniformly stirred to form composite hydrogel;
(5) Dripping the composite hydrogel into the gel containing Al by a syringe 2 (SO 4 ) 3 Stirring and crosslinking the mixture in the saturated boric acid solution to obtain gel particles;
(6) Transfer of gel particles to Na 2 SO 4 Stirring and crosslinking again in the solution to obtain the magnetic microorganism immobilization material.
Further, fe 3 O 4 The preparation method of the nanoparticle comprises the following steps:
ultrasonic treating with deionized water for 30min, adding FeCl at 80deg.C 3 ·H 2 O and FeSO 4 ·7H 2 O is dissolved for 60min;
adding a certain amount of NH 3 ·H 2 Adjusting pH to 9-10 with O, stirring for 60min, separating with magnet, washing, and vacuum drying at 70deg.C for 8 hr to obtain Fe 3 O 4 And (3) nanoparticles.
Further, feSO 4 ·7H 2 Fe in O 3+ With Fe 2+ The molar ratio of (2) was 4:3.
Further, the cross-linking is a two-step cross-linking method, and the cross-linking agents respectively contain Al 2 (SO 4 ) 3 Saturated boric acid solution and Na 2 SO 4 A solution.
Further, contains Al 2 (SO 4 ) 3 Is saturated with (2)Al in boric acid solution 2 (SO 4 ) 3 Is 2wt%, na 2 SO 4 The concentration of the solution was 0.5mol/L and the crosslinking time was 2h.
Further, the inner diameter of the syringe is 3cm, the advancing speed is 3mm/min, and the crosslinking time is 30-60min.
Further, the diameter of the obtained magnetic microorganism immobilization material is 4-5 mm, polyvinyl alcohol, sodium carboxymethyl cellulose, diatomite and Fe 3 O 4 The nano particles and the composite strain are combined through intermolecular and intramolecular hydrogen bonds and electrostatic attraction, the obtained magnetic microorganism immobilization material is a porous material, and ammonia nitrogen in the water body is removed through the combined action of material self adsorption and microorganism metabolism.
Due to the adoption of the technical scheme, the invention has the following beneficial effects compared with the prior art:
1. according to the invention, polyvinyl alcohol and sodium carboxymethyl cellulose are adopted as main components of the carrier, so that the mechanical stability of the synthesized immobilized material is high, and the problems of poor physical properties and low mechanical strength of the carrier in the prior art are solved; the good pore structure enables the magnetic microorganism immobilization material to have good mass transfer performance, and good immobilization of microorganisms is achieved.
2. The magnetic microorganism immobilization material prepared by the invention removes ammonia nitrogen in water body through the adsorption effect and microorganism metabolism effect of the carrier, and the strong adsorption capacity of the carrier to ammonia nitrogen is helpful for the uptake and metabolism of microorganism to ammonia nitrogen, thereby improving the ammonia nitrogen removal rate.
3. The magnetic microorganism immobilization material prepared by the invention has good long-term use performance, and keeps good morphology and high ammonia nitrogen removal effect after long-term use for thirty days.
Drawings
FIG. 1 is a scanning electron microscope image of a magnetic microorganism immobilization material of the present invention;
FIG. 2 is a graph showing ammonia nitrogen removal effect in the microorganism immobilized and non-immobilized magnetic material 24h according to the present invention;
fig. 3 is a schematic diagram of the long-term practical sewage ammonia nitrogen removal experiment test result.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail below by referring to the accompanying drawings and by illustrating preferred embodiments. It should be noted, however, that many of the details set forth in the description are merely provided to provide a thorough understanding of one or more aspects of the invention, and that these aspects of the invention may be practiced without these specific details.
As shown in figures 1-3, the magnetic microorganism immobilization material for removing ammonia nitrogen in water comprises polyvinyl alcohol, sodium carboxymethyl cellulose, diatomite and Fe 3 O 4 And (3) nanoparticles. Polyvinyl alcohol, sodium carboxymethyl cellulose, diatomite and Fe 3 O 4 The mass ratio of the nano particles is 10:1:1:1.
A preparation method of a magnetic microorganism immobilization material for removing ammonia nitrogen in a water body comprises the following steps:
(1) Preparation of Fe under nitrogen atmosphere by chemical coprecipitation method 3 O 4 A nanoparticle;
(2) Adding polyvinyl alcohol into water, stirring and dissolving for 120min at the temperature of 95 ℃ to obtain a polyvinyl alcohol gel solution;
(3) Adding sodium carboxymethylcellulose into the polyvinyl alcohol gel solution at the temperature of 50-55 ℃ and stirring for 120min to obtain uniform mixed hydrogel;
(4) Cooling the mixed hydrogel to 20-25 ℃, and adding diatomite and Fe into the mixed hydrogel 3 O 4 The nano particles and the composite strains are uniformly stirred to form composite hydrogel;
(5) Dripping the composite hydrogel into the gel containing Al by a syringe 2 (SO 4 ) 3 Stirring and crosslinking the mixture in the saturated boric acid solution to obtain gel particles;
(6) Transfer of gel particles to Na 2 SO 4 Stirring and crosslinking again in the solution to obtain the magnetic microorganism immobilization material.
Fe 3 O 4 The preparation method of the nanoparticle comprises the following steps:
ultrasonic treating with deionized water for 30min, adding FeCl at 80deg.C 3 ·H 2 O and FeSO 4 ·7H 2 O is dissolved for 60min, feSO 4 ·7H 2 Fe in O 3+ With Fe 2+ The molar ratio of (2) is 4:3;
adding a certain amount of NH 3 ·H 2 Adjusting pH to 9-10 with O, stirring for 60min, separating with magnet, washing, and vacuum drying at 70deg.C for 8 hr to obtain Fe 3 O 4 And (3) nanoparticles.
The crosslinking is a two-step crosslinking method, and the crosslinking agents respectively contain Al 2 (SO 4 ) 3 Saturated boric acid solution and Na 2 SO 4 A solution.
Containing Al 2 (SO4) 3 Al in a saturated boric acid solution of (C) 2 (SO 4 ) 3 Is 2wt%, na 2 SO 4 The concentration of the solution was 0.5mol/L and the crosslinking time was 2h.
The inner diameter of the syringe was 3cm, the advancing speed was 3mm/min, and the crosslinking time was 30min.
The diameter of the obtained magnetic microorganism immobilization material is 4-5 mm, polyvinyl alcohol, sodium carboxymethyl cellulose, diatomite and Fe 3 O 4 The nano particles and the composite strains are combined through intermolecular and intramolecular hydrogen bonds and electrostatic attraction, so that the obtained magnetic microorganism immobilization material is a porous material, and ammonia nitrogen in the water body is removed by the magnetic microorganism immobilization material through the self adsorption and microorganism metabolism of the material.
According to the invention, polyvinyl alcohol and sodium carboxymethyl cellulose are adopted as main components of the carrier, so that the mechanical stability of the synthesized immobilized material is high, and the problems of poor physical properties and low mechanical strength of the carrier in the prior art are solved; the good pore structure enables the magnetic microorganism immobilization material to have good mass transfer performance, and good immobilization of microorganisms is achieved.
Example 1:
the preparation method of the magnetic microorganism immobilization material comprises the following steps:
s1: weighing deionized water, performing ultrasonic treatment for 30min, heating in a constant temperature oil bath magnetic heating stirrer at 80deg.C, and adding FeCl 3 ·H 2 O and FeSO 4 ·7H 2 O，FeSO 4 ·7H 2 Fe in O 3+ With Fe 2+ The mixture was heated and stirred at a stirring rate of 360rpm for 60 minutes at a molar ratio of 4:3 to dissolve the mixture.
S2: measuring a certain amount of NH 3 ·H 2 Adding O into the above solution, adjusting pH to 9-10, heating and stirring at 360rpm for 60min to obtain Fe-containing solution 3 O 4 A solution of nanoparticles; separation of Fe by magnet 3 O 4 Washing the nano particles with hot water and absolute ethyl alcohol, and vacuum drying in a vacuum drying oven at 70deg.C for 8 hr to obtain Fe 3 O 4 And (3) nanoparticles.
S3: weighing polyvinyl alcohol, mixing with deionized water, heating and stirring for 120min at 95 ℃ to obtain a polyvinyl alcohol gel solution; then cooling to 50 ℃, adding sodium carboxymethylcellulose, heating and stirring for 120min to dissolve the sodium carboxymethylcellulose, and obtaining uniform mixed hydrogel; cooling to 25 ℃, adding diatomite and Fe into the mixed hydrogel 3 O 4 Nanoparticle and composite strain, polyvinyl alcohol, sodium carboxymethyl cellulose, diatomite and Fe 3 O 4 The mass ratio of the nano particles to the composite strain is 10:1:1:1:4 respectively, and the composite hydrogel is obtained after uniform stirring;
s4: dripping the composite hydrogel into a syringe with an inner diameter of 3cm at a propelling speed of 3mm/min 2 (SO 4 ) 3 Stirring and crosslinking for 30min to obtain gel particles with the diameter of 4-5 mm; the gel particles were then transferred again to Na at a concentration of 0.5mol/L 2 SO 4 And (3) performing second-step crosslinking in the solution, stirring and crosslinking for 120min to obtain the final magnetic microorganism immobilization material. The prepared magnetic microorganism immobilization material is shown in figure 1, and the scanning electron microscope image shows that the inside of the carrier is in a cross-linked network porous structure, and the porosity is good.
Example 2:
in order to explore the action mechanism of removing ammonia nitrogen by the material, the embodiment carries out ammonia nitrogen removal comparison experiments on the magnetic materials of fixed compound strains and unfixed compound strains, and the action mechanism of removing ammonia nitrogen by the magnetic materials is illustrated through the ammonia nitrogen removal efficiency.
Preparing ammonia nitrogen simulated wastewater: ammonia nitrogen concentration with NH 4 The mass calculation of N in Cl, the ammonia nitrogen wastewater content of 300mg/L is: NH (NH) 4 Cl：1.152g/L，NaHCO 3 ：3.516g/L，C 6 H 12 O 6 ：1.416g/L，NaCl：0.052g/L，KCl:0.024g/L，Na 2 HPO 4 :0.116g/L，CaCl 2 ·2H 2 O：0.024g/L，MgSO 4 ·7H 2 O:0.084g/L and FeSO 4 ·7H 2 O：0.05g/L。
Ammonia nitrogen removal test:
respectively adding 20g of magnetic material for fixing the compound bacteria and non-fixed magnetic material for the compound bacteria into an aeration bottle, then adding 200mL of ammonia nitrogen simulated wastewater with ammonia nitrogen concentration of 300mg/L, placing each group of three parallel ammonia nitrogen simulated wastewater into a constant-temperature water bath at 35 ℃, taking supernatant liquid at 0, 2, 4, 6, 8, 10, 12 and 24 hours respectively, and measuring the ammonia nitrogen concentration by using a national standard method (HJ 535-2009), wherein the ammonia nitrogen removal rate is calculated by a formula (1).
In E NH4 + Ammonia nitrogen removal rate,%; c (C) 0 And C t The initial concentration of ammonia nitrogen and the concentration at time t are respectively mg/L. The experimental results are shown in fig. 2, the ammonia nitrogen removal rates of the non-immobilized material and the immobilized material at 24h are 75% and 99%, respectively, which shows that the immobilized magnetic material achieves the purpose of removing ammonia nitrogen through the synergistic effect of the self-adsorption effect and the microbial metabolism effect of the material, wherein the contribution rates of the self-adsorption effect and the microbial metabolism effect are 76% and 23% respectively. The experimental result shows that the ammonia nitrogen is realized by strengthening the adsorption effect of the carrier materialAnd (5) high-efficiency removal.
Example 3:
screening the optimal addition ratio of polyvinyl alcohol
In step S3 of example 1, sodium carboxymethylcellulose, diatomaceous earth, fe were immobilized 3 O 4 The mass percentages of the nano particles and the composite strains are respectively 1wt%, 2wt%, 1wt% and 4wt%. The adding amount of the polyvinyl alcohol is changed, the mass percentages of the polyvinyl alcohol are respectively 6wt percent, 8wt percent, 10wt percent, 12wt percent and 14wt percent, the magnetic microorganism immobilization material is prepared, an experiment for simulating the ammonia nitrogen removal of the wastewater is carried out, the removal rate of the material to the ammonia nitrogen is respectively 80%, 86%, 97%, 87% and 75%, and the optimal adding amount of the polyvinyl alcohol is obtained to be 10%.
Example 4:
screening the optimal adding ratio of sodium carboxymethyl cellulose
In step S3 of example 1, polyvinyl alcohol, diatomaceous earth, fe were immobilized 3 O 4 The mass percentages of the nano particles and the composite strains are respectively 10wt%, 2wt%, 1wt% and 4wt%. Changing the adding amount of sodium carboxymethyl cellulose to ensure that the mass percent of sodium carboxymethyl cellulose is respectively 0.5wt%, 1wt%, 1.5wt% and 2wt%, preparing the magnetic microorganism immobilization material, and performing an experiment for simulating ammonia nitrogen removal of wastewater, wherein the removal rate of the material to the ammonia nitrogen is respectively 89%, 97%, 87% and 92%, so that the optimal adding amount of sodium carboxymethyl cellulose is 1%.
Example 5:
screening the optimal adding ratio of diatomite
In step S3 of example 1, polyvinyl alcohol, sodium carboxymethyl cellulose, fe are immobilized 3 O 4 The mass percentages of the nano particles and the composite strains are respectively 10wt%, 1wt% and 4wt%. Changing the adding amount of diatomite to ensure that the mass percentages of the diatomite are respectively 0wt%, 0.5wt%, 1wt%, 2wt% and 3wt%, preparing a magnetic microorganism immobilization material, and performing an experiment for simulating the ammonia nitrogen removal of wastewater, wherein the removal rate of the material on the ammonia nitrogen is respectively 88%, 91%, 99%, 93% and 94%, so as to obtain the optimal adding amount of the diatomite as 1%.
Example 6:
screening Fe 3 O 4 Optimum addition ratio of nano particles
In step S3 of example 1, the mass percentages of the immobilized polyvinyl alcohol, sodium carboxymethylcellulose, diatomaceous earth and the composite bacterial species were 10wt%, 1wt% and 4wt%, respectively. Altering Fe 3 O 4 The addition amount is that Fe 3 O 4 The mass percentages of the magnetic microorganism immobilization materials are respectively 0wt%, 0.5wt%, 1wt%, 2wt% and 3wt%, the magnetic microorganism immobilization materials are prepared, and simulated wastewater ammonia nitrogen removal experiments are carried out, and the ammonia nitrogen removal rates of the materials are respectively 82%, 89%, 99%, 91% and 85%, so that the optimal Fe is obtained 3 O 4 The addition amount was 1%.
Example 7:
the ammonia nitrogen removal effect of the magnetic microorganism immobilization material on actual sewage:
the actual sewage source is Yangjiang garbage percolate, and the ammonia nitrogen concentration of the sewage is 2500mg/L through the test analysis of the national standard method (HJ 535-2009). Adding 20g of magnetic microorganism immobilization material into an aeration bottle, then adding 200mL of diluted landfill leachate (concentration: 300 mg/L), placing the aeration bottle into a constant temperature water bath at 35 ℃, taking supernatant fluid after aeration amount is 16L/min for 24 hours for analysis and replacing new wastewater, and continuously reacting for 30 days. Three replicates per group. Ammonia nitrogen and total nitrogen concentration were measured by national standard method (HJ 535-2009 and GB 11894-1989) and the removal rate was calculated, and the experimental results are shown in FIG. 3, which shows that the magnetic microorganism immobilization material has good long-term denitrification effect and good use stability.
The magnetic microorganism immobilization material prepared by the invention has good long-term use performance, and keeps good morphology and high ammonia nitrogen removal effect after long-term use for thirty days.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. RemovingThe magnetic microorganism immobilization material for the ammonia nitrogen in the water body is characterized in that: comprises polyvinyl alcohol, sodium carboxymethyl cellulose, diatomite and Fe 3 O 4 And (3) nanoparticles.
2. The magnetic microorganism immobilization material for removing ammonia nitrogen from a water body according to claim 1, wherein: polyvinyl alcohol, sodium carboxymethyl cellulose, diatomite and Fe 3 O 4 The mass ratio of the nano particles is 10:1:1:1.
3. A method for preparing the magnetic microorganism immobilization material for removing ammonia nitrogen in a water body according to claim 1, which is characterized in that: the method comprises the following steps:
(1) Preparation of Fe under nitrogen atmosphere by chemical coprecipitation method 3 O 4 A nanoparticle;
(2) Adding polyvinyl alcohol into water, stirring and dissolving for 120min at the temperature of 90-95 ℃ to obtain a polyvinyl alcohol gel solution;
(3) Adding sodium carboxymethylcellulose into the polyvinyl alcohol gel solution at the temperature of 50-55 ℃ and stirring for 120min to obtain uniform mixed hydrogel;
(4) Cooling the mixed hydrogel to 20-25 ℃, and adding diatomite and Fe into the mixed hydrogel 3 O 4 The nano particles and the composite strains are uniformly stirred to form composite hydrogel;
(5) Dripping the composite hydrogel into the gel containing Al by a syringe 2 (SO 4 ) 3 Stirring and crosslinking the mixture in the saturated boric acid solution to obtain gel particles;
(6) Transfer of gel particles to Na 2 SO 4 Stirring and crosslinking again in the solution to obtain the magnetic microorganism immobilization material.
4. The method for preparing the magnetic microorganism immobilization material for removing ammonia nitrogen in water according to claim 3, wherein the method comprises the following steps: fe (Fe) 3 O 4 The preparation method of the nanoparticle comprises the following steps:
deionized waterUltrasonic treating for 30min, adding FeCl at 80deg.C 3 ·H 2 O and FeSO 4 ·7H 2 O is dissolved for 60min;
adding a certain amount of NH 3 ·H 2 Adjusting pH to 9-10 with O, stirring for 60min, separating with magnet, washing, and vacuum drying at 70deg.C for 8 hr to obtain Fe 3 O 4 And (3) nanoparticles.
5. The method for preparing the magnetic microorganism immobilization material for removing ammonia nitrogen in a water body according to claim 4, which is characterized in that: feSO 4 ·7H 2 Fe in O 3+ With Fe 2+ The molar ratio of (2) was 4:3.
6. The method for preparing the magnetic microorganism immobilization material for removing ammonia nitrogen in water according to claim 3, wherein the method comprises the following steps: the crosslinking is a two-step crosslinking method, and the crosslinking agents respectively contain Al 2 (SO 4 ) 3 Saturated boric acid solution and Na 2 SO 4 A solution.
7. The method for preparing the magnetic microorganism immobilization material for removing ammonia nitrogen in water according to claim 3, wherein the method comprises the following steps: containing Al 2 (SO 4 ) 3 Al in a saturated boric acid solution of (C) 2 (SO 4 ) 3 Is 2wt%, na 2 SO 4 The concentration of the solution was 0.5mol/L and the crosslinking time was 2h.
8. The method for preparing the magnetic microorganism immobilization material for removing ammonia nitrogen in water according to claim 3, wherein the method comprises the following steps: the inner diameter of the injector is 3cm, the advancing speed is 3mm/min, and the crosslinking time is 30-60min.
9. The method for preparing the magnetic microorganism immobilization material for removing ammonia nitrogen in water according to claim 3, wherein the method comprises the following steps: the diameter of the obtained magnetic microorganism immobilization material is 4-5 mm, the obtained magnetic microorganism immobilization material is a porous material, and ammonia nitrogen in the water body is removed together through the self adsorption and microbial degradation of the material.
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