CN111534507A - Immobilized microbial agent for raw ore of clay mineral, preparation method and application - Google Patents
Immobilized microbial agent for raw ore of clay mineral, preparation method and application Download PDFInfo
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- CN111534507A CN111534507A CN202010554716.1A CN202010554716A CN111534507A CN 111534507 A CN111534507 A CN 111534507A CN 202010554716 A CN202010554716 A CN 202010554716A CN 111534507 A CN111534507 A CN 111534507A
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- 239000002734 clay mineral Substances 0.000 title claims abstract description 79
- 230000000813 microbial effect Effects 0.000 title claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 241000894006 Bacteria Species 0.000 claims abstract description 33
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 22
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 22
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 11
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 11
- 239000010452 phosphate Substances 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 11
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 11
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 11
- 239000001509 sodium citrate Substances 0.000 claims abstract description 11
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000002504 physiological saline solution Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 25
- 239000000725 suspension Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 230000001580 bacterial effect Effects 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 238000012258 culturing Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000969 carrier Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000001546 nitrifying effect Effects 0.000 claims description 8
- 238000004065 wastewater treatment Methods 0.000 claims description 8
- 239000004113 Sepiolite Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052683 pyrite Inorganic materials 0.000 claims description 7
- 229910052624 sepiolite Inorganic materials 0.000 claims description 7
- 235000019355 sepiolite Nutrition 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052625 palygorskite Inorganic materials 0.000 claims description 6
- 239000011028 pyrite Substances 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910001919 chlorite Inorganic materials 0.000 claims description 3
- 229910052619 chlorite group Inorganic materials 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 229910052900 illite Inorganic materials 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052960 marcasite Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 3
- -1 rectorite Chemical compound 0.000 claims description 3
- 230000001360 synchronised effect Effects 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 13
- 238000001179 sorption measurement Methods 0.000 description 13
- 239000002068 microbial inoculum Substances 0.000 description 11
- 239000004927 clay Substances 0.000 description 9
- 241001052560 Thallis Species 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 244000005700 microbiome Species 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 208000028659 discharge Diseases 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000108664 Nitrobacteria Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 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
-
- 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
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Zoology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Wood Science & Technology (AREA)
- Water Supply & Treatment (AREA)
- Biotechnology (AREA)
- Biomedical Technology (AREA)
- Inorganic Chemistry (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The invention discloses a clay mineral raw ore immobilized microbial agent which comprises the following components in parts by weight: 1-8 parts of clay mineral raw ore, 0.5-5 parts of normal saline, 0.1-2 parts of ammonium sulfate, 1-10 parts of potassium nitrate, 2-10 parts of sodium citrate, 1-10 parts of phosphate, 0.1-2 parts of magnesium sulfate and 0.3-5 parts of composite bacteria. The invention also discloses a preparation method and application of the clay mineral raw ore immobilized microbial agent. The clay mineral raw ore immobilized microbial agent has good treatment effect on high-concentration ammonia nitrogen wastewater, and can reach the first-level discharge standard; the preparation method is simple to operate and easy to control, and can be used for large-scale batch preparation.
Description
Technical Field
The invention relates to the technical field of wastewater treatment,
in particular to a clay mineral raw ore immobilized microbial agent, a preparation method and application.
Background
Along with the excessive discharge of industrial wastewater and urban domestic water, sewage containing high-concentration ammonia nitrogen flows into rivers and lakes without being treated in large quantity, so that the water becomes eutrophic water, black and odorous water is caused, the difficulty and cost of water treatment are increased, and even toxic action is generated on human beings and organisms. The new leading-edge subject technology introduces wastewater treatment, and the wastewater treatment becomes a research hotspot in the technical field of water treatment.
The current wastewater treatment methods, such as a stripping method and a precipitation method, have the defects of overlarge power consumption, easy secondary pollution, secondary treatment for effluent which does not reach the discharge standard, and the like; the traditional biological adsorption method has the advantages of low cost, simple process, small environmental hazard, suitability for treating low-concentration waste liquid and the like, but because microorganisms are difficult to recycle, an adsorption system is difficult to naturally maintain stable for a long time and other factors, the practical application of the microbial adsorption technology is limited.
Compared with free microbial cells, the microbial immobilization has the characteristics of large enriched biomass, reusability, high mechanical strength, high microbial stability and activity and the like.
At present, the method for fixing microorganisms in the prior art still has a plurality of defects, such as the defect that the embedding method has small bonding strength and limits the activity of microorganisms and large mass transfer resistance; the covalent bonding method is difficult to prepare, the loss of cell activity is large, and the operation and control conditions are complex and harsh; the adsorption method requires processing of the immobilized carrier before adsorption, and is high in cost and not beneficial to large-scale production.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a clay mineral raw ore immobilized microbial agent, a preparation method and application thereof.
In order to solve the problems, the invention adopts the following technical scheme:
a clay mineral raw ore immobilized microbial agent comprises the following components in parts by weight: 1-8 parts of clay mineral raw ore, 0.5-5 parts of normal saline, 0.1-2 parts of ammonium sulfate, 1-10 parts of potassium nitrate, 2-10 parts of sodium citrate, 1-10 parts of phosphate, 0.1-2 parts of magnesium sulfate and 0.3-5 parts of composite bacteria.
Preferably, the clay mineral raw ore is at least one of montmorillonite, bentonite, rectorite, kaolin, illite, halloysite, palygorskite, sepiolite, attapulgite, vermiculite, chlorite and pyrite.
Preferably, the complex bacteria comprise at least two of: nitrifying bacteria, denitrifying bacteria and synchronous nitrifying and denitrifying bacteria.
Preferably, the effective components in the raw clay mineral ore comprise: SiO 22、Al2O3、TiO2、CaO、Na2O、K2O、MnO、ZnO、CuO、FeS2、Fe2O3。
The invention also provides a preparation method of the clay mineral raw ore immobilized microbial agent, which comprises the following steps:
dispersing raw clay mineral ores in deionized water, and obtaining raw clay mineral ore immobilized carriers through stirring, centrifuging, washing, standing, drying and crushing;
placing the compound bacteria in an incubator for preheating and activation, then adding a culture solution for culturing, centrifugally collecting wet bacteria, adding physiological saline, and uniformly mixing to obtain a bacterial suspension;
mixing the clay mineral raw ore immobilized carrier with the bacterial suspension, adding physiological saline and a culture solution for culturing, then washing with the physiological saline, and naturally drying to obtain the clay mineral raw ore immobilized microbial agent;
the culture solution contains the following components in parts by weight: 0.5-5 parts of normal saline, 0.1-2 parts of ammonium sulfate, 1-10 parts of potassium nitrate, 2-10 parts of sodium citrate, 1-10 parts of phosphate and 0.1-2 parts of magnesium sulfate.
Preferably, the preheating temperature of the preheating activation is 30-37 ℃, and the preheating time is 10-35 min.
The invention also provides an application of the clay mineral raw ore immobilized microbial agent in wastewater treatment, wherein the clay mineral raw ore immobilized microbial agent is added into wastewater containing ammonia nitrogen, and the reaction is carried out under stirring.
Preferably, the adding amount of the clay mineral raw ore immobilized microbial agent in the wastewater is 1-10 g/L; the stirring time is 1-16 h, and the reaction temperature is 15-45 ℃.
Compared with the prior art, the invention has the technical effects that:
(1) compared with the common clay adsorption in the prior art, the clay mineral raw ore has the characteristics of low price, low cost and no need of secondary processing;
(2) the clay mineral raw ore disclosed by the invention contains natural components, so that the bacteria-carrying quantity and activity are better than those of clay commonly used in the prior art, the treatment effect on high-concentration ammonia nitrogen wastewater is good, and the primary discharge standard can be reached;
(3) according to the invention, raw clay mineral ores are used as an adsorption carrier of the composite microbial inoculum, and the adsorption property and cation exchange property of the raw clay mineral ores enable the composite microbial inoculum to be adsorbed on the surface of the raw clay mineral ores through bridging by cations released among layers; polysaccharide and functional groups on the surface of the composite microbial inoculum can be more stably fixed on the surface of the raw ore of the clay mineral and in structural gaps inside the raw ore of the clay mineral; compared with other adsorbing materials, the clay mineral raw ore disclosed by the invention can adsorb the microbial agent more quickly and efficiently;
(4) the preparation method of the clay mineral raw ore immobilized microbial agent is simple to operate and easy to control, and can be used for large-scale batch preparation.
Drawings
FIG. 1 is an XRD pattern of crude and purified rectorite in example 1 of the present invention;
FIG. 2 is an SEM image of a raw rough rectorite ore of example 1 of the present invention;
FIG. 3 is a diagram showing the OD600 of a complex microbial inoculum immobilized on different carriers prepared in example 4 of the present invention;
FIG. 4 is a diagram showing the effect of the microbial composite inoculum immobilized by different carriers on ammonia nitrogen removal prepared in example 5 of the present invention.
In fig. 1, a, crude rectorite raw ore, B, crude rectorite after mineral separation and purification; in fig. 3, 1, 2, 3, 4, 5 respectively represent sodium-modified pure rectorite, sodium-modified raw rectorite, pure rectorite, crude rectorite, and fine rectorite, and 6 represents a blank sample; in fig. 4, 10, 20, 30, 40, and 50 represent microbial agents prepared by taking sodium-modified pure rectorite, sodium-modified raw rectorite, pure rectorite, coarse raw rectorite, and fine raw rectorite as carriers, respectively, and 60 represents a blank control, namely the initial concentration of ammonia nitrogen in wastewater; and the ordinate Y represents the concentration of the residual ammonia nitrogen after the wastewater is treated by the microbial agent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a clay mineral raw ore immobilized microbial agent which comprises the following components in parts by weight: 1-8 parts of clay mineral raw ore, 0.5-5 parts of normal saline, 0.1-2 parts of ammonium sulfate, 1-10 parts of potassium nitrate, 2-10 parts of sodium citrate, 1-10 parts of phosphate, 0.1-2 parts of magnesium sulfate and 0.3-5 parts of composite bacteria. The concentration of the physiological saline is 0.87-0.9%.
Wherein the clay mineral raw ore is at least one of montmorillonite, bentonite, rectorite, kaolin, illite, halloysite, palygorskite, sepiolite, attapulgite, vermiculite, chlorite and pyrite. The composite bacteria comprise at least two of the following bacteria: nitrifying bacteria, denitrifying bacteria and synchronous nitrifying and denitrifying bacteria. The effective components in the raw clay mineral include but are not limited to: SiO 22、Al2O3、TiO2、CaO、Na2O、K2O、MnO、ZnO、CuO、FeS2、Fe2O3。
The embodiment of the invention also provides a preparation method of the clay mineral raw ore immobilized microbial agent, which comprises the following steps:
(1) dispersing raw clay mineral ores in deionized water, stirring at 150-200 r/min, centrifuging at 3000-6000 r/min, washing for 2-4 times, standing for 5-40 min, drying at 40-100 ℃ for 12-24 h, and crushing to obtain raw clay mineral ore immobilized carriers;
(2) placing the compound bacteria in an incubator for preheating and activation, then adding a culture solution for culturing, centrifugally collecting wet bacteria, adding physiological saline, and uniformly mixing to obtain a bacterial suspension;
(3) mixing the clay mineral raw ore immobilized carrier with the bacterial suspension, adding physiological saline and a culture solution for culturing, then washing with the physiological saline, and naturally drying to obtain the clay mineral raw ore immobilized microbial agent.
Wherein the preheating temperature for preheating activation in the step (2) is 30-37 ℃, and the preheating time is 10-35 min. The culture solution contains the following components in parts by weight: 0.5-5 parts of normal saline, 0.1-2 parts of ammonium sulfate, 1-10 parts of potassium nitrate, 2-10 parts of sodium citrate, 1-10 parts of phosphate and 0.1-2 parts of magnesium sulfate. The culture temperature is 30-35 ℃, the oscillation frequency is 170-200 r/min, and the culture time is 20-24 h; the centrifugal speed is 6000-6500 r/min, and the centrifugal time is 5-8 min.
The embodiment of the invention also provides an application of the clay mineral raw ore immobilized microbial agent in wastewater treatment, when the clay mineral raw ore immobilized microbial agent is used, the clay mineral raw ore immobilized microbial agent is added into wastewater containing ammonia nitrogen, and after the mixture is stirred and reacts for a period of time, the clay mineral raw ore immobilized microbial agent and reclaimed water are obtained through separation, wherein the adding amount of the clay mineral raw ore immobilized microbial agent in 1L of high ammonia nitrogen wastewater is 1-10 g/L; the stirring time is 1-16 h, and the stirring reaction temperature is 15-45 ℃.
Compared with the common clay adsorption in the prior art, the clay mineral raw ore has the characteristics of low price, low cost and no need of secondary processing; in addition, the clay mineral raw ore disclosed by the invention contains natural components, so that the bacteria-carrying quantity and activity are better than those of the clay commonly used in the prior art, the treatment effect on high-concentration ammonia nitrogen wastewater is good, and the primary discharge standard can be reached; according to the invention, raw clay mineral ores are used as an adsorption carrier of the composite microbial inoculum, and the adsorption property and cation exchange property of the raw clay mineral ores enable the composite microbial inoculum to be adsorbed on the surface of the raw clay mineral ores through bridging by cations released among layers; polysaccharide and functional groups on the surface of the composite microbial inoculum can be more stably fixed on the surface of the raw ore of the clay mineral and in structural gaps inside the raw ore of the clay mineral; compared with other adsorbing materials, the clay mineral raw ore disclosed by the invention can adsorb the microbial agent more quickly and efficiently; the preparation method of the clay mineral raw ore immobilized microbial agent is simple to operate and easy to control, and can be used for large-scale batch preparation.
The following is a further description with reference to specific examples.
Example 1
The embodiment 1 of the invention provides a crude rectorite raw ore immobilized microbial agent and a preparation method thereof. The preparation method comprises the following steps:
(1) taking 1g of crude rectorite raw ore, adding 20 times of secondary deionized water (ddH) by mass2O), stirring for 1 h, centrifuging for 10min by a 4000 r/min centrifuge, and removing supernate and bottom impurities. The above operation was repeated 3 times. Adding the secondary deionized water again, stirring, standing for 30min, collecting the suspension, drying at 60 deg.C for 24h, and pulverizing to 100 mesh to obtain clay mineral raw ore immobilized carrier;
(2) 0.3g of composite bacteria of nitrobacteria and denitrifying bacteria stored in a refrigerator at 4 ℃ is taken to be preheated for 30min in an incubator at 30 ℃, then culture solution is added, and the culture is carried out for 24h at 30 ℃ and 150 r/min. Immediately centrifuging the taken bacterial mixed solution at 6000r/min for 10min, collecting wet thalli, washing with sterile physiological saline for 3 times, and then uniformly mixing the sterile physiological saline and the wet thalli to obtain bacterial suspension;
(3) mixing 0.1g of clay mineral raw ore immobilized carrier with 2mL of bacterial suspension, adding 18mL of physiological saline and 10mL of culture solution for culturing, washing with physiological saline, and naturally drying to obtain the clay mineral raw ore immobilized microbial agent.
The culture solution in the step (2) and the step (3) contains the following components: 0.5g of physiological saline, 0.1g of ammonium sulfate, 1g of potassium nitrate, 2g of sodium citrate, 1g of phosphate and 0.1g of magnesium sulfate.
XRD patterns of crude rectorite raw ore and purified rectorite are shown as the figure1, as can be seen from fig. 1, in the XRD spectrum of the crude rectorite raw ore, a series of relatively obvious characteristic peaks of rectorite exist at 2 θ =17.90 °, 18.74 °, 19.97 °, 25.37 °, 26.51 °, 27.46 °, 29.09 °, 35.15 ° and 62.61 °; compared with the rectorite after beneficiation and purification, the peaks appearing at 33.06 degrees, 37.11 degrees, 40.77 degrees, 47.42 degrees and 56.28 degrees of the crude rectorite crude ore are derived from FeS existing in the crude rectorite crude ore2. The SEM test of the raw rough rectorite ore of this example is performed, and the test result is shown in fig. 2, and it can be seen from fig. 2 that a part of pyrite having a larger particle size exists in the raw rough rectorite ore in addition to the large amount of small-particle rectorite clay flakes dispersed therein.
Example 2
The embodiment 2 of the invention provides a sepiolite raw ore immobilized microbial agent and a preparation method thereof. The preparation method comprises the following steps:
(1) 5g of sepiolite raw ore is taken, secondary deionized water (ddH 2O) with the mass being 20 times that of the sepiolite raw ore is added, after stirring for 1 h, the sepiolite raw ore is centrifuged for 10min by a centrifuge with the speed of 3000 r/min, and supernatant and bottom impurities are discarded. The above operation was repeated 3 times. Adding the secondary deionized water again, stirring, standing for 30min, collecting the suspension, drying at 100 ℃ for 12h, and crushing to 100 meshes to obtain the clay mineral raw ore immobilized carrier;
(2) preheating 5g of nitrifying bacteria and denitrifying bacteria compound bacteria stored in a 4 ℃ refrigerator in a 37 ℃ incubator for 10min, adding culture solution, and culturing at 30 ℃ and 100 r/min for 10 h. Centrifuging the mixed solution at 5000 r/min for 5 min, collecting wet thallus, washing with sterile physiological saline for 3 times, and mixing with sterile physiological saline to obtain bacterial suspension;
(3) mixing 0.1g of clay mineral raw ore immobilized carrier with 2mL of bacterial suspension, adding 18mL of physiological saline and 10mL of culture solution for culturing, washing with physiological saline, and naturally drying to obtain the clay mineral raw ore immobilized microbial agent.
The culture solution in the step (2) and the step (3) contains the following components: 3g of physiological saline, 2g of ammonium sulfate, 5g of potassium nitrate, 7g of sodium citrate, 5g of phosphate and 1g of magnesium sulfate.
Example 3
The embodiment 3 of the invention provides a kaolin crude ore immobilized microbial agent and a preparation method thereof. The preparation method comprises the following steps:
(1) taking 8g of kaolin crude ore, adding secondary deionized water (ddH 2O) with the mass of 20 times of the kaolin crude ore, stirring for 1 h, centrifuging for 10min by a 5000 r/min centrifugal machine, and removing supernatant and bottom impurities. The above operation was repeated 3 times. Adding the secondary deionized water again, stirring, standing for 20 min, collecting the suspension, drying at 40 deg.C for 24h, and pulverizing to 100 mesh to obtain clay mineral raw ore immobilized carrier;
(2) preheating 5g of nitrifying bacteria and denitrifying bacteria compound bacteria stored in a 4 ℃ refrigerator in a 37 ℃ incubator for 10min, adding culture solution, and culturing at 37 ℃ and 150 r/min for 12 h. Immediately centrifuging the taken bacterial mixed solution for 5 min at 4000 r/min, collecting wet thalli, washing with sterile physiological saline for 3 times, and then uniformly mixing the sterile physiological saline and the wet thalli to obtain bacterial suspension;
(3) mixing 0.1g of clay mineral raw ore immobilized carrier with 2mL of bacterial suspension, adding 18mL of physiological saline and 10mL of culture solution for culturing, washing with physiological saline, and naturally drying to obtain the clay mineral raw ore immobilized microbial agent.
The culture solution in the step (2) and the step (3) contains the following components: 2g of physiological saline, 1g of ammonium sulfate, 10g of potassium nitrate, 10g of sodium citrate, 10g of phosphate and 2g of magnesium sulfate.
Example 4
The embodiment 4 of the invention provides a method for verifying different adsorption effects of different types of rectorite as carriers on a microbial composite inoculant, which comprises the following steps:
(1) taking 0.1g of sodium-modified pure rectorite, fine rectorite raw ore, sodium-modified rectorite raw ore and coarse rectorite raw ore, and respectively adding 20 times of secondary deionized water (ddH) by mass2O), stirring for 1 h, centrifuging for 10min by a 4000 r/min centrifuge, and removing supernate and bottom impurities. The above operation was repeated 3 times. Adding deionized water again, stirring, standing for 30min, collecting suspension, drying at 60 deg.C for 18 hr, and pulverizing to 100 mesh to obtain powderTo 5 rectorite mineral carriers.
(2) 0.5g of composite bacteria of nitrobacteria and denitrifying bacteria stored in a refrigerator at 4 ℃ is preheated in an incubator at 30 ℃ for 30min, then culture solution is added, and the culture is carried out for 24h at 30 ℃ and 150 r/min. And (3) immediately centrifuging the taken bacterial mixed solution for 10min at 6000r/min, collecting wet thalli, washing with sterile physiological saline for 3 times, and then uniformly mixing the sterile physiological saline and the wet thalli to obtain bacterial suspension.
(3) And (3) sterilizing the 5 samples in the step (1) at high temperature, cooling to room temperature, adding the samples into 5 50mL centrifuge tubes, adding 2mL of the bacterial suspension in the step (2), adding physiological saline to 20mL, adding 10mL of culture solution to adsorb and form a membrane for 1 day, adding 5 mL of culture solution to culture for one day, and taking the bacterial suspension only and the clay mineral raw ore carrier not as a blank control group. The culture solution in the step (2) and the step (3) contains the following components: 0.5g of physiological saline, 0.2g of ammonium sulfate, 1g of potassium nitrate, 1g of sodium citrate, 1g of phosphate and 0.2g of magnesium sulfate.
(4) 6 samples obtained in step (3) were allowed to stand in an incubator at 30 ℃ for 12 hours, and the suspension was taken out to determine the OD value, and the results are shown in FIG. 3.
As can be seen from fig. 3, the crude rectorite ore carrier of this embodiment has the best adsorption effect on the complex microbial inoculum, and compared with other common clays of the prior art, the clay ore has a larger number of immobilized microorganisms.
Example 5
The microbial agent fixed by different rectorite mineral carriers prepared in the embodiment 4 of the invention is used for treating wastewater containing high ammonia nitrogen, and the specific steps are as follows:
(1) and (3) washing the mixed phase obtained in the step (3) in the embodiment 4 for 3 times by using normal saline, and naturally drying the washed mixed phase in an incubator at the temperature of 30 ℃ for 24 hours to obtain 5 different rectorite mineral carrier-immobilized microbial composite inocula.
(2) 5 kinds of microorganism compound microbial inoculum fixed by different rectorite mineral carriers are put into an aqueous solution with the ammonia nitrogen concentration of 134 mg/L, the initial pH of the solution is adjusted to 7.2, and the mixture is stirred and reacts for 24 hours at 25 ℃, wherein in 1L of ammonia nitrogen-containing wastewater, the adding amount of the clay raw ore fixed microbial inoculum is 5 g/L, the temperature of a constant temperature oscillator is controlled to be 30 ℃, the rotating speed is 200 r/min, and the clay raw ore fixed microbial inoculum and the reclaimed water which can adsorb and remove pollutants are obtained by filtering after 24 hours of reaction. The ammonia nitrogen content in the solution before and after the reaction was tested, and the test results are shown in fig. 4. As can be seen from FIG. 4, the immobilized microbial agent for crude rectorite crude ore has the best effect of removing ammonia nitrogen, and the ammonia nitrogen can be removed by the clay crude ore up to 123.37 mg/L, i.e., the removal rate of ammonia nitrogen can be up to 92.13%.
The removal rates of ammonia nitrogen in wastewater by the clay mineral raw ore immobilized microbial agents prepared in the examples 1, 2 and 3 of the present invention were tested in the same manner, and the removal rates of ammonia nitrogen were calculated to be 92.35%, 91.86% and 92.84%, respectively.
The present invention is not limited to the above-described specific embodiments, and various modifications and variations are possible. Any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention should be included in the scope of the present invention.
Claims (8)
1. The clay mineral raw ore immobilized microbial agent is characterized by comprising the following components in parts by weight: 1-8 parts of clay mineral raw ore, 0.5-5 parts of normal saline, 0.1-2 parts of ammonium sulfate, 1-10 parts of potassium nitrate, 2-10 parts of sodium citrate, 1-10 parts of phosphate, 0.1-2 parts of magnesium sulfate and 0.3-5 parts of composite bacteria.
2. The immobilized microbial agent of claim 1, wherein the raw clay mineral is at least one of montmorillonite, bentonite, rectorite, kaolin, illite, halloysite, palygorskite, sepiolite, attapulgite, vermiculite, chlorite and pyrite.
3. The immobilized microbial agent for raw clay mineral according to claim 1, wherein the complex bacteria comprise at least two of the following: nitrifying bacteria, denitrifying bacteria and synchronous nitrifying and denitrifying bacteria.
4. The immobilized microbial agent for raw clay minerals according to claim 2, wherein the effective components in the raw clay minerals comprise: SiO 22、Al2O3、TiO2、CaO、Na2O、K2O、MnO、ZnO、CuO、FeS2、Fe2O3。
5. A preparation method of a clay mineral raw ore immobilized microbial agent is characterized by comprising the following steps:
dispersing raw clay mineral ores in deionized water, and obtaining raw clay mineral ore immobilized carriers through stirring, centrifuging, washing, standing, drying and crushing;
placing the compound bacteria in an incubator for preheating and activation, then adding a culture solution for culturing, centrifugally collecting wet bacteria, adding physiological saline, and uniformly mixing to obtain a bacterial suspension;
mixing the clay mineral raw ore immobilized carrier with the bacterial suspension, adding physiological saline and a culture solution for culturing, then washing with the physiological saline, and naturally drying to obtain the clay mineral raw ore immobilized microbial agent;
the culture solution contains the following components in parts by weight: 0.5-5 parts of normal saline, 0.1-2 parts of ammonium sulfate, 1-10 parts of potassium nitrate, 2-10 parts of sodium citrate, 1-10 parts of phosphate and 0.1-2 parts of magnesium sulfate.
6. The method for preparing the immobilized microbial agent for raw clay mineral according to claim 5, wherein the preheating temperature for preheating activation is 30-37 ℃ and the preheating time is 10-35 min.
7. The application of the clay mineral raw ore immobilized microbial agent to wastewater treatment according to any one of claims 1 to 4, wherein the clay mineral raw ore immobilized microbial agent is added into wastewater containing ammonia nitrogen, and the reaction is carried out under stirring.
8. The application of the clay mineral raw ore immobilized microbial agent in wastewater treatment according to claim 7, wherein the adding amount of the clay mineral raw ore immobilized microbial agent in wastewater is 1-10 g/L; the stirring time is 1-16 h, and the reaction temperature is 15-45 ℃.
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