CN114686472B - Immobilized nitrifying bacteria and immobilization method thereof - Google Patents
Immobilized nitrifying bacteria and immobilization method thereof Download PDFInfo
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- 241000894006 Bacteria Species 0.000 title claims abstract description 88
- 230000001546 nitrifying effect Effects 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000004964 aerogel Substances 0.000 claims abstract description 67
- 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 40
- 238000002156 mixing Methods 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000725 suspension Substances 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 19
- 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 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 14
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 14
- 239000000661 sodium alginate Substances 0.000 claims abstract description 14
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000004448 titration Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000001179 sorption measurement Methods 0.000 claims description 19
- 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
- 238000003756 stirring Methods 0.000 claims description 14
- 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
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000006228 supernatant 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
- 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
- 239000000126 substance 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
- 230000035484 reaction time Effects 0.000 claims description 2
- 241001052560 Thallis Species 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000000203 mixture Substances 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 16
- 230000000593 degrading effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000011268 mixed slurry Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000011790 ferrous sulphate Substances 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
- 238000002360 preparation method Methods 0.000 description 3
- 239000010865 sewage 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
- 239000012876 carrier material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 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
- 239000011777 magnesium Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 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
- 230000001580 bacterial 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
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure 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
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010802 sludge 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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- 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
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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- 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
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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- 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
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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
- 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
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Abstract
The invention relates to an immobilized nitrifying bacteria and an immobilization method thereof, wherein humic acid modified aerogel is adopted, then metal ions are loaded, and then the mixture is uniformly mixed with active carbon to prepare an immobilization carrier; mixing the carrier with nitrifying bacteria suspension, adsorbing and centrifuging to obtain a solid; preparing polyvinyl alcohol and sodium alginate gel, adding the gel into solid, mixing, and dripping CaCl 2 And (3) in saturated boric acid solution, after titration, crosslinking and fixing for a certain time, and washing to obtain the immobilized nitrifying bacteria. The immobilization method adopts the specific immobilization material, has good adsorptivity to nitrifying bacteria, can enhance the binding force between the material and thalli, and can avoid nitrifying bacteria 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 nitrifying bacteria and an immobilization method thereof.
Background
Nitrifying bacteria belong to autotrophic microorganisms, grow and propagate slowly, strain is easy to run off in the application process, poor tolerance to adverse environment, easy to inhibit activity, small in concentration of thalli in activated sludge, and difficult to obtain a good denitrification effect in a short time. The enhancement of biological denitrification processes by 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 fix pure-breed separated or functionally-determined microorganisms in a certain space by adopting a proper carrier, so that the microorganisms are not diluted or washed away by flowing water, and the biocatalysis reaction can be effectively and continuously carried out. The current immobilization methods include adsorption, carrier binding, embedding, crosslinking, and the like, each of which has advantages and disadvantages. The embedding method has the defects of low mechanical strength and the like, and the adsorption method has limited large-scale application due to small surface area and easy detachment of biological films. At present, researchers mostly carry out a great deal of work on the aspects of material selection, proportioning, carrier modification, immobilization method and the like.
CN201510557050.4 discloses an immobilization method of ammonia nitrogen degrading bacteria for treating ammonia nitrogen wastewater, firstly adding sodium alginate, polyvinyl alcohol and clinoptilolite into water, 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 the mixed slurry to prepare mixed slurry containing the ammonia nitrogen degrading bacteria; dropwise adding the mixed slurry containing ammonia nitrogen degrading bacteria into CaCl with the mass fraction of 1% -10% 2 And (3) standing the solution for 2 to 24 hours at the temperature of between 0 and 10 ℃ and then flushing the solution with normal saline or water. According to the method provided by the invention, ammonia nitrogen degrading bacteria cannot be lost along with the water body, the system stability and the ammonia nitrogen removal efficiency are improved, and the obtained immobilized ammonia nitrogen degrading bacteria particles are used for treating the wastewater with the ammonia nitrogen concentration of 256.9mg/L to more than 15.11mg/L within 60 hours. According to the method, ammonia nitrogen degrading bacteria are embedded in immobilized particles, and although the bacteria cannot be lost, the ammonia nitrogen removal rate can be influenced, and the treatment time is up to 60 hours.
CN201610595544.6 discloses a method for treating ammonia nitrogen wastewater by using porous cellulose aerogel immobilized microorganism bacteria, which mainly comprises the steps of preparing porous cellulose aerogel, adsorbing and fixing nitrifying bacteria and denitrifying bacteria on the porous cellulose aerogel by adopting a carrier combination method, and fixing microorganisms on the porous cellulose aerogel to treat ammonia nitrogen wastewater, thereby being beneficial to synchronous nitrification and denitrification reaction. The immobilized microorganism obtained by the method is added into 50-100L of 100-500mg/L ammonia nitrogen wastewater 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 cellulose aerogel to adsorb thalli, belongs to surface adsorption, and can also generate falling-off phenomenon in long-term treatment due to weak bonding force between thalli and an adsorption material.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides an immobilized nitrifying bacteria and an immobilization method thereof. The immobilization method is realized by the prepared immobilization material, the immobilization material has good adsorptivity to nitrifying bacteria, the binding force between the material and thalli can be enhanced, and nitrifying bacteria can be prevented from falling off in the long-term use process.
The invention provides a nitrifying bacteria immobilization method, which comprises the following steps:
(1) Preparing an immobilization carrier: adopting humic acid modified aerogel, loading metal ions, and uniformly mixing with active carbon to prepare an immobilized carrier;
(2) Adsorption of nitrifying bacteria: mixing the immobilized carrier with nitrifying bacteria suspension, and centrifuging after adsorption to obtain solid substances for adsorbing nitrifying bacteria;
(3) Embedding and crosslinking after adsorption: preparing polyvinyl alcohol and sodium alginate gel, adding the gel into the solid in the step (2), uniformly mixing, and dripping CaCl 2 And (3) in saturated boric acid solution, after titration, crosslinking and fixing for a certain time, and washing to obtain the immobilized nitrifying bacteria.
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. Is usually obtained by self-making or commercial purchase, and the specific surface area of the aerogel is 600-1100 m 2 And/g, wherein the porosity is 80% -98%.
The process of modifying aerogel by humic acid in the step (1) comprises the following steps: (a) Placing the aerogel in acetic acid solution for water bath oscillation, taking out and washing to be neutral; (b) Dissolving humic acid in Fe (OH) 3 SolutionMixing the mixture with the aerogel obtained in the step (a), carrying out water bath reaction at 50-70 ℃, and washing to be neutral after the reaction 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 acetic acid solution for water bath reaction, wherein the reaction temperature is 30-50 ℃ and the reaction time is 1.0-2.0 h. The aerogel is removed and washed to a neutral pH, typically 6.5 to 7.5.
Fe (OH) as described in step (b) 3 The concentration of the solution is 0.5 to 0.8mol/L, fe (OH) 3 The 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) 3 In the mixed system of the solution, the water bath reaction is carried out for 3 to 5 hours at the temperature of 50 to 70 ℃, and the pH value is generally 6.5 to 7.5 after the reaction and washing.
In the step (1) of the invention, metal ions are loaded on the humic acid modified aerogel, and a loading method conventional in the field can be adopted. The metal ion is Cu 2+ 、Fe 2+ 、Mg 2+ At least one of the above, preferably contains Fe 2+ . Wherein, the metal ion load is 1% -5% of metal oxide based on the total mass.
The metal ions loaded on the humic acid modified aerogel in the step (1) can be specifically carried out by the following method: adding humic acid modified aerogel into metal ion solution for soaking, stirring for a certain time, taking out for heat treatment, and drying to obtain metal-loaded modified aerogel. The metal ion solution is generally a soluble salt solution of metal ions, and the concentration of the metal ion solution is 4-10mol/L. The impregnation can be equal volume impregnation or excessive impregnation, one or more times of impregnation can be adopted, and the impregnation is carried out for 6-10 hours under the stirring condition of 60-70 ℃. The heat treatment is carried out by treating at 90-120deg.C for 1-5 hr, and then treating at 150-300deg.C for 1-5 hr. The drying is to dry for 1-2 hours at the constant temperature of 100-120 ℃ to obtain the modified aerogel loaded with metal. Further, betaine is added into the metal ion solution, and the mass ratio of the added amount of betaine to the metal ion is 1:1-1:5.
The mass ratio of the activated carbon to the metal-loaded modified aerogel in the step (1) is 1:1-1:10. The mesh number of the activated carbon is 100-500 mesh.
The nitrifying bacteria suspension is obtained by settling nitrifying bacteria culture solution obtained by culture in the step (2), removing supernatant until the settling ratio is 80% -90%, 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. Mixing, adsorbing at 28-30deg.C and 100-200r/min for 60-180min, and centrifuging at 400-600r/min for 2-10min.
Further, the polyethyleneimine is added in the step (2), and the addition amount is 1% -5% of the volume of the nitrifying bacteria suspension.
Step (3) of the present invention is entrapping crosslinking by methods well known in the art. Specifically, the gel is 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 20-30g/L; and then adding the gel into the solid in the step (2) according to the volume ratio of 2-3:1, and stirring and uniformly mixing. Said CaCl 2 The saturated boric acid solution with the mass fraction of 3-5% is continuously stirred, crosslinked and fixed for 24-48h at the temperature of 4-5 ℃ after titration is finished, and finally the saturated boric acid solution is washed three times by using physiological saline with the mass fraction of 0.9%, so that the immobilization of nitrifying bacteria is completed, and the nitrified bacteria is stored at the temperature of 0-5 ℃.
The immobilized nitrifying bacteria of the present invention are prepared by the above-described method of the present invention. The immobilized nitrifying bacteria are prepared by loading metal ions on humic acid modified aerogel, mixing the metal ions with activated carbon to prepare an immobilized carrier, adsorbing nitrifying bacteria 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, metal ions are loaded, then the humic acid modified aerogel is mixed with activated carbon to serve as an immobilized carrier, then the immobilized carrier is used for adsorbing nitrifying bacteria, and finally the immobilized nitrifying bacteria are prepared through embedding and crosslinking, so that the impact of high-concentration ammonia nitrogen on nitrifying bacteria can be relieved, the efficient and stable treatment effect is ensured, and nitrifying bacteria and the carrier are firmly combined, so that the bacterial body is prevented from falling off.
(2) The immobilized carrier material is prepared by adopting humic acid modified aerogel and metal ion load, and through synergistic effect, all substances are tightly combined, so that microorganism adhesion and adsorption are finally facilitated, and the immobilized carrier material has strong binding force.
(3) The betaine is added into the metal ion impregnation solution, so that the bonding strength of the metal ions and the aerogel is improved, and meanwhile, the bonding force of the metal ions and microorganisms is enhanced, thereby being beneficial to further avoiding the falling of the microorganisms in the long-term treatment process.
(4) The polyethyleneimine is added in the process of adsorbing microorganisms by the carrier, so that the affinity of the microorganisms to the carrier is improved, the number of the microorganisms immobilized by the carrier in unit volume is large, the adsorption time is shortened, and the immobilization efficiency is improved.
(5) The immobilization method of nitrifying bacteria 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 process and effects of the present invention are described in further detail by the following examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
In the embodiment of the invention, the ammonia nitrogen concentration is measured by GB7478-87 determination of water quality ammonium-distillation and titration method; the concentration of the suspension was measured by the method of measuring the suspension in water-weight of GB 11901-89.
Example 1
(1) Preparing an immobilization carrier:
the humic acid modified carbon aerogel is adopted: (a) Will have a specific surface area of 800m 2 Immersing/g carbon aerogel with the porosity of 80% in 1.5mol/L acetic acid solution for water bath reaction at the temperature of 40 ℃, oscillating for 1.5h, taking out, and washing with deionized waterTo pH7.0; (b) Preparation of 0.6mol/L Fe (OH) 3 Solutions according to Fe (OH) 3 The mass ratio of the solution to the humic acid is 2:1, and the humic acid is dissolved in Fe (OH) 3 And (3) mixing the solution with the carbon aerogel treated in the step (a), reacting for 4 hours in a water bath at 60 ℃, taking out, and washing with deionized water to pH7.0 to obtain the humic acid modified aerogel.
Loading metal ions: preparing a ferrous sulfate solution with the concentration of 4mol/L, adding the humic acid modified aerogel into the solution, and soaking for 8 hours under the stirring condition of 65 ℃. The sample was taken out and treated at 100℃for 3 hours and then at 200℃for 3 hours. And drying at 110 ℃ for 1.5h after heat treatment to obtain the metal-loaded modified aerogel.
Mixing with activated carbon: mixing 100-200 meshes of activated carbon with metal-loaded modified aerogel according to the mass ratio of 1:5 to prepare the immobilized carrier.
(2) Adsorption of nitrifying bacteria:
settling freshly cultured nitrifying bacteria culture solution, removing supernatant until the settling ratio is 90%, namely nitrifying bacteria suspension, uniformly mixing the nitrifying bacteria suspension with an immobilization carrier according to a liquid-solid ratio of 10mL:1g, adsorbing for 60min at 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 25g/L; and then adding the gel into the solid in the step (2) according to the volume ratio of 2:1, and stirring and uniformly mixing. Said CaCl 2 The saturated boric acid solution with the mass fraction of 4% is continuously stirred, crosslinked and fixed for 24 hours at the temperature of 4 ℃ after titration is finished, and finally the saturated boric acid solution is washed three times by using physiological saline with the mass fraction of 0.9%, so that the immobilization of nitrifying bacteria is completed, and the nitrified bacteria is stored at the temperature of 4 ℃.
Example 2
(1) Preparing an immobilization carrier:
the humic acid modified carbon aerogel is adopted: (a) Will have a specific surface area of 800m 2 Immersing/g carbon aerogel with porosity of 80% in 1.0mol/L acetic acid solution for water bath reaction at 30deg.C, oscillating for 1 hr to obtainWashing the product with deionized water to pH6.5; (b) Preparation of 0.5mol/LFe (OH) 3 Solutions according to Fe (OH) 3 The mass ratio of the solution to the humic acid is 1:1, and the humic acid is dissolved in Fe (OH) 3 And (3) mixing the solution with the carbon aerogel treated in the step (a), oscillating for 3 hours in a water bath at 50 ℃, and then washing with deionized water to pH6.5 to obtain the humic acid modified aerogel.
Loading metal ions: preparing a ferrous sulfate solution with the concentration of 4mol/L, adding the humic acid modified aerogel into the solution, and soaking for 10 hours under the stirring condition at 60 ℃. The sample was taken out and treated at 90℃for 5 hours and then at 150℃for 5 hours. And then drying for 2 hours at the constant temperature of 100 ℃ to obtain the metal-loaded modified aerogel.
Mixing with activated carbon: mixing 200-300 mesh activated carbon and metal-loaded modified aerogel according to a mass ratio of 1:8 to prepare an immobilization carrier.
(2) Adsorption of nitrifying bacteria:
settling freshly cultured nitrifying bacteria culture solution, removing supernatant until the settling ratio is 90%, namely nitrifying bacteria suspension, uniformly mixing the nitrifying bacteria suspension with an immobilization 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.
(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 20g/L; and then adding the gel into the solid in the step (2) according to the volume ratio of 3:1, and stirring and uniformly mixing. Said CaCl 2 The saturated boric acid solution with the mass fraction of 3 percent is continuously stirred, crosslinked and fixed for 36 hours at the temperature of 4 ℃ after titration is finished, and finally the saturated boric acid solution is washed three times by normal saline with the mass fraction of 0.9 percent, so that the immobilization of nitrifying bacteria is finished, and the nitrified bacteria is stored at the temperature of 4 ℃.
Example 3
(1) Preparing an immobilization carrier:
the humic acid modified carbon aerogel is adopted: (a) Will have a specific surface area of 1000m 2 Immersing/g carbon aerogel with porosity of 98% in 2.0mol/L acetic acid solution for water bath reaction at the temperature ofShaking for 2 hours at 50 ℃, taking out, and washing with deionized water to pH7.5; (b) Preparation of 0.8mol/LFe (OH) 3 Solutions according to Fe (OH) 3 The mass ratio of the solution to the humic acid is 3:1, and the humic acid is dissolved in Fe (OH) 3 And (3) mixing the solution with the carbon aerogel treated in the step (a), oscillating for 5 hours in a water bath at 70 ℃, and then washing with deionized water to pH7.5 to obtain the humic acid modified aerogel.
Loading metal ions: preparing a ferrous sulfate solution with the concentration of 4mol/L, adding the humic acid modified aerogel into the solution, and soaking for 6 hours under the stirring condition of 70 ℃. The sample was taken out and treated at 120℃for 1 hour and 300℃for 1 hour. And then drying for 1h at the constant temperature of 120 ℃ to obtain the metal-loaded modified aerogel.
Mixing with activated carbon: mixing 400-500 mesh activated carbon and metal-loaded modified aerogel according to a mass ratio of 1:10 to prepare the immobilized carrier.
(2) Adsorption of nitrifying bacteria:
settling the freshly cultured nitrifying bacteria culture solution, removing supernatant until the settling ratio is 90%, namely nitrifying bacteria suspension, uniformly mixing the nitrifying bacteria suspension with an immobilization carrier according to the liquid-solid ratio of 15mL to 1g, and centrifuging for 10min under the conditions of adsorption at 30 ℃ and 200r/min for 180min and 600r/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 80g/L, and the content of the sodium alginate is 30g/L; and then adding the gel into the solid in the step (2) according to the volume ratio of 3:1, and stirring and uniformly mixing. Said CaCl 2 The saturated boric acid solution with the mass fraction of 5% is continuously stirred, crosslinked and fixed for 48 hours at the temperature of 4 ℃ after titration is finished, and finally the saturated boric acid solution is washed three times by using physiological saline with the mass fraction of 0.9%, so that the immobilization of nitrifying bacteria is completed, and the nitrified bacteria is stored at the temperature of 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 1000m 2 And/g, porosity 85%. Finally, the immobilized nitrifying bacteria are prepared and stored at 4 ℃.
Example 5
The difference from example 1 is that: the cellulose aerogel is adopted to replace the carbon aerogel, and the specific surface area of the cellulose aerogel is 900m 2 And/g, the porosity is 95%. Finally, the immobilized nitrifying bacteria are prepared and stored at 4 ℃.
Example 6
The difference from example 1 is that: the metal ion adopts Cu 2+ A 4mol/L copper chloride solution was prepared in place of the ferric sulfate solution. Finally, the immobilized nitrifying bacteria are prepared and stored at 4 ℃.
Example 7
The difference from example 1 is that: the metal ion adopts Mg 2+ A magnesium sulfate solution of 4mol/L was prepared instead of the ferric sulfate solution. Finally, the immobilized nitrifying bacteria are prepared and stored at 4 ℃.
Example 8
The difference from example 1 is that: betaine is added into the metal salt solution, and the mass ratio of the added amount of betaine to metal ions is 1:3. Finally, the immobilized nitrifying bacteria are prepared and stored at 4 ℃.
Example 9
The difference from example 1 is that: and (2) adding polyethylenimine into the nitrifying bacteria suspension, wherein the adding amount is 5% of the volume of the nitrifying bacteria suspension. Finally, the immobilized nitrifying bacteria are prepared and stored at 4 ℃.
Example 10
The difference from example 8 is that: and (2) adding polyethylenimine into the nitrifying bacteria suspension, wherein the adding amount is 3% of the volume of the nitrifying bacteria suspension. Finally, the immobilized nitrifying bacteria are prepared and stored at 4 ℃.
Comparative example 1
The difference from example 1 is that: the aerogel modification step (b) does not use humic acid and only loads metal ions. Finally, the immobilized nitrifying bacteria are prepared and stored at 4 ℃.
Comparative example 2
The difference from example 1 is that: after the aerogel is modified by humic acid, the humic acid is dissolved in water, and no metal ion is loaded, namely Fe (OH) is not adopted 3 A solution. Finally, the immobilized nitrifying bacteria are prepared,preserving at 4 ℃.
Comparative example 3
The difference from example 1 is that: step (a) is omitted when the aerogel humic acid is modified, and only step (b) is adopted. Finally, the immobilized nitrifying bacteria are prepared and stored at 4 ℃.
Comparative example 4
The difference from example 1 is that: no heat treatment is used in the process of loading the metal ions. Finally, the immobilized nitrifying bacteria are prepared and stored at 4 ℃.
Test case
The immobilized nitrifying bacteria prepared in examples 1-10 and comparative examples 1-4 were treated with sewage, and mixed with sewage to be treated at a solid-to-liquid ratio of 1:5, and the concentration of ammonia nitrogen in the sewage was 300mg/L. The treatment is carried out for 48 hours, and the ammonia nitrogen removal condition and the suspended matter condition of the effluent are examined, and the effect is shown in table 1.
TABLE 1
As is clear from Table 1, the immobilized nitrifying bacteria prepared by the method of the invention has better treatment effect, and the bacteria are firmly combined, and after long-term treatment, the effluent suspended matters are less.
Claims (21)
1. A nitrifying bacteria immobilization method is characterized by comprising the following steps:
(1) Preparing an immobilization carrier: adopting humic acid modified aerogel, loading metal ions, and uniformly mixing with active carbon to prepare an immobilized carrier; the process of modifying aerogel by humic acid comprises the following steps: (a) Placing the aerogel in acetic acid solution for water bath oscillation, taking out and washing to be neutral; (b) Dissolving humic acid in Fe (OH) 3 Mixing the solution with the aerogel obtained in the step (a), performing water bath reaction at 50-70 ℃, and washing to be neutral after the reaction to obtain humic acid modified aerogel; the metal ion is Cu 2+ 、Fe 2+ 、Mg 2+ At least one of (a) and (b);
(2) Adsorption of nitrifying bacteria: mixing the immobilized carrier with nitrifying bacteria suspension, and centrifuging after adsorption to obtain solid substances for adsorbing nitrifying bacteria;
(3) Embedding and crosslinking after adsorption: preparing polyvinyl alcohol and sodium alginate gel, adding the gel into the solid in the step (2), uniformly mixing, and dripping CaCl 2 And (3) in saturated boric acid solution, after titration, crosslinking and fixing for a certain time, and washing to obtain the immobilized nitrifying bacteria.
2. The method according to claim 1, characterized in that: the aerogel in the step (1) is at least one of carbon aerogel, silicon aerogel and cellulose aerogel.
3. The method according to claim 2, characterized in that: the aerogel in the step (1) is carbon aerogel.
4. A method according to claim 1 or 2 or 3, characterized in that: the specific surface area of the aerogel is 600-1100 m 2 And/g, wherein the porosity is 80% -98%.
5. The method according to claim 1, characterized in that: the concentration of the acetic acid solution in the step (a) is 1.0-2.0 mol/L; immersing aerogel in acetic acid solution for water bath reaction, wherein the reaction temperature is 30-50 ℃ and the reaction time is 1.0-2.0 h; taking out the aerogel, and washing to pH 6.5-7.5.
6. The method according to claim 1, characterized in that: fe (OH) as described in step (b) 3 The concentration of the solution is 0.5 to 0.8mol/L, fe (OH) 3 The mass ratio of the solution to the humic acid is 1:1-3:1.
7. The method of claim 1, 5 or 6, wherein: immersing the aerogel of step (a) in humic acid and Fe (OH) 3 In the mixed system of the solution, the water bath reaction is carried out for 3 to 5 hours at the temperature of 50 to 70 ℃, and the pH value is washed to 6.5 to 7.5 after the reaction.
8. The method according to claim 1, characterized in that: step (1) loading metal ions on humic acid modified aerogel, wherein the metal ions are Fe 2+ 。
9. The method according to claim 1 or 8, characterized in that: in the step (1), the metal ion load is 1% -5% of metal oxide based on the total mass.
10. The method according to claim 1, characterized in that: the step (1) of loading metal ions on the humic acid modified aerogel adopts the following method: adding humic acid modified aerogel into metal ion solution for soaking, stirring and soaking for a period of time, taking out for heat treatment, and drying to obtain metal-loaded modified aerogel.
11. The method according to claim 10, wherein: the metal ion solution adopts a soluble salt solution of metal ions, and the concentration of the metal ion solution is 4-10mol/L; adding humic acid modified aerogel, stirring and soaking for 6-10h at 60-70 ℃.
12. The method according to claim 10, wherein: the heat treatment is carried out by treating at 90-120deg.C for 1-5 hr, and then treating at 150-300deg.C for 1-5 hr.
13. The method according to claim 10 or 11, characterized in that: betaine is added into the metal ion solution, and the mass ratio of the added amount of betaine to the metal ion is 1:1-1:5.
14. The method according to claim 1, characterized in that: 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 according to claim 1, characterized in that: and (2) settling the nitrifying bacteria culture solution obtained by culture, removing supernatant until the settling ratio is 80% -90%, namely nitrifying bacteria suspension, and mixing the nitrifying bacteria suspension with the immobilization 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: and (3) uniformly mixing the materials in the step (2), adsorbing for 60-180min at the temperature of 28-30 ℃ and the speed of 100-200r/min, and centrifuging for 2-10min at the speed 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 in the step (2), wherein the addition amount is 1-5% of the volume of the nitrifying bacteria suspension.
18. The method according to claim 1, characterized in that: 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 20-30g/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 stirring and uniformly mixing.
20. The method according to claim 1, characterized in that: caCl as described in step (3) 2 The mass fraction of the saturated boric acid solution is 3-5%, the saturated boric acid solution is crosslinked and fixed for 24-48h at the temperature of 4-5 ℃ after titration, and finally the saturated boric acid solution is washed by physiological saline with the mass fraction of 0.9%.
21. An immobilized nitrifying bacterium characterized by being produced by the method according to any one of claims 1 to 20.
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