CN114686472A - Immobilized nitrobacteria and immobilization method thereof - Google Patents
Immobilized nitrobacteria and immobilization method thereof Download PDFInfo
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- CN114686472A CN114686472A CN202011621210.4A CN202011621210A CN114686472A CN 114686472 A CN114686472 A CN 114686472A CN 202011621210 A CN202011621210 A CN 202011621210A CN 114686472 A CN114686472 A CN 114686472A
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- 238000000034 method Methods 0.000 title claims abstract description 58
- 241000108664 Nitrobacteria Species 0.000 title claims abstract description 57
- 239000004964 aerogel Substances 0.000 claims abstract description 68
- 239000004021 humic acid Substances 0.000 claims abstract description 43
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 38
- 241000894006 Bacteria Species 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 230000001546 nitrifying effect Effects 0.000 claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 14
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000661 sodium alginate Substances 0.000 claims abstract description 13
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 13
- 229940005550 sodium alginate Drugs 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
- 238000004448 titration Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000001110 calcium chloride Substances 0.000 claims abstract description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 16
- 239000004966 Carbon aerogel Substances 0.000 claims description 15
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 10
- 239000001913 cellulose Substances 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 9
- 229960003237 betaine Drugs 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002504 physiological saline solution Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000012258 culturing Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 230000007774 longterm Effects 0.000 abstract description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 19
- 244000005700 microbiome Species 0.000 description 15
- 230000000593 degrading effect Effects 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000011268 mixed slurry Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 4
- 241001052560 Thallis Species 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- -1 humic acid modified carbon Chemical class 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 238000011866 long-term treatment Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 230000001651 autotrophic effect Effects 0.000 description 1
- 230000002210 biocatalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/04—Enzymes or microbial cells immobilised on or in an organic carrier entrapped within the carrier, e.g. gel or hollow fibres
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
- C12N11/082—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C12N11/084—Polymers containing vinyl alcohol units
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
- C12N11/12—Cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention relates to an immobilized nitrobacteria and an immobilization method thereof, wherein humic acid is adopted to modify aerogel, then metal ions are loaded, and then the aerogel and active carbon are mixed uniformly to prepare an immobilized carrier; mixing the carrier and the nitrifying bacteria suspension, adsorbing and centrifuging to obtain a solid matter; preparing polyvinyl alcohol and sodium alginate gel, adding gel into solid, mixing, and dripping CaCl2And (3) in a saturated boric acid solution, crosslinking and fixing for a certain time after titration is finished, and washing to obtain the immobilized nitrobacteria. The immobilization method of the invention adopts specific immobilization materials, has good adsorption to nitrobacteria, can enhance the binding force between the materials and the bacteria, and can avoid the nitrobacteria from falling off in the long-term use process.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to immobilized nitrobacteria and an immobilization method thereof.
Background
Nitrobacteria belong to autotrophic microorganisms, grow and reproduce slowly, strains are easy to lose in the application process, the tolerance to adverse environment is poor, the activity is easy to be inhibited, the concentration of thalli in activated sludge is small, and a good denitrification effect is difficult to obtain in a short time. The enhancement of biological denitrification process by utilizing immobilized microorganism technology is one of the hot spots of research in the field of biological denitrification in recent years.
The microorganism immobilization technology is to adopt a proper carrier to fix pure-species separated or functionally determined microorganisms in a certain space so as to prevent the microorganisms from being diluted or washed away by running water and ensure that the biocatalytic reaction can be efficiently and continuously carried out. The current immobilization methods include adsorption, carrier binding, entrapment, and cross-linking, each of which has advantages and disadvantages. The embedding method has the defects of low mechanical strength and the like, and the large-scale application is limited due to the small surface area and easy separation of the biological membrane of the adsorption method. At present, researchers mostly develop a lot of work from the aspects of material selection, proportioning, carrier modification, immobilization method combination and the like.
CN201510557050.4 discloses an ammonia nitrogen degrading bacteria immobilization method for treating ammonia nitrogen wastewater, which comprises the steps of firstly adding sodium alginate, polyvinyl alcohol and clinoptilolite into water, and stirring at 70-100 ℃ to obtain mixed slurry; cooling the mixed slurry to 30-45 ℃, adding ammonia nitrogen degrading bacteria into the mixed slurry, and stirring to prepare mixed slurry containing the ammonia nitrogen degrading bacteria; dropwise adding the mixed slurry containing the ammonia nitrogen degrading bacteria into 1-10% of CaCl by mass2Standing the solution at 0-10 ℃ for 2-24 h, and washing with normal saline or water. The ammonia nitrogen degrading bacteria provided by the method can not run off along with a water body, the system stability and the ammonia nitrogen removal efficiency are improved, and when the obtained immobilized ammonia nitrogen degrading bacteria particles are applied, the waste water with the ammonia nitrogen concentration of 256.9mg/L is treated to be more than 15.11mg/L within 60 hours. According to the method, the ammonia nitrogen degrading bacteria are embedded in the immobilized particles, although the bacteria cannot be lost, the ammonia nitrogen removal rate is influenced, and the treatment time is as long as 60 hours.
CN201610595544.6 discloses a method for treating ammonia nitrogen wastewater by utilizing porous cellulose aerogel immobilized microorganism bacteria, which mainly comprises the steps of preparing the porous cellulose aerogel, adsorbing and fixing nitrobacteria and denitrifying bacteria on the porous cellulose aerogel by adopting a carrier combination method, and fixing the microorganisms on the porous cellulose aerogel to treat the ammonia nitrogen wastewater, thereby being beneficial to the synchronous nitration and denitrification reaction. The immobilized microorganism strain obtained by the method is added into 50-100L of 100-one ammonia nitrogen wastewater of 500mg/L according to 20-30g/L, the hydraulic retention time is 30-40h, and the ammonia nitrogen removal rate after treatment is 68-89%. However, the method utilizes the cellulose aerogel to adsorb thalli, belongs to surface adsorption, and still has a shedding phenomenon in long-term treatment due to weak binding force between the thalli and an adsorbing material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an immobilized nitrobacteria and an immobilization method thereof. The immobilization method is realized by the prepared immobilization material, the immobilization material has good adsorption to nitrobacteria, can enhance the binding force between the material and the bacteria, and can prevent the nitrobacteria from falling off in the long-term use process.
The invention provides an immobilization method of nitrifying bacteria, which comprises the following steps:
(1) preparing an immobilized carrier: humic acid is adopted to modify aerogel, then metal ions are loaded, and then the aerogel and active carbon are mixed uniformly to prepare an immobilized carrier;
(2) adsorption of nitrifying bacteria: mixing the immobilized carrier and the nitrobacteria suspension, adsorbing and centrifuging to obtain a solid matter adsorbing nitrobacteria;
(3) embedding and crosslinking after adsorption: preparing polyvinyl alcohol and sodium alginate gel, adding the gel into the solid matter obtained in the step (2), uniformly mixing, and dripping CaCl2And (3) in a saturated boric acid solution, crosslinking and fixing for a certain time after titration is finished, and washing to obtain the immobilized nitrobacteria.
The aerogel in the step (1) of the present invention is at least one of carbon aerogel, silicon aerogel, cellulose aerogel, etc., preferably carbon aerogel. Usually by usingObtained by self-making or commercial purchase, and the specific surface area of the aerogel is 600-1100 m2The porosity is 80-98 percent.
The process of modifying the aerogel by adopting humic acid in the step (1) comprises the following steps: (a) placing the aerogel in an acetic acid solution for water bath oscillation, taking out and washing to be neutral; (b) dissolving humic acid in Fe (OH)3And (b) mixing the solution with the aerogel obtained in the step (a), carrying out water bath reaction at 50-70 ℃, and washing the reacted solution to be neutral to obtain the humic acid modified aerogel.
The concentration of the acetic acid solution in the step (a) is 1.0-2.0 mol/L. Immersing the aerogel in an acetic acid solution for water bath reaction at the temperature of 30-50 ℃ for 1.0-2.0 h. And taking out the aerogel, and washing until the pH value is neutral, wherein the pH value is generally 6.5-7.5.
Fe (OH) according to step (b)3The concentration of the solution is 0.5-0.8 mol/L, Fe (OH)3The mass ratio of the solution to the humic acid is 1: 1-3: 1. Immersing the aerogel of step (a) in humic acid and Fe (OH)3And in a mixed system of the solution, performing water bath reaction for 3-5 hours at 50-70 ℃, and washing the solution after the reaction until the pH value is neutral, generally 6.5-7.5.
The step (1) of the invention loads metal ions on the humic acid modified aerogel, and a conventional loading method in the field can be adopted. The metal ion is Cu2+、Fe2+、Mg2+Etc., preferably contains Fe2+. Wherein, the metal ion loading is 1-5% of metal oxide based on the total mass.
The step (1) of the invention can load metal ions on the humic acid modified aerogel by adopting the following method: adding the humic acid modified aerogel into the metal ion solution for soaking, stirring for a certain time, taking out, carrying out heat treatment, and drying to obtain the metal-loaded modified aerogel. The metal ion solution is soluble salt solution of metal ion, and the concentration of the metal ion solution is 4-10 mol/L. The impregnation can adopt equal-volume impregnation or excess impregnation, and can adopt one or more times of impregnation, and the impregnation is carried out for 6 to 10 hours under the condition of stirring at the temperature of between 60 and 70 ℃. The heat treatment is carried out at 90-120 ℃ for 1-5h, and then at 150-300 ℃ for 1-5 h. And drying at a constant temperature of 100-120 ℃ for 1-2 h to obtain the metal-loaded modified aerogel. Furthermore, betaine is added into the metal ion solution, and the mass ratio of the added amount of the betaine to the metal ions is 1:1-1: 5.
The mass ratio of the activated carbon in the step (1) to the metal-loaded modified aerogel is 1:1-1: 10. The mesh number of the active carbon is 100-500 meshes.
After the nitrifying bacteria culture solution obtained by culture is settled in the step (2), the supernatant is removed until the settlement ratio is 80-90%, and the supernatant is the nitrifying bacteria suspension, and the nitrifying bacteria suspension is mixed with the immobilized carrier in the step (1) according to the liquid-solid ratio of 10-20mL:1 g. After mixing, adsorbing for 60-180min at 28-30 ℃ under the condition of 100-.
Further, polyethyleneimine is added in the step (2), and the adding amount is 1-5% of the volume of the nitrobacteria suspension.
Step (3) of the present invention is carried out for inclusion crosslinking using methods well known in the art. Specifically, the gel can be prepared by dissolving polyvinyl alcohol and sodium alginate in distilled water at the water bath temperature of 90-95 ℃, wherein the content of the polyvinyl alcohol is 70-80g/L, and the content of the sodium alginate is 20-30 g/L; and (3) adding the gel into the solid in the step (2) according to the volume ratio of 2-3:1, and stirring and uniformly mixing. The CaCl is2The mass fraction of the saturated boric acid solution is 3-5%, continuously stirring, carrying out cross-linking fixation at 4-5 ℃ for 24-48h after titration, finally washing with physiological saline with the mass fraction of 0.9% for three times to complete the immobilization of nitrobacteria, and storing at 0-5 ℃.
The immobilized nitrobacteria of the present invention are prepared by the above-described method of the present invention. The immobilized nitrobacteria is prepared by loading metal ions on humic acid modified aerogel, mixing with activated carbon to prepare an immobilized carrier, adsorbing the nitrobacteria on the immobilized carrier, and finally embedding and crosslinking.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, humic acid modified aerogel is adopted, loaded with metal ions, mixed with activated carbon to serve as an immobilized carrier and used for adsorbing nitrobacteria, and finally the immobilized nitrobacteria is prepared through embedding and crosslinking, so that the impact influence of high-concentration ammonia nitrogen on the nitrobacteria can be relieved, the high-efficiency and stable treatment effect is ensured, the nitrobacteria and the carrier are firmly combined, and thallus shedding is avoided.
(2) The humic acid modified aerogel and the metal ion load are adopted to prepare the immobilized carrier material, and the substances are tightly combined through the synergistic effect, so that the immobilized carrier material is finally convenient for microorganism adhesion and adsorption and has strong binding force.
(3) The betaine is added into the metal ion dipping solution, so that the bonding strength of the metal ions and the aerogel is improved, the bonding force of the metal ions and the microorganisms is enhanced, and the microbial shedding is further avoided in the long-term treatment process.
(4) The polyethyleneimine is added in the process of adsorbing the microorganisms by the carrier, so that the affinity of the microorganisms and the carrier is improved, the number of the microorganisms immobilized by the carrier per unit volume is large, the adsorption time is shortened, and the immobilization efficiency is improved.
(5) The immobilization method of nitrobacteria has little damage to microorganisms, and the obtained microorganism particles have good mass transfer performance, are not easy to damage and have long service life.
Detailed Description
The method and effects of the present invention will be described in further detail by examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
In the embodiment of the invention, the ammonia nitrogen concentration is measured by GB7478-87 'determination of ammonium in water quality-distillation and titration method'; the concentration of suspended matters is measured by GB11901-89 weight method for measuring suspended matters in water.
Example 1
(1) Preparing an immobilized carrier:
adopting humic acid modified carbon aerogel: (a) the specific surface area is 800m2Immersing carbon aerogel with the porosity of 80% in 1.5mol/L acetic acid solution for water bath reaction at the temperature of 40 ℃, shaking for 1.5h, taking out, and washing with deionized water to pH7.0; (b) preparation of 0.6mol/L Fe (OH)3Solution according to Fe (OH)3The mass ratio of the solution to the humic acid is 2:1, and the humic acid is dissolved in Fe (OH)3And (b) mixing the solution with the carbon aerogel treated in the step (a), reacting in a water bath at 60 ℃ for 4 hours, taking out, washing with deionized water to pH7.0, and obtaining the humic acid modified aerogel.
Loading metal ions: preparing a 4mol/L ferrous sulfate solution, adding the humic acid modified aerogel into the solution, and soaking for 8 hours at 65 ℃ under the condition of stirring. After being taken out, the mixture is treated at 100 ℃ for 3h and then at 200 ℃ for 3 h. And drying at 110 ℃ for 1.5h after heat treatment to obtain the metal-loaded modified aerogel.
Mixing with activated carbon: mixing 100-mesh and 200-mesh activated carbon and the metal-loaded modified aerogel according to the mass ratio of 1:5 to prepare the immobilized carrier.
(2) Adsorption of nitrifying bacteria:
settling a freshly cultured nitrobacteria culture solution, removing supernatant until the settling ratio is 90%, namely nitrobacteria suspension, uniformly mixing the nitrobacteria suspension with an immobilized carrier according to the liquid-solid ratio of 10mL to 1g, adsorbing for 60min at the temperature of 28 ℃ under the condition of 100r/min, and centrifuging for 3min under the condition of 400r/min to obtain a solid.
(3) Embedding and crosslinking after adsorption: preparing gel by using polyvinyl alcohol and sodium alginate dissolved in distilled water at the water bath temperature of 90 ℃, wherein the content of the polyvinyl alcohol is 75g/L, and the content of the sodium alginate is 25 g/L; and (3) adding the gel into the solid in the step (2) according to the volume ratio of 2:1, and stirring and uniformly mixing. The CaCl is2The mass fraction of the saturated boric acid solution is 4 percent, the mixture is continuously stirred, the mixture is cross-linked and fixed for 24 hours at 4 ℃ after titration is finished, and finally, the mixture is washed three times by physiological saline with the mass fraction of 0.9 percent to finish the immobilization of nitrobacteria and is stored at 4 ℃.
Example 2
(1) Preparing an immobilized carrier:
adopting humic acid modified carbon aerogel: (a) the specific surface area is 800m2Immersing carbon aerogel with the porosity of 80% in 1.0mol/L acetic acid solution for water bath reaction at the temperature of 30 ℃, shaking for 1h, taking out and washing with deionized water to pH6.5; (b) preparation 0.5mol/LFe (OH)3Solution according to Fe (OH)3The mass ratio of the solution to the humic acid is 1:1, and the humic acid is dissolved in Fe (OH)3And (b) mixing the solution with the carbon aerogel treated in the step (a), oscillating the mixture in a water bath at 50 ℃ for 3 hours, and then washing the mixture with deionized water until the pH value is 6.5 to obtain the humic acid modified aerogel.
Loading metal ions: preparing a 4mol/L ferrous sulfate solution, adding the humic acid modified aerogel into the solution, and soaking for 10 hours at the temperature of 60 ℃ under the stirring condition. After taking out, the mixture is treated at 90 ℃ for 5h and then at 150 ℃ for 5 h. And then drying for 2h at the constant temperature of 100 ℃ to obtain the metal-loaded modified aerogel.
Mixing with activated carbon: mixing 200-mesh 300-mesh activated carbon and the metal-loaded modified aerogel according to the mass ratio of 1:8 to prepare the immobilized carrier.
(2) Adsorption of nitrifying bacteria:
settling a freshly cultured nitrobacteria culture solution, removing supernatant until the settling ratio is 90%, namely nitrobacteria suspension, uniformly mixing the nitrobacteria suspension with an immobilized carrier according to the liquid-solid ratio of 20mL:1g, adsorbing for 120min at 29 ℃ under the condition of 150r/min, and centrifuging for 5min under the condition of 500r/min to obtain a solid matter.
(3) Embedding and crosslinking after adsorption: preparing gel by using polyvinyl alcohol and sodium alginate dissolved in distilled water at the water bath temperature of 90 ℃, wherein the content of the polyvinyl alcohol is 70g/L, and the content of the sodium alginate is 20 g/L; and (3) adding the gel into the solid in the step (2) according to the volume ratio of 3:1, and stirring and uniformly mixing. The CaCl is2The mass fraction of the saturated boric acid solution is 3 percent, the mixture is continuously stirred, the mixture is cross-linked and fixed for 36 hours at 4 ℃ after titration is finished, and finally, the mixture is washed three times by physiological saline with the mass fraction of 0.9 percent to finish the immobilization of nitrobacteria and is stored at 4 ℃.
Example 3
(1) Preparing an immobilized carrier:
adopting humic acid modified carbon aerogel: (a) the specific surface area is 1000m2Immersing carbon aerogel with porosity of 98% in 2.0mol/L acetic acid solution for water bath reaction at 50 ℃, shaking for 2h, taking out and washing with deionized water to pH7.5; (b) preparation of 0.8mol/LFe (OH)3Solution according to Fe (OH)3The mass ratio of the solution to the humic acid is 3:1, and the humic acid is dissolved in Fe (OH)3And (b) mixing the solution with the carbon aerogel treated in the step (a), oscillating the mixture in a water bath at 70 ℃ for 5 hours, and then washing the mixture with deionized water until the pH value is 7.5 to obtain the humic acid modified aerogel.
Loading metal ions: preparing a 4mol/L ferrous sulfate solution, adding the humic acid modified aerogel into the solution, and soaking for 6 hours at the temperature of 70 ℃ under the stirring condition. After taking out, the mixture is treated at 120 ℃ for 1h and then at 300 ℃ for 1 h. And drying at the constant temperature of 120 ℃ for 1h to obtain the metal-loaded modified aerogel.
Mixing with activated carbon: mixing 400-mesh 500-mesh activated carbon and the metal-loaded modified aerogel according to the mass ratio of 1:10 to prepare the immobilized carrier.
(2) Adsorption of nitrifying bacteria:
settling a freshly cultured nitrobacteria culture solution, removing supernatant until the settling ratio is 90%, namely nitrobacteria suspension, uniformly mixing the nitrobacteria suspension with an immobilized carrier according to the liquid-solid ratio of 15mL:1g, adsorbing for 180min at 30 ℃, under the condition of 200r/min, and centrifuging for 10min at 600r/min, thus obtaining a solid matter.
(3) Embedding and crosslinking after adsorption: preparing gel by using polyvinyl alcohol and sodium alginate dissolved in distilled water at the water bath temperature of 90 ℃, wherein the content of the polyvinyl alcohol is 80g/L, and the content of the sodium alginate is 30 g/L; and (3) adding the gel into the solid in the step (2) according to the volume ratio of 3:1, and stirring and uniformly mixing. The CaCl is2The mass fraction of the saturated boric acid solution is 5 percent, the stirring is carried out continuously, the crosslinking and fixation are carried out for 48 hours at 4 ℃ after the titration is finished, and finally, the normal saline with the mass fraction of 0.9 percent is used for washing for three times to finish the immobilization of the nitrobacteria, and the nitrobacteria are stored at 4 ℃.
Example 4
The difference from example 1 is that: silicon aerogel is adopted to replace carbon aerogel, and the specific surface area of the silicon aerogel is 1000m2In terms of a/g, the porosity is 85%. Finally, the immobilized nitrobacteria is prepared and stored at 4 ℃.
Example 5
The difference from example 1 is that: cellulose aerogel is adopted to replace carbon aerogel, and the specific surface area of the cellulose aerogel is 900m2Per g, porosity 95%. Finally, the immobilized nitrobacteria is prepared and stored at 4 ℃.
Example 6
The difference from example 1 is that: the metal ions adopt Cu2+And preparing 4mol/L copper chloride solution instead of ferric sulfate solution. Finally, the immobilized nitrobacteria is prepared and stored at 4 ℃.
Example 7
The difference from example 1 is that: the metal ions adopt Mg2+A4 mol/L magnesium sulfate solution is prepared to replace a ferric sulfate solution. Finally, the immobilized nitrobacteria is prepared and stored at 4 ℃.
Example 8
The difference from example 1 is that: and adding betaine into the metal salt solution, wherein the mass ratio of the added betaine to the metal ions is 1: 3. Finally, the immobilized nitrobacteria is prepared and stored at 4 ℃.
Example 9
The difference from example 1 is that: and (2) adding polyethyleneimine into the nitrobacteria suspension, wherein the addition amount is 5% of the volume of the nitrobacteria suspension. Finally, the immobilized nitrobacteria is prepared and stored at 4 ℃.
Example 10
The difference from example 8 is that: and (2) adding polyethyleneimine into the nitrobacteria suspension, wherein the addition amount is 3% of the volume of the nitrobacteria suspension. Finally preparing the immobilized nitrobacteria, and storing at 4 ℃.
Comparative example 1
The difference from example 1 is that: and (b) carrying metal ions only without humic acid. Finally, the immobilized nitrobacteria is prepared and stored at 4 ℃.
Comparative example 2
The difference from example 1 is that: the aerogel is modified by humic acid, the humic acid is dissolved in water and is not loaded with metal ions, namely Fe (OH) is not adopted3And (3) solution. Finally, the immobilized nitrobacteria is prepared and stored at 4 ℃.
Comparative example 3
The difference from example 1 is that: and (3) omitting the step (a) when the aerogel humic acid is modified, and only adopting the step (b). Finally, the immobilized nitrobacteria is prepared and stored at 4 ℃.
Comparative example 4
The difference from example 1 is that: the metal ion loading process does not adopt heat treatment. Finally, the immobilized nitrobacteria is prepared and stored at 4 ℃.
Test example
The immobilized nitrifying bacteria prepared in examples 1 to 10 and comparative examples 1 to 4 were mixed with wastewater to be treated at a solid-to-liquid ratio of 1:5, and the ammonia nitrogen concentration in the wastewater was 300 mg/L. And treating for 48h, and inspecting the ammonia nitrogen removal condition and the suspended matter condition of the water, wherein the effect is shown in the table 1.
TABLE 1
As can be seen from Table 1, the immobilized nitrifying bacteria prepared by the method of the invention have good treatment effect, firm thallus combination and less effluent suspended matters after long-term treatment.
Claims (21)
1. A nitrifying bacteria immobilization method is characterized by comprising the following steps:
(1) preparing an immobilization carrier: humic acid is adopted to modify aerogel, then metal ions are loaded, and then the aerogel and active carbon are mixed uniformly to prepare an immobilized carrier;
(2) adsorption of nitrifying bacteria: mixing the immobilized carrier and the nitrobacteria suspension, adsorbing and centrifuging to obtain a solid matter adsorbing nitrobacteria;
(3) embedding and crosslinking after adsorption: preparation of polyvinyl alcohol and sodium alginateGelling, adding the gel into the solid matter in the step (2), uniformly mixing, and dripping CaCl2And (3) in a saturated boric acid solution, crosslinking and fixing for a certain time after titration is finished, and washing to obtain the immobilized nitrobacteria.
2. The method of claim 1, wherein: the aerogel in the step (1) is at least one of carbon aerogel, silicon aerogel, cellulose aerogel and the like, and preferably the carbon aerogel.
3. The method according to claim 1 or 2, characterized in that: the specific surface area of the aerogel is 600-1100 m2The porosity is 80-98 percent.
4. The method of claim 1, wherein: the process of modifying the aerogel by adopting humic acid in the step (1) comprises the following steps: (a) placing the aerogel in an acetic acid solution for water bath oscillation, taking out and washing to be neutral; (b) dissolving humic acid in Fe (OH)3And (b) mixing the solution with the aerogel obtained in the step (a), carrying out water bath reaction at 50-70 ℃, and washing the reacted solution to be neutral to obtain the humic acid modified aerogel.
5. The method of claim 4, wherein: the concentration of the acetic acid solution in the step (a) is 1.0-2.0 mol/L; immersing the aerogel in an acetic acid solution to carry out water bath reaction, wherein the reaction temperature is 30-50 ℃, and the reaction time is 1.0-2.0 h; and taking out the aerogel, and washing to pH6.5-7.5.
6. The method of claim 4, wherein: fe (OH) according to step (b)3The concentration of the solution is 0.5-0.8 mol/L, Fe (OH)3The mass ratio of the solution to the humic acid is 1: 1-3: 1.
7. The method of claim 4, 5 or 6, wherein: immersing the aerogel of step (a) in humic acid and Fe (OH)3In a mixed system of the solution, water bath is carried out at 50-70 DEG CReacting for 3-5 h, and washing to pH 6.5-7.5 after reaction.
8. The method of claim 1, wherein: loading metal ions on the humic acid modified aerogel, wherein the metal ions are Cu2+、Fe2+、Mg2+Preferably contains Fe2+。
9. The method according to claim 1 or 8, characterized in that: in the step (1), the metal ion loading amount is 1-5% by metal oxide based on the total mass.
10. The method of claim 1, wherein: the method for loading metal ions on the humic acid modified aerogel in the step (1) comprises the following steps: adding the humic acid modified aerogel into a metal ion solution for soaking, taking out the humic acid modified aerogel after stirring and soaking for time, carrying out heat treatment, and drying to obtain the metal-loaded modified aerogel.
11. The method of claim 10, wherein: the metal ion solution is soluble salt solution of metal ions, and the concentration of the metal ion solution is 4-10 mol/L; adding humic acid modified aerogel, stirring and soaking at 60-70 ℃ for 6-10 h.
12. The method of claim 10, wherein: the heat treatment is carried out at 90-120 ℃ for 1-5h, and then at 150-300 ℃ for 1-5 h.
13. The method according to claim 10 or 11, characterized in that: and adding betaine into the metal ion solution, wherein the mass ratio of the added betaine to the metal ions is 1:1-1: 5.
14. The method of claim 1, wherein: the mass ratio of the activated carbon to the metal-loaded modified aerogel in the step (1) is 1:1-1: 10.
15. The method of claim 1, wherein: and (2) settling the nitrifying bacteria culture solution obtained by culturing, removing the supernatant until the settling ratio is 80-90%, thus obtaining nitrifying bacteria suspension, and mixing the nitrifying bacteria suspension with the immobilized carrier in the step (1) according to the liquid-solid ratio of 10-20mL:1 g.
16. The method according to claim 1 or 15, characterized in that: after the step (2) is mixed evenly, the mixture is adsorbed for 60-180min under the conditions of 28-30 ℃ and 100-200r/min, and is centrifuged for 2-10min under the conditions of 400-600 r/min.
17. The method according to claim 1 or 15, characterized in that: and (3) adding polyethyleneimine into the mixed system obtained in the step (2), wherein the addition amount of polyethyleneimine is 1-5% of the volume of the nitrobacteria suspension.
18. The method of claim 1, wherein: the embedding crosslinking in the step (3) is to prepare gel by dissolving polyvinyl alcohol and sodium alginate in distilled water at the water bath temperature of 90-95 ℃, wherein the content of the polyvinyl alcohol is 70-80g/L, and the content of the sodium alginate is 20-30 g/L.
19. The method according to claim 1 or 18, characterized in that: and (3) adding the gel into the solid in the step (2) according to the volume ratio of 2-3:1, and uniformly stirring.
20. The method of claim 1, wherein: CaCl described in step (3)2The mass fraction of the saturated boric acid solution is 3-5%, after titration, the saturated boric acid solution is cross-linked and fixed for 24-48h at 4-5 ℃, and finally the saturated boric acid solution is washed by physiological saline with the mass fraction of 0.9%.
21. An immobilized nitrifying bacterium, which is characterized by being prepared by the method of the invention.
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