CN113122529B - Microorganism immobilization material and preparation method and application thereof - Google Patents
Microorganism immobilization material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 244000005700 microbiome Species 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004964 aerogel Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 27
- 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 24
- 239000004021 humic acid Substances 0.000 claims abstract description 24
- 238000012986 modification Methods 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 35
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 26
- 239000004966 Carbon aerogel Substances 0.000 claims description 22
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 241000894006 Bacteria Species 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229960003237 betaine Drugs 0.000 claims description 9
- 230000000593 degrading effect Effects 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 239000002351 wastewater Substances 0.000 claims description 9
- 239000001913 cellulose Substances 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 241000108664 Nitrobacteria Species 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 230000003100 immobilizing effect Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000011866 long-term treatment Methods 0.000 abstract description 5
- 230000000813 microbial effect Effects 0.000 abstract description 3
- 230000035755 proliferation Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011268 mixed slurry Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 241001052560 Thallis Species 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000011790 ferrous sulphate Substances 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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001546 nitrifying effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 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 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 230000009286 beneficial 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
- 238000004132 cross linking Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 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
- 238000002156 mixing Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 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
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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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
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Genetics & Genomics (AREA)
- Wood Science & Technology (AREA)
- Biomedical Technology (AREA)
- Microbiology (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Biotechnology (AREA)
- Inorganic Chemistry (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Biological Treatment Of Waste Water (AREA)
Abstract
The invention relates to a microorganism immobilization material and a preparation method thereof, comprising (1) aerogel pretreatment; (2) humic acid modification; (3) carrying metal ions; and (4) drying. The microbial immobilized material prepared by the invention not only can adsorb microbes, but also can promote the proliferation of the adsorbed microbes, particularly can enhance the binding force between the material and the microbes, and can prevent the microbes from falling off in the long-term treatment process.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a microorganism immobilization material, and a preparation method and application thereof.
Background
The microorganism immobilization technology is to adopt a proper carrier to fix pure 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 nitrobacteria have slow growth and reproduction and small flora concentration, and strains are easy to lose, poor in adverse environment tolerance and easy to inhibit activity in the application process, so that the biomass in the system can be obtained and maintained by adopting a microorganism immobilization technology, and the treatment effect of the ammonia-containing sewage is ensured.
Current immobilization methods include adsorption, carrier binding, entrapment, and cross-linking, each of which has advantages and disadvantages. The embedding and immobilizing technology has the defects of low mechanical strength and the like, and the surface adsorption technology has limited large-scale application due to small surface area and easy separation of biological membranes. 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 wt% of CaCl 2 Standing in the solution at 0-10 deg.c for 2-24 hr and flushing with normal saline or water. The ammonia nitrogen degrading bacteria provided by the method can not run off 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 can treat the wastewater with the ammonia nitrogen concentration of 256.9mg/L to be more than 15.11mg/L within 60 hours when being applied. 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 immobilized microorganism bacteria of porous cellulose aerogel, which mainly comprises preparing porous cellulose aerogel, adsorbing and immobilizing nitrifying bacteria and denitrifying bacteria on the porous cellulose aerogel by carrier combination method, immobilizing microorganism on the porous cellulose aerogel to treat ammonia nitrogen wastewater, facilitating synchronous nitrification and denitrification reaction, having good ammonia nitrogen removal capability, high reaction efficiency and strong stability, adding 20-30g/L of the immobilized microorganism into 50-100L of 100-500mg/L ammonia nitrogen wastewater, hydraulic retention time of 30-40h, and ammonia nitrogen removal rate of 68-89% after treatment. The method utilizes cellulose aerogel to adsorb and fix thalli, belongs to surface adsorption, and has the phenomenon of falling off in long-term treatment due to weak binding force between the thalli and an adsorbing material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a microorganism immobilization material, a preparation method and application thereof. The microbial immobilized material prepared by the invention not only can adsorb microbes, but also can promote the proliferation of the adsorbed microbes, particularly can enhance the binding force between the material and the microbes, and can avoid the shedding of the microbes in the long-term treatment process.
The invention relates to a preparation method of a microorganism immobilization material, which comprises the following steps:
(1) Pretreating the aerogel: placing the aerogel into an acetic acid solution for water bath oscillation, taking out and washing until the pH value is neutral;
(2) Modification of humic acid: dissolving humic acid in Fe (OH) 3 Adding aerogel into the solution, performing water bath reaction at 50-70 ℃, and washing to be neutral to obtain modified aerogel;
(3) And (3) loading metal ions: loading metal ions on the modified aerogel by adopting an impregnation method, and then carrying out heat treatment;
(4) And (4) drying the product obtained in the step (3) to obtain the immobilized material.
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. Is usually obtained by a self-made or commercial purchase mode, and the specific surface area is 600-1100 m 2 The porosity is 80-98 percent.
In the invention, the concentration of the acetic acid solution in the step (1) is 1.0-2.0 mol/L. Immersing the aerogel in an acetic acid solution for water bath, wherein the water bath temperature is 30-50 ℃, and shaking for 1.0-2.0 h. And taking out the aerogel, and washing the aerogel for multiple times by using deionized water until the pH value of the washing water is 6.5-7.5.
In the present invention, fe (OH) in the step (2) 3 The concentration of the solution is 0.5-0.8 mol/L. Fe (OH) 3 The mass ratio of the solution to the humic acid is 1.
In the invention, the water bath in the step (2) is vibrated for 3-5 h at 50-70 ℃, and the obtained product is washed with deionized water for many times after being taken out until the pH value of the washing water is 6.5-7.5, so as to obtain the modified aerogel.
In the invention, the metal ion in the step (3) is Cu 2+ 、Fe 2+ 、Mg 2+ Etc., preferably contains Fe 2+ . Generally, the metal ion soluble salt solution is adopted, and the concentration of the metal ion solution is 4-10mol/L.
In the invention, the dipping method in the step (3) refers to adding the modified aerogel into a solution containing metal ions, and stirring or shaking the modified aerogel at the temperature of between 60 and 70 ℃ for 6 to 10 hours. The impregnation method can adopt equal volume or excess impregnation, and can adopt one or more times of impregnation.
Further, in the step (3), betaine is added into the impregnation liquid containing the metal ions, and the mass ratio of the added amount of the betaine to the metal ions is 1.
In the invention, the step (4) is dried for 1 to 2 hours at the constant temperature of between 100 and 120 ℃.
The microorganism immobilization material of the present invention is prepared by the above-described method of the present invention. In the prepared immobilization material, the density of the aerogel is 100-1000kg/m 3 Wherein the metal content accounts for 1-20% of the modified aerogel by weight and the humic acid accounts for 0.1-10% of the modified aerogel by weight. Further, betaine is also included, and accounts for 0.1-10% of the modified aerogel.
The microorganism immobilization material is applied to immobilizing autotrophic microorganisms such as nitrobacteria and the like. The method specifically comprises the following steps: mixing the immobilization material with the nitrobacteria suspension according to the solid-to-liquid ratio of 1-5-10 to perform immobilization reaction, and completing the immobilization of ammonia nitrogen degrading bacteria for treating ammonia nitrogen-containing wastewater when the ammonia nitrogen concentration reaches 300-500mg/L and the ammonia nitrogen removal rate is more than 90% within 24 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) The microorganism immobilization material prepared from the humic acid modified aerogel has a pore structure suitable for attachment growth of microorganisms, can adsorb the microorganisms, can promote proliferation of the adsorbed microorganisms, is particularly convenient for metal ion loading, can enhance the binding force of the aerogel and the microorganisms, and can prevent the microorganisms from falling off in a long-term treatment process.
(2) The humic acid aerogel material is loaded with humic acid and metal ions by two modes of modification and loading, and substances are tightly combined through the synergistic adsorption effect of the humic acid aerogel material and the metal ions, so that microorganisms are conveniently attached and adsorbed, and the binding force is strong.
(3) According to the invention, the betaine is added into the metal ion solution, so that the bonding strength of the metal ions and the aerogel is improved, the bonding force of the metal ions and microorganisms is enhanced, and the microbial shedding can be further avoided in the long-term treatment process.
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.
Example 1
Carbon aerogel pretreatment: and (3) putting the carbon aerogel into 1.5 mol/L acetic acid solution, immersing the carbon aerogel into the acetic acid solution, carrying out water bath at the water bath temperature of 40 ℃, shaking for 1.5h, taking out the carbon aerogel, and washing the carbon aerogel with deionized water until the pH value is 7.0.
Modification of humic acid: preparation of 0.6 mol/LFe (OH) 3 Solution according to Fe (OH) 3 The mass ratio of the solution to the humic acid is 2 3 And adding the pretreated carbon aerogel into the solution, oscillating in a water bath at 60 ℃ for 4h, taking out, and washing with deionized water to pH7.0 to obtain the modified aerogel.
Preparing a 4mol/L ferrous sulfate solution, adding the modified aerogel into the solution, and soaking for 8 hours at 65 ℃ under the stirring condition. Taking out and drying at the constant temperature of 110 ℃ for 1.5h to obtain the immobilized material.
Example 2
Carbon aerogel pretreatment: and (3) putting the carbon aerogel into 1mol/L acetic acid solution, immersing the carbon aerogel into the acetic acid solution to carry out water bath, wherein the water bath temperature is 30 ℃, shaking for 1h, taking out the carbon aerogel, and washing the carbon aerogel with deionized water until the pH value is 6.5.
Modification of humic acid: preparation of 0.5 mol/LFe (OH) 3 Colloidal suspension, humic acid is dissolved in Fe (OH) according to the mass ratio of the suspension to the humic acid of 1 3 And adding the pretreated carbon aerogel into the colloidal suspension, oscillating in a water bath at 50 ℃ for 3h, taking out, and washing with deionized water until the pH value is 6.5 to obtain the modified aerogel.
Preparing a ferrous sulfate solution of 3mol/L, adding the modified aerogel into the solution, and shaking and dipping for 6 hours at the temperature of 60 ℃. Taking out and drying at constant temperature of 100 ℃ for 1h to obtain the immobilized material. Example 3
Carbon aerogel pretreatment: and (3) putting the carbon aerogel into 2.0mol/L acetic acid solution, immersing the carbon aerogel into the acetic acid solution to carry out water bath, wherein the water bath temperature is 50 ℃, shaking for 2h, taking out the carbon aerogel, and washing the carbon aerogel with deionized water until the pH value is 7.5.
Modification of humic acid: preparation of 0.8mol/LFe (OH) 3 Colloidal suspension, humic acid is dissolved in Fe (OH) according to the mass ratio of the suspension to the humic acid of 3 3 And adding the pretreated carbon aerogel into the colloidal suspension, shaking in a water bath at 70 ℃ for 5 hours, taking out the mixture, and washing the mixture with deionized water until the pH value is 7.5 to obtain the modified aerogel.
5mol/L ferrous sulfate solution is prepared, the modified aerogel is added into the solution, and the solution is stirred and dipped for 10 hours at 70 ℃. Taking out and drying at constant temperature of 120 ℃ for 2h to obtain the immobilized material.
Example 4
The difference from example 1 is that: a silicon aerogel is used.
Example 5
The difference from example 1 is that: cellulose aerogel is used.
Example 6
The same as example 1, except that: using metal ions as Cu 2+ To prepare a 4mol/L copper chloride solution.
Example 7
The difference from example 1 is that: the metal ions are Mg 2+ To prepare a 4mol/L magnesium sulfate solution.
Example 8
The difference from example 1 is that: and adding betaine into the metal salt solution, wherein the mass ratio of the added amount of the betaine to the metal ions is 1.
Comparative example 1
The difference from example 1 is that: the aerogel was not pretreated.
Comparative example 2
The difference from example 1 is that: and no humic acid is added during modification of aerogel humic acid.
Comparative example 3
The difference from example 1 is that: the aerogel humic acid is modified without adding Fe (OH) 3 。
Comparative example 4
The difference from example 1 is that: the modified aerogel is not loaded with metal ions.
Test example
The immobilization materials prepared in examples 1-8 and comparative examples 1-4 are mixed with nitrobacteria suspension according to a solid-to-liquid ratio of 1.
The immobilized microorganism is used for treating ammonia-containing wastewater, the concentration of ammonia nitrogen in the wastewater is 300mg/L, after one month of treatment, the removal condition of ammonia nitrogen and the condition of suspended matters in effluent are investigated, and the specific effects are shown in Table 1.
TABLE 1
As can be seen from Table 1, the immobilization material prepared by the method of the invention can immobilize more nitrifying bacteria, and the two are tightly combined, so that the treatment effect is good. Without the immobilized material prepared by the method, thalli fall off from the immobilized material under the same time and condition, so that the removal rate of ammonia nitrogen is gradually reduced to 60 percent.
Claims (9)
1. A preparation method of a microorganism immobilization material is characterized by comprising the following steps:
(1) Pretreating the aerogel: placing the aerogel into an acetic acid solution for water bath oscillation, taking out and washing until the pH value is neutral; (2) humic acid modification: dissolving humic acid in Fe (OH) 3 Adding aerogel into the solution, performing water bath reaction at 50-70 ℃, and washing to be neutral to obtain modified aerogel; (3) metal ion loading: loading metal ions on the modified aerogel by adopting an impregnation method, and then carrying out heat treatment; the metal ion being Cu 2+ 、Fe 2+ 、Mg 2+ At least one of; (4) Drying the product obtained in the step (3) to obtain an immobilized material;
the concentration of the acetic acid solution in the step (1) is 1.0-2.0 mol/L; immersing the aerogel in an acetic acid solution for water bath, wherein the water bath temperature is 30-50 ℃, and oscillating for 1.0-2.0 h; taking out the aerogel, and washing with deionized water until the pH value of washing water is 6.5-7.5;
step (2) said Fe (OH) 3 The concentration of the solution is 0.5-0.8 mol/L; fe (OH) 3 The mass ratio of the solution to the humic acid is 1; performing water bath oscillation for 3-5 h at 50-70 ℃, taking out, and washing with deionized water until the pH value of washing water is 6.5-7.5 to obtain modified aerogel;
the metal ion load in the step (3) adopts a soluble salt solution of the metal, and the concentration of the metal ion solution is 4-10mol/L; the dipping method is stirring or shaking at 60-70 ℃ for 6-10h;
and (4) drying at the constant temperature of 100-120 ℃ for 1-2 h.
2. The method of claim 1, wherein: the aerogel in the step (1) is at least one of carbon aerogel, silicon aerogel and cellulose aerogel.
3. The method of claim 2, wherein: the aerogel in the step (1) is carbon aerogel.
4. The method of claim 1, wherein: the metal ion in the step (3) is Fe 2+ 。
5. The method of claim 1, wherein: and (3) adding betaine into the impregnation liquid containing the metal ions, wherein the mass ratio of the addition amount of the betaine to the metal ions is 1-1.
6. A microorganism-immobilizing material, characterized by being produced by the method of any one of claims 1 to 5.
7. The immobilization material according to claim 6, wherein: in the prepared immobilization material, the density of the aerogel is 100-1000kg/m 3 Wherein the metal content accounts for 1-20% of the modified aerogel by weight and the humic acid accounts for 0.1-10% of the modified aerogel by weight.
8. The immobilization material according to claim 7, wherein: the prepared immobilized material also comprises betaine which accounts for 0.1-10% of the mass of the modified aerogel.
9. Use of the immobilization material according to any one of claims 6 to 8, wherein: the method is used for immobilizing nitrobacteria, an immobilization material is mixed with nitrobacteria suspension according to the solid-to-liquid ratio of 1-5 to 10 to perform immobilization reaction, and when the ammonia nitrogen concentration reaches 300-500mg/L and the removal rate of ammonia nitrogen is more than 90% within 24h, the immobilization for treating ammonia nitrogen degrading bacteria by ammonia-containing wastewater is completed.
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Citations (3)
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| CN103962107A (en) * | 2014-03-14 | 2014-08-06 | 四川师范大学 | Preparation method of metal-modified humic acid defluorination adsorbing material |
| CN106186352A (en) * | 2016-07-25 | 2016-12-07 | 江苏星鑫分离设备制造有限公司 | A kind of method utilizing porous cellulose aeroge immobilized microorganism bacterium to process ammonia nitrogen waste water |
| CN108251410A (en) * | 2018-01-24 | 2018-07-06 | 南京大学 | A kind of immobilized microorganism preparation method for embedding aeroge |
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