CN107434305B - Water purifying agent with defect-rich carbon carrier immobilized microorganisms and preparation method thereof - Google Patents

Water purifying agent with defect-rich carbon carrier immobilized microorganisms and preparation method thereof Download PDF

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CN107434305B
CN107434305B CN201710910358.1A CN201710910358A CN107434305B CN 107434305 B CN107434305 B CN 107434305B CN 201710910358 A CN201710910358 A CN 201710910358A CN 107434305 B CN107434305 B CN 107434305B
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carbon
defect
carbon carrier
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water purifying
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CN107434305A (en
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李洁
肖艳春
陈浩霖
黄婧
陈彪
张燕青
陈阳
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Institute of Agricultural Engineering Technology of Fujian Academy of Agricultural Sciences
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Institute of Agricultural Engineering Technology of Fujian Academy of Agricultural Sciences
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/347Use of yeasts or fungi
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F2003/001Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
    • C02F2003/003Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like

Abstract

The invention belongs to the technical field of microbial water purifying agents, and particularly relates to a water purifying agent with a defect-rich carbon carrier and immobilized microorganisms and a preparation method thereof. And (3) placing the defect-rich carbon carrier in a culture medium, simultaneously inoculating the composite strain to the culture medium, and performing shake co-culture to obtain the water purifying agent. Because the surface of the carbon carrier of the water purifying agent has oxygen-containing functional groups, the problem of hydrophobicity of a common carbon carrier is solved, and the surface of the carbon carrier is rich in defects and secondary pore structures, more active sites are provided for adsorption reaction, and the adsorption efficiency of pollutants is improved; the co-culture of the defect-rich carbon carrier containing hydrophilic groups and microorganisms is beneficial to the adsorption and fixation of the carbon carrier on the microorganisms, and simultaneously, organic matters and pollutants adsorbed on the carrier carbon are efficiently utilized and degraded by the microorganisms respectively, so that the water purifying agent has the characteristics of hydrophilicity and easiness in precipitation, double purification effects of carbon adsorption and biodegradation and the like, and is very suitable for the large-scale treatment of the aquaculture anaerobic sewage.

Description

Water purifying agent with defect-rich carbon carrier immobilized microorganisms and preparation method thereof
Description
Technical Field
The invention belongs to the technical field of microbial water purifying agents, and particularly relates to a water purifying agent with a defect-rich carbon carrier and immobilized microorganisms and a preparation method thereof.
Technical Field
In the large-scale development of animal husbandry, the cost is reduced and the economic benefit is improved by unified management, but serious environmental pollution caused by a large amount of concentrated sewage discharge is urgently needed to be treated. The domestic and foreign treatment modes of the aquaculture sewage mainly comprise two categories of resource utilization and standard discharge, which are summarized into a returning mode, a natural treatment mode and an industrial treatment 3 modes, and each mode has advantages and disadvantages. The purpose of the treatment of the breeding sewage in China is to control and reduce the harm caused by the breeding sewage, develop comprehensive utilization, finally realize the aims of reduction, reclamation, harmlessness and standard discharge, reduce the influence on the soil quality of crops and the quality of the crops, and reduce the potential pollution risk to water, soil environment and climate environment.
In recent years, researchers systematically research treatment methods and processes of aquaculture sewage according to the property characteristics of agricultural environmental pollutants, respectively utilize chemical methods and biological methods to adsorb, separate and biologically/chemically degrade nitrogen, phosphorus, heavy metal ions and organic matter molecules, and a single treatment mode achieves the aims of reduction and recycling to a certain extent, but hardly achieves complete harmlessness and national emission standards. In the research process, the activated carbon is usually used as an adsorbent for sewage pollutants, the activated carbon has improved chromaticity and turbidity of the sewage, and simultaneously has a macroporous, mesoporous and microporous structure, so that the activated carbon can also have an adsorption effect on small molecules and heavy metal ions, and can also be pressed into columnar small particles to be used as carriers of biological water purifying agents for purification treatment of the anaerobic biogas slurry for livestock and poultry breeding, and a single bacterial strain is fixed on the bacterial carbon water purifying agent formed by the carbon carriers, and the sewage purification effect of the bacterial carbon water purifying agent is often not as ideal as that of the bacterial carbon purifying agent formed by the composite bacterial strains. The patent with publication number CN 104261570A discloses a livestock and poultry breeding anaerobic sewage purifying agent, which consists of a compound microorganism strain and an activated carbon carrier, wherein the activated carbon carrier is coal columnar activated carbon, and the activated carbon carrier is solid columnar activated carbon prepared by shaping the coal activated carbon with 2-10 meshes. The coal-based activated carbon and commercially available carbon materials (activated carbon AC, carbon nanotube CNT, graphite GC and the like) have various advantages, such as high porosity, large specific surface, good stability, no toxicity, no pollution, environmental friendliness and the like; but the surface functional groups are few and do not contain hydrophilic groups (-COOH, -OH), so the purifying agent has poor dispersibility in water, prevents the purifying agent from fully contacting pollutants in sewage, hardly generates electrostatic interaction with ammonia nitrogen substances containing hydrogen bonds and lone electron pairs, and cannot fully exert the adsorption effect of carbon-based carriers on the pollutants, thereby the regulation and control of the surface hydrophilicity/hydrophobicity of the carbon material are very necessary. The method commonly used at present is to use concentrated acid (concentrated HNO)3Concentrated H2SO4) Activating the surface of inert carbon and oxidizing the surface carbon to form oxygen-containing functional groups (-COOH, -OH, -C ═ O), and simultaneously generating polluted nitrogen oxides and sulfur oxides to cause secondary pollution; and reacting alkali at the high temperature of about 600-900 ℃ with carbon in an inert gas environment to etch a secondary pore structure and a surface active site, wherein the reaction conditions of the methods are harsh, and the reaction vessel is required to be resistant to acid, alkali and high temperature, so that a plurality of defects exist in the actual operation and application processes.
Disclosure of Invention
The invention aims to provide a water purifying agent of a defect-rich carbon carrier immobilized microorganism and a preparation method thereof aiming at the defects of the prior art. The carbon carrier used is rich in hydrophilic groups, so that the purifying agent has better intermiscibility with water, the problem of hydrophobicity of a common carbon carrier is solved, the adsorption and fixation of microbial strains are facilitated, the contact property with pollutants is better, the adsorption efficiency of the pollutants is improved, and the adsorption of the pollutants is increased due to the fact that the carbon carrier is rich in secondary pore structures and surface active sites. The water purifying agent with the defect-rich carbon carrier fixing microorganism has double purifying effects of carbon adsorption and biodegradation, and realizes the cyclic utilization of organic matters and the synergistic efficient degradation of pollutants by the microorganism.
In order to achieve the purpose, the invention adopts the following technical scheme:
a water purifying agent with a defect-rich carbon carrier immobilized microorganisms comprises: placing the defect-rich carbon carrier in a Luria-Bertani culture medium, simultaneously inoculating the composite strain to the Luria-Bertani culture medium, and preparing a water purifying agent after shaking co-culture and drying; the preparation method of the defect-rich carbon carrier comprises the following steps:
(1) putting 90g of mixed alkali of NaOH and KOH into a 200mL reaction kettle inner container, and melting for 2h at 165 ℃ to obtain clear molten alkali liquor;
(2) adding glucose and urea serving as raw materials into clear molten alkali liquor to react for 12 hours to generate a defect-rich powdered carbon precursor material;
(3) washing the carbon precursor material with water and absolute ethyl alcohol in sequence, and drying at 80 ℃ for 12h to obtain a powdered carbon precursor;
(4) calcining the powdered carbon precursor in a muffle furnace at 300 ℃ for 2 hours to obtain the porous defect-rich carbon powder material (the total pore volume is about 0.05-0.06 cm)3/g);
(5) Dispersing the porous defect-rich carbon powder material in ethanol, then dripping polyethylene glycol into the dispersion liquid, fully stirring to form jelly, and then pressing and molding to prepare the carbon carrier of the microbial water purifying agent.
The formula of the Luria-Bertani culture medium is as follows: 10g of tryptone, 5g of yeast extract, 10g of NaCl, 1000mL of distilled water and pH 7.0.
The mass ratio of NaOH to KOH in the mixed alkali in the step (1) is 46.5: 43.5.
A method for preparing the water purifying agent containing the defective carbon-rich carrier immobilized microorganisms, which comprises the following steps: adding 10g of defect-rich carbon carrier into 50-150mL of Luria-Bertani culture medium, inoculating Bacillus licheniformis, Rhodopseudomonas palustris, Chlorella vulgaris, Streptococcus Streptococcus and Thiobacillus thiooxidans into the Luria-Bertani culture medium according to the mass ratio of 4:5:1:4:1, wherein the inoculation amount of the composite strain is 1-2%, carrying out shake co-culture for 48-72 h under the conditions of 4 ℃ and 150rpm, and finally fishing out the carbon carrier and placing the carbon carrier in a thermostat at 4 ℃ for drying to obtain the water purifying agent; the number of effective viable bacteria on the carbon carrier is 7 multiplied by 108~6×109CFU/g, the bacterial carbon binding rate reaches 97.8 percent.
During the co-culture process of the defect-rich carbon carrier and microorganisms, hydrophilic gram-negative bacteria (thiobacillus thiooxidans/rhodopseudomonas palustris) are electropositive because the cell surface components are mainly lipopolysaccharides and can be adsorbed and fixed on the carbon carrier with negative charge groups through electrostatic interaction; the cell wall of gram-positive bacteria (chlorella/bacillus/streptococcus) consists of 5 layers of thick and compact glycine cross-linked peptidoglycan and teichoic acid, the surface electronegativity enables the gram-positive bacteria to present hydrophobicity, the hydrophobicity can be utilized to diffuse in nutrient solution in the early culture and growth stage, various resources are obtained to meet the proliferation requirement, the hydrophobicity of microorganisms is reduced in the growth process, the microorganisms can freely float in water body without environmental stress, the survival capability is improved, the hydrophilicity of the microorganisms is further increased in the later growth stage, and the microorganisms are convenient to adsorb and fix on a hydrophilic carbon carrier with a negative electricity group, so that the carbon carrier containing the hydrophilic functional group is beneficial to the adsorption and fixation of microorganism strains.
The water purifying agent of the defected carbon-rich carrier immobilized microorganism is stored at 4 ℃, and is placed at normal temperature for 8-12 hours before use to recover the biological activity and then is applied to the aspect of treating the culture anaerobic sewage.
The species used in the above raw materials may be those which are conveniently isolated from nature by conventional species identification and isolation methods by those skilled in the art, or those which are publicly available through commercial channels. The strain adopted by the invention can be purchased from suppliers such as Chinese microbial strain net-Beijing Beinanna Biotechnology research institute and the like.
The above strains are cultured according to the conventional method:
i culture medium of Bacillus licheniformis: tryptone 5g, yeast extract 15g, K2HPO43g, 2g of glucose, 1000mL of distilled water and pH 7.5;
II culture medium of rhodopseudomonas palustris: NH (NH)4Cl 1.0g,K2HPO40.5g,NaHCO33.0g, 2.0g of yeast extract, 1000mL of distilled water and pH 7.2;
III common culture solution formula of chlorella: NH (NH)4NO350-100 mg,K2HPO45 mg,FeC6H5O70.1-0.5mg, 1000mL of seawater;
culture medium of streptococcus iv: 10.0g of beef powder, 20.g of tryptone, 2.0g of glucose and NaHCO32.0g,NaCl2.0g,Na2HPO40.4g, 1000mL of distilled water and pH value of 7.8;
culture medium of thiobacillus valoxidans: tryptone 5.0g, KH2PO41.0g,MgSO4·7H20.5g of O, 10g of glucose and 1000mL of distilled water.
The invention has the beneficial effects that:
1) the microbial water purifying agent is put into the culture anaerobic sewage, and can degrade macromolecular organic matters in the sewage by using microbes, so that most pollutants in the sewage can be removed, and the aim of purifying the sewage is fulfilled;
2) because the carbon carrier of the microbial water purifying agent adopts organic compounds as raw materials, oxygen-containing functional groups (-OH, -COOH and the like) on the surface of the prepared carbon carrier are rich, and the charged groups and hydrogen protons/hydroxide ions in water generate electrostatic interaction, so that the carbon carrier has better intermiscibility with water, the problem of hydrophobicity of common carbon carriers is solved, and the carbon carrier has better contact with pollutants; meanwhile, charged groups on the surface of the carbon carrier can generate electrostatic interaction with lone pair electrons of nitrogen, phosphorus and sulfur, so that the adsorption efficiency of pollutants is improved; secondly, the purity and porosity of the carbon powder are improved in the calcination process at 300 ℃, and the molten solid alkali environment enables the carbon material to obtain surface defects and secondary pore structures, so that more active sites are provided for adsorption reaction, and the adsorption of pollutants is increased;
3) the effective viable count of the carbon carrier of the water purifying agent prepared by co-culturing the hydrophilic carbon carrier and microorganisms is 7 multiplied by 108~6×109CFU/g, the binding rate of bacteria and carbon reaches 97.8%, and the adsorption and fixation efficiency of the carbon carrier to microorganisms is improved;
4) the microorganism-immobilized water purifying agent with the carbon-rich carrier has the advantages that the microorganisms planted on the activated carbon efficiently degrade organic matters and the like adsorbed on the carbon as nutrient substances, so that the water quality is purified, the products of metabolism of the microorganism-immobilized water purifying agent can be used as nutrient substrates which are mutually utilized, the activity of the microorganism is improved, and the microbial flora is promoted to synergistically degrade pollutants, so that the water purifying agent has the double purification effects of carbon adsorption and biodegradation, is hydrophilic but easy to precipitate, has a stable purification effect, is easy to treat and the like, and is very suitable for large-scale treatment of aquaculture anaerobic sewage.
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
A preparation method of a water purifying agent with a defect-rich carbon carrier immobilized microorganisms comprises the following specific steps:
1. preparation of carbon carrier with hydrophilic functional group and defect on surface
1) Putting 90g of NaOH and KOH (NaOH: KOH: 46.5:43.5, mass ratio) into a 200mL inner container of a reaction kettle, and melting at 165 ℃ for 2h to obtain clear molten alkali liquor;
2) adding glucose and urea serving as raw materials into clear molten alkali liquor to react for 12 hours to generate a defect-rich powdered carbon precursor material A;
3) washing the carbon precursor A with water until the pH value of washing liquor is about 7, removing water-soluble impurities, and then carrying out centrifugal separation to obtain a lower-layer precipitate; washing the lower-layer precipitate with absolute ethyl alcohol to remove organic impurities insoluble in water, and finally drying the centrifuged precipitate at 80 ℃ overnight to obtain a defect-rich powdered carbon precursor sample A;
4) placing the carbon precursor sample A in a muffle furnace at 300 ℃ to calcine for 2h to obtain porous defect-rich carbon powder B (the total pore volume is about 0.05-0.06 cm)3/g);
5) Placing 0.5-1.0 g of porous defect-rich carbon powder B into an agate mortar, adding 2-4mL of ethanol, stirring for 30 minutes to uniformly disperse the carbon powder in the ethanol, adding 1-2mL of polyethylene glycol (PEG400), fully stirring to form powder carbon into a jelly, placing the jelly into a tabletting groove (cylindrical or tablet) of a tabletting machine or a pressure-resistant die, drying for 24 hours in an environment of 80 ℃, and finally pressing and molding under the pressure of 10-15MPa to prepare the carbon carrier of the microbial water purifying agent.
2. Adding 10g of defect-rich carbon carrier into 50-150mL of Luria-Bertani culture medium, inoculating Bacillus licheniformis, rhodopseudomonas palustris, Chlorella vulgaris, Streptococcus and Thiobacillus thiooxidans into the Luria-Bertani culture medium according to the mass ratio of 4:5:1:4:1, wherein the inoculation amount of the composite strain is 1-2%, carrying out shake co-culture for 48-72 h under the conditions of 4 ℃ and 150rpm, and finally fishing out the carbon carrier and placing the carbon carrier in a thermostat at 4 ℃ for drying to obtain the water purifying agent; the number of effective viable bacteria on the carbon carrier is 7 multiplied by 108~6×109CFU/g, the bacterial carbon binding rate reaches 97.8%; the water purifying agent stored at 4 deg.C is stored at room temperature for 8-12 deg.C before useThe biological activity is recovered in hours, and the sewage can be directly put into sewage.
Example 1
A preparation method of a water purifying agent with a defect-rich carbon carrier immobilized microorganisms comprises the following specific steps:
(1) preparation of carbon carrier with hydrophilic functional group and defect on surface
1) Putting 90g of NaOH and KOH (NaOH: KOH: 46.5:43.5, mass ratio) into a 200mL inner container of a reaction kettle, and melting at 165 ℃ for 2h to obtain clear molten alkali liquor;
2) adding glucose and urea serving as raw materials into clear molten alkali liquor to react for 12 hours to generate a defect-rich powdered carbon precursor material A;
3) washing the carbon precursor A with water until the pH value of washing liquor is about 7, removing water-soluble impurities, and then carrying out centrifugal separation to obtain a lower-layer precipitate; washing the lower-layer precipitate with absolute ethyl alcohol to remove organic impurities insoluble in water, and finally drying the centrifuged precipitate at 80 ℃ overnight to obtain a defect-rich powdered carbon precursor sample A;
4) placing the carbon precursor A in a muffle furnace at 300 ℃ to calcine for 2h to obtain a porous defect-rich carbon powder material B;
5) placing 0.8 g of porous defect carbon powder B in an agate mortar, adding 3mL of ethanol, stirring for 30 minutes to uniformly disperse the carbon powder in the ethanol, adding 1.6mL of polyethylene glycol (PEG400), fully stirring to form jelly, placing the jelly into a tabletting groove (cylindrical or tablet) of a tabletting machine or a pressure-resistant die, drying for 24 hours in an environment of 80 ℃, and finally pressing and molding under the pressure of 15MPa to prepare the carbon carrier of the microbial water purifying agent.
(2) Adding 10g of defect-rich carbon carrier into 150mL of Luria-Bertani culture medium, inoculating Bacillus licheniformis, rhodopseudomonas palustris, Chlorella vulgaris, Streptococcus and Thiobacillus thiooxidans into the Luria-Bertani culture medium according to the mass ratio of 4:5:1:4:1, inoculating the composite strain in an amount of 1%, carrying out shake co-culture for 72h under the conditions of 4 ℃ and 150rpm, taking out the carbon carrier, placing the carbon carrier in a constant temperature box at 4 ℃ and drying to obtain the water purifying agent(ii) a The number of effective viable bacteria on the carbon carrier is 6 multiplied by 109CFU/g, the bacterial carbon binding rate reaches 97.8%; the water purifying agent stored at 4 ℃ is placed at normal temperature for 10 hours before use to recover the biological activity, and then the water purifying agent can be directly put into sewage.
Example 2
A preparation method of a water purifying agent with a defect-rich carbon carrier immobilized microorganisms comprises the following specific steps:
(1) preparation of carbon carrier with hydrophilic functional group and defect on surface
1) Putting 90g of NaOH and KOH (NaOH: KOH: 46.5:43.5, mass ratio) into a 200mL inner container of a reaction kettle, and melting at 180 ℃ for 2h to obtain clear molten alkali liquor;
2) adding glucose and urea serving as raw materials into clear molten alkali liquor to react for 10 hours to generate a defect-rich powdered carbon precursor material A;
3) washing the carbon precursor A with water until the pH value of washing liquor is about 7, removing water-soluble impurities, and then carrying out centrifugal separation to obtain a lower-layer precipitate; washing the lower-layer precipitate with absolute ethyl alcohol to remove organic impurities insoluble in water, and finally drying the centrifuged precipitate at 80 ℃ overnight to obtain a defect-rich powdered carbon precursor sample A;
4) placing the carbon precursor A in a muffle furnace at 300 ℃ to calcine for 2h to obtain a porous defect-rich carbon powder material B;
5) placing 0.5g of porous defect carbon powder B in an agate mortar, adding 2mL of ethanol, stirring for 30 minutes to uniformly disperse the carbon powder in the ethanol, adding 1.0mL of dropwise polyethylene glycol (PEG400), fully stirring to form jelly, placing the jelly into a tabletting groove (cylindrical or tablet) of a tabletting machine or a pressure-resistant die, drying for 24 hours in an environment of 80 ℃, and finally pressing and molding under the pressure of 10MPa to prepare the carbon carrier of the microbial water purifying agent.
(2) Adding 10g of the defect-rich carbon carrier into 100mL of Luria-Bertani culture medium, and inoculating Bacillus licheniformis, Rhodopseudomonas palustris, Rhodopseudomonas rhodochrans pallusis, Chlorella vulgaris, Streptococcus Streptococci, Thiobacillus thiooxidans and Thiobacillus thiooxidans into the Luria-Bertani culture medium according to the mass ratio of 4:5:1:4:1Wherein the inoculation amount of the composite strain is 2%, the composite strain is subjected to shaking co-culture for 60 hours at the temperature of 4 ℃ and at the speed of 150rpm, and finally the carbon carrier is fished out and placed in a constant temperature box at the temperature of 4 ℃ for drying to obtain the water purifying agent; the number of effective viable bacteria on the carbon carrier is 1 × 109CFU/g, the bacterial carbon binding rate reaches 97.4%; the water purifying agent stored at 4 ℃ is placed at normal temperature for 10 hours before use to recover the biological activity, and then the water purifying agent can be directly put into sewage.
Example 3
A preparation method of a water purifying agent with a defect-rich carbon carrier immobilized microorganisms comprises the following specific steps:
(1) preparation of carbon carrier with hydrophilic functional group and defect on surface
1) Putting 90g of NaOH and KOH (NaOH: KOH: 46.5:43.5, mass ratio) into a 200mL inner container of a reaction kettle, and melting at 200 ℃ for 2h to obtain clear molten alkali liquor;
2) adding glucose and urea serving as raw materials into clear molten alkali liquor to react for 8 hours to generate a defect-rich powdered carbon precursor material A;
3) washing the carbon precursor A with water until the pH value of washing liquor is about 7, removing water-soluble impurities, and then carrying out centrifugal separation to obtain a lower-layer precipitate; washing the lower-layer precipitate with absolute ethyl alcohol to remove organic impurities insoluble in water, and finally drying the centrifuged precipitate at 80 ℃ overnight to obtain a defect-rich powdered carbon precursor sample A;
4) placing the carbon precursor A in a muffle furnace at 300 ℃ to calcine for 2h to obtain a porous defect-rich carbon material B;
5) placing 1.0 g of porous defect carbon powder B in an agate mortar, adding 4mL of ethanol, stirring for 30 minutes to uniformly disperse the carbon powder in the ethanol, adding 2mL of polyethylene glycol (PEG400), fully stirring to form jelly, placing the jelly into a tabletting groove (cylindrical or tablet) of a tabletting machine or a pressure-resistant die, placing the jelly in an environment of 80 ℃ for drying for 24 hours, and finally, performing compression molding under the pressure of 15MPa to prepare the carbon carrier of the microbial water purifying agent.
(2) Adding 10g of the carbon-rich vector to 50mL of Luria-Bertani medium, and adding Bacillus licheniformis, Rhodopseudomonas palustris, Rhodopseudomonas aeruginosa, pelletsInoculating algae Chlorella vulgaris, Streptococcus Streptococci and Thiobacillus thiooxidans into a Luria-Bertani culture medium according to the mass ratio of 4:5:1:4:1, wherein the inoculation amount of the composite strain is 1%, carrying out shake co-culture for 48h at 4 ℃ and 150rpm, taking out the carbon carrier, and placing in a thermostat at 4 ℃ for drying to obtain the water purifying agent; the number of effective viable bacteria on the carbon carrier is 7 multiplied by 108CFU/g, the bacterial carbon binding rate reaches 97.1%; the water purifying agent stored at 4 ℃ is placed at normal temperature for 10 hours before use to recover the biological activity, and then the water purifying agent can be directly put into sewage.
Comparative example 1
Substantially the same as in examples 1 to 3, a water purifying agent of a defective-carbon-rich carrier-immobilized microorganism was prepared, except that the carbon carrier prepared in the first three steps (1) was different, and in comparative example 1, a commercially available column-type activated carbon carrier (specific surface area about 1100 m)2Per g, pore volume of 0.75cm3/g)。
And (3) performance testing:
firstly, putting activated carbon carriers with different shapes into the culture anaerobic sewage, and comparing the adsorption effect. Respectively weighing 100g of activated carbon carriers (i.e. granular coal activated carbon A, spherical coal activated carbon B, cylindrical coal activated carbon C and defect-rich columnar carbon D) in various shapes, adding into 10L of aquaculture anaerobic sewage, and measuring CODcr and BOD of the aquaculture anaerobic sewage after 3.5 days by using untreated aquaculture anaerobic sewage as reference5And calculating the adsorption rate of the activated carbon to each index in the culture anaerobic sewage according to the technical indexes of ammonia nitrogen, total phosphorus and the like.
The results are shown in Table 1-1. The experimental results show that the cylindrical coal activated carbon in the three components has better adsorption capacity on the culture anaerobic sewage, and COD and BOD of the coal activated carbon5The adsorption rates of ammonia nitrogen, total phosphorus and the like are higher than those of the former two; the adsorption effect of the defect-rich columnar carbon in the patent is superior to A, B, C, and COD and BOD5The adsorption rates of ammonia nitrogen and total phosphorus are obviously improved, the adsorption of pollutants is promoted by the cooperation of oxygen-containing functional groups on the surface and surface defects, and the decontamination effect is superior to that of the active carbon with different shapes sold in the market.
TABLE 1-1 carbon carriers of different shapes have effect on treatment of anaerobic culture sewage
Secondly, five culture anaerobic sewage tanks (10L) with the same size and water quality are taken for testing, and the microbial water purifying agent in the embodiment 1 is put in the first tank; secondly, the microbial water purifying agent of the embodiment 2 is added; thirdly, the microbial water purifying agent of the embodiment 3 is added; fourthly, the bacterial carbon water purifying agent of the comparative example 1 is added; the fifth, without any water purifying agent, served as a blank control group.
100g of water purifying agent is respectively put into the culture anaerobic sewage tanks, and after 3.5 days, the water quality of all the culture anaerobic sewage tanks is measured. The basis of the water quality measurement is GB11607-89 national standard fishery water quality of the people's republic of China and NY5051-2001 pollution-free food freshwater aquaculture water quality, and the measurement indexes and data are shown in the following tables 1-2 and tables 1-3.
TABLE 1-23.5 days later, the effect of different bacteria carbon purifiers on the index concentration of sewage
TABLE 1-33.5 days later, the effect of carbon purifiers of different bacteria on removing pollutants
As can be seen from the data in the table, the water quality indexes of the examples 1 to 3 are all superior to those of the comparative example 1, and are more obviously superior to those of the control group.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be made by those skilled in the art without inventive work within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.

Claims (3)

1. A water purifying agent with a defect-rich carbon carrier immobilized microorganisms is characterized in that: placing the defect-rich carbon carrier in a Luria-Bertani culture medium, simultaneously inoculating the composite strain to the Luria-Bertani culture medium, and preparing a water purifying agent after shaking co-culture and drying; the preparation method of the defect-rich carbon carrier comprises the following steps:
(1) putting 90g of mixed alkali of NaOH and KOH into a 200mL reaction kettle inner container, and melting for 2h at 165 ℃ to obtain clear molten alkali liquor; the mass ratio of NaOH to KOH in the mixed alkali is 46.5: 43.5;
(2) adding glucose and urea serving as raw materials into clear molten alkali liquor to react for 12 hours to generate a defect-rich powdered carbon precursor material;
(3) washing the carbon precursor material with water and absolute ethyl alcohol in sequence, and drying at 80 ℃ for 12h to obtain a powdered carbon precursor;
(4) calcining the powdered carbon precursor in a muffle furnace at 300 ℃ for 2 hours to obtain a product with a total pore volume of 0.05-0.06 cm3A porous defect-rich carbon powder material per gram;
(5) dispersing the porous defect-rich carbon powder material in ethanol, then dripping polyethylene glycol into the dispersion liquid, fully stirring to form jelly, and performing compression molding to obtain a defect-rich carbon carrier;
adding 10g of defect-rich carbon carrier into 50-150mL of Luria-Bertani culture medium, inoculating Bacillus licheniformis, Rhodopseudomonas palustris, Rhodopseudomonas aeruginosa palustris, Chlorella vulgaris, Streptococcus Streptococcus, Thiobacillus thiooxidans and Thiobacillus thiooxidans into the Luria-Bertani culture medium according to the mass ratio of 4:5:1:4:1, wherein the inoculation amount of the composite strain is 1-2%, performing shake culture at 4 ℃ and 150rpm for 48-72 h, and finally fishing out the carbon carrier and placing the carbon carrier in a constant temperature box at 4 ℃ for drying to obtain the water purifying agent; the number of effective viable bacteria on the carbon carrier is 7 multiplied by 108~6×109CFU/g。
2. The water purifying agent with microorganism immobilized on carbon-rich carrier of claim 1, which is characterized in that: the formula of the Luria-Bertani culture medium is as follows: 10g of tryptone, 5g of yeast extract, 10g of NaCl, 1000mL of distilled water and pH 7.0.
3. Use of the water purifying agent of claim 1 for treating aquaculture anaerobic wastewater.
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CN109897869B (en) * 2018-08-28 2022-06-17 福建省农业科学院农业工程技术研究所 Biological activated carbon cultured by high-sugar wastewater and using ficus microcarpa leaves as carbon source carrier
CN109894076B (en) * 2018-08-28 2021-12-17 福建省农业科学院农业工程技术研究所 Porous defect-rich carbon ferrite for adsorbing light-degraded organic matters in aquaculture wastewater and preparation method thereof
CN109896703B (en) * 2018-08-28 2021-10-26 福建省农业科学院农业工程技术研究所 Light-enzyme composite catalytic function microorganism water purifying agent for culturing anaerobic sewage
CN109894132B (en) * 2018-08-28 2021-12-21 福建省农业科学院农业工程技术研究所 Method for preparing carbon-doped titanium oxide visible-light-driven photocatalyst by using waste as carbon source
CN109896574B (en) * 2018-09-30 2021-10-22 福建省农业科学院农业工程技术研究所 Carbon ferrite-titanium oxide multifunctional water purification material and preparation method thereof

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