CN113998787A - Microbial composite material and preparation method and application thereof - Google Patents

Microbial composite material and preparation method and application thereof Download PDF

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Publication number
CN113998787A
CN113998787A CN202010740710.3A CN202010740710A CN113998787A CN 113998787 A CN113998787 A CN 113998787A CN 202010740710 A CN202010740710 A CN 202010740710A CN 113998787 A CN113998787 A CN 113998787A
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photosynthetic bacteria
porous inorganic
inorganic carrier
heavy metal
composite material
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宋秋芳
李捍东
杨峥
范蕾
贺凤
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Songshan Lake Materials Laboratory
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Songshan Lake Materials Laboratory
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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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
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    • C02F2101/20Heavy metals or heavy metal compounds

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Abstract

The embodiment of the application provides a microbial composite material and a preparation method and application thereof, belonging to the technical field of environment application materials. The preparation method of the microbial composite material comprises the following steps: pretreatment of the porous inorganic carrier: the porous inorganic carrier is soaked in an acid solution, washed to be neutral, soaked in an alkali solution, and sterilized after being washed to be neutral. Preparing a microbial composite material: placing the pretreated porous inorganic carrier in the photosynthetic bacteria fermentation liquor in logarithmic phase, and carrying out illumination culture under the anoxic condition to load the photosynthetic bacteria on the porous inorganic carrier. The method can load more photosynthetic bacteria on the porous inorganic carrier so as to achieve better effect of adsorbing heavy metals.

Description

Microbial composite material and preparation method and application thereof
Technical Field
The application relates to the technical field of environment application materials, in particular to a microbial composite material and a preparation method and application thereof.
Background
In the prior art, a treatment method for heavy metals comprises the following steps: electrolytic processes (treatment of heavy metal wastewater containing cyanogen), float process (heavy metal hydroxides and sulfides in wastewater can be removed by air-blowing float process, wherein the float process is most effective by pressurized dissolved air), ion flotation process (adding anionic surfactant such as sodium xanthate, sodium dodecylbenzenesulfonate, gelatin, etc. to heavy metal wastewater to form complex or chelate having surface activity with heavy metal ions therein), ion exchange and adsorption (heavy metal in wastewater, if present in cationic form, is treated with cation exchange resin or other cation exchanger; if present in anionic form, is treated with anion exchange resin), and membrane processes (mainly electrodialysis and reverse osmosis).
Disclosure of Invention
The application aims to provide a microbial composite material, a preparation method and application thereof, and provides a novel microbial composite material for treating heavy metal wastewater, so that the heavy metal wastewater is treated by the adsorption of the microbial composite material.
In a first aspect, the application provides an application of a microbial composite material in adsorption of heavy metal ions in wastewater. The microbial composite material is formed by loading photosynthetic bacteria on a porous inorganic material.
In the prior art, microorganisms are generally used for treating organic wastewater because microorganisms cannot normally grow and reproduce in heavy metal wastewater (oligotrophic), and in the prior art, microorganisms are not used for treating heavy metal wastewater.
In the present application, the photosynthetic bacteria are autotrophic microorganisms which are rod-shaped, heterotrophic in light energy, gram-negative, and capable of growing in oligotrophic environments, and therefore, the inventors have carried the photosynthetic bacteria on a porous inorganic carrier according to the characteristics of the photosynthetic bacteria, and then adsorbed heavy metal ions in wastewater by a microbial adsorption method.
In one possible embodiment, the heavy metal ion is zinc ion or copper ion, and the concentration of the heavy metal ion is 80-150 mg/L.
The concentration of heavy metal ions in the wastewater is lower, on one hand, the microbial composite material has better adsorption effect on the wastewater, and the adsorption rate can reach more than 90%; on the other hand, the heavy metal ions do not influence the activity of the photosynthetic bacteria, so that the photosynthetic bacteria can continuously adsorb the heavy metal ions.
In one possible embodiment, the method for adsorbing heavy metal ions in wastewater comprises: and (3) placing the microbial composite material in a solution containing heavy metal ions for anoxic adsorption. Wherein the solid-to-liquid ratio of the microbial composite material to the solution is 30-50mg/mL, the adsorption temperature is 29-30 ℃, and the adsorption is carried out for 20-30h under the condition of oscillation.
Compared with a physical adsorption method, the microbial adsorption method has the advantages that the adsorption time is longer, the photosynthetic bacteria can adsorb heavy metal ions under the long-term action in the wastewater, and the adsorption effect on the heavy metal ions is better.
In a second aspect, the present application provides a method for preparing a microbial composite, comprising the steps of: pretreatment of the porous inorganic carrier: the porous inorganic carrier is soaked in an acid solution, washed to be neutral, soaked in an alkali solution, and sterilized after being washed to be neutral. Preparing a microbial composite material: placing the pretreated porous inorganic carrier in the photosynthetic bacteria fermentation liquor in logarithmic phase, and carrying out illumination culture under the anoxic condition to load the photosynthetic bacteria on the porous inorganic carrier.
The porous inorganic carrier is soaked by acid and alkali, so that on one hand, the porous inorganic carrier can be cleaned, and the subsequent load of photosynthetic bacteria is facilitated; on the other hand, the pore structure of the porous inorganic carrier can be adjusted, and the specific surface area of the porous inorganic carrier is increased, so that more photosynthetic bacteria can be loaded. The photosynthetic bacteria fermentation liquor in the logarithmic phase and the pretreated porous inorganic carrier are mixed for illumination culture, on one hand, the photosynthetic bacteria fermentation liquor is in the logarithmic phase, the proliferation speed of the photosynthetic bacteria is high, and the photosynthetic bacteria are easier to load on the porous inorganic carrier in the proliferation process, and on the other hand, after the photosynthetic bacteria are loaded, the photosynthetic bacteria and the porous inorganic carrier have a certain synergistic effect and can have a better adsorption effect on heavy metal ions.
In one possible embodiment, the porous inorganic support has a particle size of 4 to 10 mm. The porous inorganic carrier is of a particle structure, so that on one hand, the photosynthetic bacteria in the logarithmic phase are loaded on the granular porous inorganic carrier in the proliferation process, and the effective adsorption of heavy metal ions is facilitated; on the other hand, the microbial composite material is beneficial to recycling after adsorbing heavy metal ions, and secondary pollution is avoided.
In one possible embodiment, the porous inorganic support is a natural zeolite having a particle size of 6 to 9 mm. Is beneficial to the load of photosynthetic bacteria and the adsorption of heavy metal ions.
In one possible embodiment, the porous inorganic carrier is volcanic ceramsite, and the particle size of the volcanic ceramsite is 4-6 mm. Is beneficial to the load of photosynthetic bacteria and the adsorption of heavy metal ions.
In one possible embodiment, the photosynthetic bacteria fermentation broth has a bacteria content of 10 × 108-20×108The solid-liquid ratio of the porous inorganic carrier to the photosynthetic bacteria fermentation liquid is 0.05-0.1 g/mL. More photosynthetic bacteria can be loaded on the porous inorganic carrier so as to adsorb heavy metal ions in the subsequent process.
In one possible embodiment, the incubation time is 20-30h, the illumination is 1000-3000lx, and the incubation temperature is 29-30 ℃.
The photosynthetic bacteria can be more uniformly loaded on the porous inorganic carrier, more photosynthetic bacteria can be loaded, and the proliferation of the photosynthetic bacteria is facilitated.
In one possible embodiment, the light culture is performed in a light shaking table, the membrane culture is performed under water flow, and the rotation speed of the shaking table is 120-.
Cultivate in illumination shaking table, cultivate comparatively simply, and carry out the mode that the biofilm culturing was cultivateed under rivers, can make the load between photosynthetic bacteria and the porous inorganic carrier more firm, when adsorbing heavy metal ion, photosynthetic bacteria is difficult for following the carrier and drops, is favorable to adsorbing the in-process of heavy metal ion, photosynthetic bacteria and carrier's cooperation in coordination, and subsequent adsorption effect is better.
In one possible embodiment, the strain of photosynthetic bacteria is inoculated into the first liquid culture medium and cultured under the conditions of oxygen deficiency, illumination intensity of 1000-. Inoculating the seed culture solution according to the inoculation amount of 5-15% by mass, culturing in a second liquid culture medium for 3-4 days under the conditions of oxygen deficiency, illumination intensity of 1000-3000lx and temperature of 29-30 ℃ to obtain the photosynthetic bacteria fermentation broth in logarithmic phase.
The mother liquor of the photosynthetic bacteria has lower activity, the photosynthetic bacteria are activated by the first culture, the seed liquor with high activity can be obtained, and the seed liquor is enlarged and cultured for the second time, so that more photosynthetic bacteria fermentation liquor is obtained, and the photosynthetic bacteria fermentation liquor is favorably loaded on a porous inorganic carrier subsequently.
In one possible embodiment, the first liquid culture medium and the second liquid culture medium are each prepared by a method comprising: mixing 0.8-1.2g/L ammonium chloride, 0.8-1.2g/L sodium bicarbonate, 2.5-3.5g/L sodium acetate, 1.5-2.5g/L sodium chloride, 0.1-0.3g/L dipotassium hydrogen phosphate, 0.1-0.3g/L magnesium sulfate heptahydrate, 0.05-0.15g/L yeast extract, 8-12mL growth factor and 8-12mL microelement solution, adjusting pH value to 6.8-7.2, and sterilizing. Is favorable for the division and proliferation of photosynthetic bacteria.
In a third aspect, the present application provides a microbial composite, prepared as described above. Is favorable for adsorbing heavy metal ions and can treat the wastewater polluted by the heavy metal.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments are briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive efforts and also belong to the protection scope of the present application.
FIG. 1 is a flow chart of a method for preparing a microbial composite provided herein;
FIG. 2 is a microscope photograph of the fermentation broth of photosynthetic bacteria provided in step (1) of example 1 of the present application;
FIG. 3 is a microscope photograph of natural clinoptilolite provided in step (2) of example 1 of the present application;
FIG. 4 is a microscope photograph of the microbial composite provided in step (3) of example 1 of the present application;
FIG. 5 is a microscope photograph of natural clinoptilolite provided in step (2) of example 4 of the present application;
FIG. 6 is a microscope photograph of the microbial composite provided in step (3) of example 4 of the present application.
Detailed Description
In the prior art, microorganisms generally treat organic pollutants for the following reasons: most microorganisms are heterotrophic, and organic pollutants can provide abundant nutrition for the microorganisms, so that the microorganisms can normally reproduce, and the organic pollutants are treated. However, the nutrition of heavy metal wastewater is generally deficient, so microorganisms are not generally used for treating heavy metal wastewater in the prior art.
The inventor researches and discovers that the photosynthetic bacteria are autotrophic microorganisms which are rod-shaped, heterotrophic in light energy and gram-negative and can grow in an oligotrophic environment, so the inventor uses the photosynthetic bacteria to treat the heavy metal wastewater and provides a novel material and a novel method for treating the heavy metal wastewater.
The application provides a microbial composite material, which is prepared by loading photosynthetic bacteria on a porous inorganic carrier so as to adsorb heavy metal ions in wastewater by a microbial adsorption method.
Optionally, the heavy metal ions are zinc ions or copper ions, and the concentration of the heavy metal ions in the wastewater is 80-150 mg/L. The concentration of heavy metal ions in the wastewater is lower, on one hand, the microbial composite material has better adsorption effect on the wastewater, and the adsorption rate can reach more than 90%; on the other hand, the heavy metal ions have little influence on the activity of the photosynthetic bacteria, so that the photosynthetic bacteria can continuously adsorb the heavy metal ions.
Further, the method for adsorbing heavy metal ions comprises the following steps: and (3) placing the microbial composite material in a solution containing heavy metal ions for anoxic adsorption. Wherein the solid-to-liquid ratio of the microbial composite material to the solution is 30-50mg/mL, the adsorption temperature is 29-30 ℃, and the adsorption is carried out for 20-30h under the condition of oscillation.
Compared with a physical adsorption method, the microbial adsorption method has the advantages that the adsorption time is longer, the photosynthetic bacteria can adsorb heavy metal ions under the long-term action in the wastewater, and the adsorption effect on the heavy metal ions is better.
Optionally, the adsorption is performed in a shaking table, and the oscillation frequency of the shaking table is 120-.
Fig. 1 is a flow chart of a method for preparing a microbial composite material provided by the present application. Referring to fig. 1, the preparation method of the microbial composite material includes the following steps:
s10, preparing photosynthetic bacteria fermentation liquor:
inoculating the strain of the photosynthetic bacteria into a first liquid culture medium, and culturing for 2-3 days under the conditions of oxygen deficiency, illumination intensity of 1000-. Inoculating the seed culture solution according to the inoculum size of 5-15% by mass, culturing in a second liquid culture medium under the conditions of oxygen deficiency, illumination intensity of 1000-8-20×108one/mL photosynthetic bacteria fermentation broth. The photosynthetic bacteria fermentation liquor is photosynthetic bacteria fermentation liquor in logarithmic phase, and the subsequent division and proliferation are faster.
Activating strains in the first 1-3 days to obtain a seed culture solution with higher activity, then re-inoculating after culturing for 2-3 days, and re-inoculating the seed culture solution into the culture solution by using the first culture solution as the seed culture solution, so that the two cultures are performed, and the culture periods are 2-3 days and 3-4 days respectively. The OD600 of the photosynthetic bacteria at different culture times is measured to determine whether the photosynthetic bacteria are in logarithmic phase, the slope is the maximum at the time of about 40-60h of culture, the OD600 reading of the photosynthetic bacteria is between 0.8-1.0, and the OD600 value of the photosynthetic bacteria in stationary phase is about 1.2 after 96h of culture.
The preparation method of the first liquid culture medium and the second liquid culture medium comprises the following steps: mixing 0.8-1.2g/L ammonium chloride, 0.8-1.2g/L sodium bicarbonate, 2.5-3.5g/L sodium acetate, 1.5-2.5g/L sodium chloride, 0.1-0.3g/L dipotassium hydrogen phosphate, 0.1-0.3g/L magnesium sulfate heptahydrate, 0.05-0.15g/L yeast extract, 8-12mL growth factor and 8-12mL microelement solution, adjusting pH value to 6.8-7.2, and sterilizing. Is favorable for the division and proliferation of photosynthetic bacteria.
For example: the first liquid culture medium and the second liquid culture medium are prepared as follows: mixing 1g/L ammonium chloride, 1g/L sodium bicarbonate, 3g/L sodium acetate, 2g/L sodium chloride, 0.2g/L dipotassium hydrogen phosphate, 0.2g/L magnesium sulfate heptahydrate, 0.1g/L yeast extract, 10mL growth factor and 10mL microelement solution, adjusting pH to 7, sterilizing in a steam sterilizing pot under 0.1MPa at 115 deg.C for 20 min.
S20, pretreatment of the porous inorganic carrier: the porous inorganic carrier is soaked in an acid solution, washed to be neutral, soaked in an alkali solution, and sterilized after being washed to be neutral.
The porous inorganic carrier is soaked by acid and alkali, so that on one hand, the porous inorganic carrier can be cleaned, and the subsequent load of photosynthetic bacteria is facilitated; on the other hand, the pore structure of the porous inorganic carrier can be adjusted, and the specific surface area of the porous inorganic carrier is increased, so that more photosynthetic bacteria can be loaded. And the washing between the acid treatment and the alkali treatment is neutral, so that the influence of stronger acid-alkali neutralization reaction on the load of the subsequent photosynthetic bacteria is avoided.
The particle size of the porous inorganic carrier is 4-10 mm. The porous inorganic carrier is of a particle structure, on one hand, the photosynthetic bacteria in the logarithmic phase are loaded on the granular porous inorganic carrier in the proliferation process and then are beneficial to effectively adsorbing heavy metal ions (for the photosynthetic bacteria loaded on the granular porous inorganic carrier, an adsorption method is adopted, and if the photosynthetic bacteria are loaded on the powdery porous inorganic carrier, an embedding method is adopted, and the embedding method is not beneficial to the adsorption of the heavy metal ions); on the other hand, the microbial composite material is beneficial to recycling after adsorbing heavy metal ions, and secondary pollution is avoided.
Alternatively, the acid solution and the base solution are both dilute solutions, such as: the mass concentration of the acid solution is 2-10%, the mass concentration of the alkali solution is 2-10%, and the porous inorganic carrier can be treated without damaging the whole structure.
Illustratively, the acid solution has a mass concentration of 2%, 5%, or 10%; the mass concentration of the alkali solution is 2%, 5% or 10%.
In one embodiment, the porous inorganic support is a natural zeolite having a particle size of 6-9 mm. The natural zeolite is a natural mineral material, the components of which are complex, and the natural zeolite can be subjected to chemical reaction in the processes of acid treatment and alkali treatment, so that part of components on the surface of the natural zeolite are corroded, microscopic pores are generated on the surface, and the specific surface area of the natural zeolite is increased; meanwhile, certain components in the natural zeolite are combined with hydroxyl and hydrogen ions to form charged charges, so that the load of photosynthetic bacteria is facilitated, and the adsorption of heavy metal ions is facilitated.
Further, washing natural clinoptilolite with the particle size of 6-9mm with deionized water, soaking for 2h with 5% hydrochloric acid solution, washing to neutrality, soaking for 2h with 5% sodium hydroxide solution, washing again to neutrality, sterilizing for 30min with high pressure steam, taking out, and air drying for later use.
In another embodiment, the porous inorganic carrier is volcanic ceramsite, and the particle size of the volcanic ceramsite is 4-6 mm. The volcanic ceramsite is also a mineral material, has complex components, and can react with the volcanic ceramsite in the processes of acid treatment and alkali treatment, so that part of the components on the surface of the volcanic ceramsite are corroded, microscopic pores are generated on the surface of the volcanic ceramsite, and the specific surface area of the volcanic ceramsite is increased; meanwhile, certain components in the volcanic ceramsite are combined with hydroxyl and hydrogen ions to form charged charges, so that the load of photosynthetic bacteria is facilitated, and the adsorption of heavy metal ions is facilitated.
Further, washing volcanic ceramsite with the particle size of 4-6mm with deionized water, soaking for 2h with 5% hydrochloric acid solution, washing to be neutral, soaking for 2h with 5% sodium hydroxide solution, washing again to be neutral, sterilizing for 30min with high-pressure steam, taking out, and airing for later use.
S30, preparing the microbial composite material: placing the pretreated porous inorganic carrier in the photosynthetic bacteria fermentation liquor in logarithmic phase, and carrying out illumination culture under the anoxic condition to load the photosynthetic bacteria on the porous inorganic carrier.
The microbial growth curve includes four phases: the photosynthetic bacteria fermentation liquor in the logarithmic phase and the pretreated porous inorganic carrier are mixed for illumination culture, on one hand, the photosynthetic bacteria growth rate in the logarithmic phase is fastest, the metabolism is vigorous, the enzyme system is active, the number of live bacteria and the total number of bacteria are approximately close, and the chemical composition morphology physicochemical properties of cells are basically consistent, so the photosynthetic bacteria in the logarithmic phase are more easily loaded on the porous inorganic carrier, the load of the photosynthetic bacteria is higher, the preparation time is shortened, and the preparation cost is reduced; on the other hand, after the photosynthetic bacteria are loaded, the photosynthetic bacteria and the porous inorganic carrier have a certain synergistic effect, and the adsorption effect on heavy metal ions can be better.
In the embodiment of the application, the bacteria content of the fermentation liquor of the photosynthetic bacteria is 10 multiplied by 108-20×108The solid-liquid ratio of the porous inorganic carrier to the photosynthetic bacteria fermentation liquid is 0.05-0.1 g/mL. More photosynthetic bacteria can be loaded on the porous inorganic carrier so as to adsorb heavy metal ions in the subsequent process.
In some possible embodiments, the photosynthetic bacteria fermentation broth has a bacteria content of 10 × 1082/mL, 12X 108one/mL, 16X 108one/mL or 20X 108Per mL; the solid-liquid ratio of the porous inorganic carrier to the photosynthetic bacteria fermentation broth is 0.05g/mL, 0.08g/mL or 0.1 g/mL.
Optionally, when the photosynthetic bacteria are loaded, the culture time is 20-30h, the illumination intensity is 1000-3000lx, and the culture temperature is 29-30 ℃. Is favorable for the division and proliferation of the photosynthetic bacteria in logarithmic phase. In some possible embodiments, the incubation time is 20h, 24h, 28h or 30h, the illumination intensity is 1000lx, 1500lx, 2000lx, 2500lx or 3000lx, and the incubation temperature is 29 ℃, 29.5 ℃ or 30 ℃.
Furthermore, the light culture is membrane-forming culture in a light shaking table, the membrane-forming culture is carried out under water flow, and the rotation speed of the shaking table is 120-. Optionally, the rotational speed of the rocking platforms is 120r/min, 140r/min, 160r/min or 180 r/min.
Cultivate in illumination shaking table, cultivate comparatively simply, and carry out the mode that the biofilm culturing was cultivateed under rivers, can make the load between photosynthetic bacteria and the porous inorganic carrier more firm, when adsorbing heavy metal ion, photosynthetic bacteria is difficult for following the carrier and drops, is favorable to adsorbing the in-process of heavy metal ion, photosynthetic bacteria and carrier's cooperation in coordination, and subsequent adsorption effect is better.
The bacteria content of the culture in step S10 is 10X 108-20×108Putting 200mL of photosynthetic bacteria fermentation liquor into a triangular flask, putting 20g of the natural clinoptilolite carrier treated in the step S20, putting the photosynthetic bacteria fermentation liquor into a light irradiation shaking table under an anoxic condition for biofilm culturing, pouring the residual photosynthetic bacteria liquid after 24 hours under the conditions of illumination of 1000-.
The microbial composite material prepared by the method is characterized in that the porous inorganic carrier is loaded with photosynthetic bacteria, and the porous inorganic carrier and the photosynthetic bacteria can be cooperatively matched, so that heavy metal ions in the wastewater can be effectively adsorbed, and the wastewater polluted by the heavy metals can be treated.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
A preparation method of a microbial composite material comprises the following steps:
(1) preparing photosynthetic bacteria fermentation liquor:
mixing 1g/L ammonium chloride, 1g/L sodium bicarbonate, 3g/L sodium acetate, 2g/L sodium chloride, 0.2g/L dipotassium hydrogen phosphate, 0.2g/L magnesium sulfate heptahydrate, 0.1g/L yeast extract, 10mL growth factor and 10mL microelement solution, adjusting pH value to 7, sterilizing in a steam sterilizing pot (sterilizing condition is 0.1MPa, temperature is 115 ℃, time is 20min), and sterilizing for later use.
Selecting photosynthetic bacteria strain (Beijing Ordoo sky Biotechnology research institute, Inc.), inoculating the strain into the liquid culture medium, culturing under illumination of 2000lx under oxygen-deficient condition at 29.5 deg.C for 2.5 days to obtain seed culture solution; inoculating the other liquid culture medium according to the inoculum size of 10% of the mass fraction, culturing under the condition of oxygen deficiency and illumination intensity of 2000lx for 3.5 days at the temperature of about 29.5 ℃ to obtain the photosynthetic bacteria fermentation liquor in logarithmic phase.
(2) And pretreating natural clinoptilolite:
washing natural clinoptilolite with particle size of about 8mm with deionized water, soaking in 5% hydrochloric acid solution for 2h, washing to neutrality, soaking in 5% sodium hydroxide solution for 2h, washing again to neutrality, sterilizing with high pressure steam for 30min, taking out, and air drying.
(3) Preparing the microbial composite material:
and (2) putting 200mL of the photosynthetic bacteria fermentation liquor cultured in the step (1) into a triangular flask, adding 20g of the natural clinoptilolite carrier treated in the step (2), putting the natural clinoptilolite carrier into a light-irradiation shaking table under an anoxic condition, and performing biofilm culturing under water flow, wherein the biofilm culturing condition is that the illuminance is 2000lx, the temperature is about 29.5 ℃, the rotating speed is 150r/min, pouring out the residual photosynthetic bacteria liquid after 24 hours, slightly leaching the natural clinoptilolite with normal saline, and airing for later use.
Example 2
Example 2 provides a preparation method substantially identical to that provided in example 1, except that the particle size of natural clinoptilolite is 1 mm.
Example 3
The preparation method provided in example 3 is substantially the same as the preparation method provided in example 1, and is different in that the cultivation is not performed by a biofilm culturing mode, that is, the rotation speed of a shaking table is 0, the cultivation is performed in a light shaking table under an anoxic condition, the cultivation condition is that the illumination is 2000lx and the temperature is about 29.5 ℃, after 24 hours, the residual photosynthetic bacteria liquid is poured out, the natural clinoptilolite is lightly leached by normal saline, and the natural clinoptilolite is dried for standby.
Example 4
The preparation method provided in example 4 is substantially the same as the preparation method provided in example 1, except that the natural clinoptilolite having a particle size of about 8mm is adjusted to volcanic ceramsite having a particle size of about 5 mm.
Comparative example 1
The preparation method provided in comparative example 1 is substantially identical to the preparation method provided in example 1, except that natural clinoptilolite is not subjected to acid treatment and alkali treatment.
Comparative example 2
Comparative example 2 provides a production method substantially identical to that provided in example 1, except that natural clinoptilolite is subjected to acid treatment and alkali treatment, but a step of washing to neutrality is not performed between the acid treatment and the alkali treatment.
Comparative example 3
The preparation method provided in comparative example 3 is substantially identical to the preparation method provided in example 1, except that the time for the scale-up culture is 6 days, so that the fermentation broth of the photosynthetic bacteria is in the stationary phase.
Comparative example 4
200mL of the photosynthetic bacteria fermentation liquor obtained in the step (1) in the example 1 is taken, a small amount of the fermentation liquor is centrifuged at normal temperature for many times, the centrifugation speed is 8000rpm, supernatant and precipitate are removed, deionized water is added, and then the mixture is blown and uniformly mixed by a liquid transfer gun and is repeated for 3 times to obtain photosynthetic bacteria precipitate for later use.
Comparative example 5
The natural clinoptilolite obtained in step (2) of example 1 was subjected to membrane-mounting culture.
Comparative example 6
And (3) carrying out blank biofilm culturing on the volcanic ceramsite obtained in the step (2) in the example 4.
Experimental example 1
The preparation conditions of the wastewater treatment agents are shown in table 1:
TABLE 1 preparation conditions of wastewater treatment agents
Figure BDA0002605429800000111
Figure BDA0002605429800000121
0.2085g of zinc chloride is taken in a beaker, added with a proper amount of deionized water, stirred and dissolved, transferred into a 1000mL volumetric flask, and transferred into a 1000mL reagent bottle for standby after the deionized water has a constant volume to obtain Zn2+The zinc chloride solution with the concentration of 100mg/L is ready for use.
0.3929g of blue vitriol is taken to be put in a beaker, added with a proper amount of deionized water to be stirred and dissolved, transferred into a 1000mL volumetric flask, and transferred into a 1000mL reagent bottle for standby after the deionized water has constant volume to obtain Cu2+The copper sulfate solution with the concentration of 100mg/L is ready for use.
Taking 50mL of the heavy metal ion solution, putting the heavy metal ion solution into a 150mL conical flask, adding 2g of the treating agent shown in the table 1, putting the conical flask into an illumination shaking table, placing the conical flask into an illumination shaking table, extracting more than 0.3mL of the solution by using a needle tube provided with a filter membrane (0.45 mu m) after the illumination is 2000lx, the temperature is about 29.5 ℃, the rotating speed is 150r/min, adsorbing for 24 hours, diluting the absorbed solution to a certain multiple, measuring the absorbance at the maximum absorption wavelength of the heavy metal ions by using an ultraviolet spectrophotometer, comparing with a standard curve, and determining the concentration of the heavy metal ions in the solution before and after adsorption to obtain the table 2.
TABLE 2 adsorption results of heavy metal ions
Zinc chloride solution Copper sulfate solution
Example 1 95.7% 98.34%
Example 2 94.21% 96.8%
Example 3 93.2% 95.5%
Example 4 59.83% 98.2%
Comparative example 1 94.2% 96.1%
Comparative example 2 93.3% 96.4%
Comparative example 3 92.5% 93.8%
Comparative example 4 47.4% 45.59%
Comparative example 5 41.4% 51.3%
Comparative example 6 7.2% 10.2%
It can be seen from the correspondence between table 1 and table 2 that the microbial composite provided in the embodiments of the present application can effectively adsorb heavy metal ions in low-concentration wastewater.
As can be seen from examples 1, 4 and 5 (examples 4, 4 and 6), the adsorption effect of the microbial composite material provided by the application on heavy metal ions is higher than the sum of the adsorption effects of a carrier alone and a photosynthetic bacterium alone, which shows that the microbial composite material provided by the application has a good synergistic effect on the adsorption effect on heavy metal ions.
As can be seen from the comparison between example 1 and example 2, the natural clinoptilolite has a large particle size, and is favorable for the adsorption of heavy metal ions by the microbial composite material.
As can be seen from comparison between examples 1 and 3, when the microbial composite material is cultured without being cultured under water, the adsorption effect of the cultured microbial composite material on heavy metal ions is slightly poor, which may be due to the slightly poor binding fastness of some photosynthetic bacteria to the carrier, thereby reducing the adsorption effect.
As can be seen from the comparison of example 1 and comparative example 1, the loading effect of the photosynthetic bacteria is decreased without the pretreatment of the carrier, thereby decreasing the adsorption effect on heavy metal ions. The reasons for this may be: the activity of the photosynthetic bacteria is affected and the specific surface area is slightly smaller because of no pretreatment, so that the loading effect of the photosynthetic bacteria is poor.
As can be seen from the comparison between example 1 and comparative example 2, during pretreatment, acid soaking is performed first, then alkali soaking is performed, and washing is not performed between the acid soaking and the alkali soaking until the carrier is neutral, so that the obtained carrier has poor loading effect on photosynthetic bacteria, and the adsorption effect on heavy metal ions is reduced. The reasons for this may be: as the acid-base neutralization reaction is a strong reaction, the structure of the carrier is damaged to a certain extent.
As can be seen from the comparison between example 1 and comparative example 3, the effect of loading photosynthetic bacteria on the carrier is not good in the treatment stabilization period of photosynthetic bacteria when preparing the microbial composite material. The reasons for this may be: the speed of division and proliferation of the photosynthetic bacteria is slowed down, thereby reducing the load quantity of the photosynthetic bacteria.
Experimental example 2
Fig. 2 is a microscope picture of photosynthetic bacteria fermentation broth provided in step (1) of example 1 of the present application, fig. 3 is a microscope picture of natural clinoptilolite provided in step (2) of example 1 of the present application, and fig. 4 is a microscope picture of microbial composite provided in step (3) of example 1 of the present application. As can be seen from fig. 2 to 4, in the microbial composite material provided in example 1 of the present application, photosynthetic bacteria are supported on natural clinoptilolite.
Fig. 5 is a microscope photograph of natural clinoptilolite provided in step (2) of example 4 of the present application, and fig. 6 is a microscope photograph of a microbial composite provided in step (3) of example 4 of the present application. As can be seen from fig. 2, 5 and 6, in the microbial composite material provided in example 4 of the present application, the volcanic ceramsite is loaded with photosynthetic bacteria.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Claims (10)

1. The preparation method of the microbial composite material is characterized by comprising the following steps of:
pretreatment of the porous inorganic carrier: soaking a porous inorganic carrier in an acid solution, washing to be neutral, then soaking in an alkali solution, and carrying out sterilization treatment after washing to be neutral;
preparing a microbial composite material: and placing the pretreated porous inorganic carrier in a photosynthetic bacteria fermentation liquor in a logarithmic phase, and carrying out illumination culture under an anoxic condition to load the photosynthetic bacteria on the porous inorganic carrier.
2. The production method according to claim 1, wherein the porous inorganic carrier has a particle size of 4 to 10 mm;
optionally, the porous inorganic carrier is natural zeolite, and the particle size of the natural zeolite is 6-9 mm;
optionally, the porous inorganic carrier is volcanic ceramsite, and the particle size of the volcanic ceramsite is 4-6 mm.
3. The method according to claim 1, wherein the photosynthetic bacteria fermentation broth has a bacteria content of 10 x 108-20×108The solid-liquid ratio of the porous inorganic carrier to the photosynthetic bacteria fermentation broth is 0.05-0.1 g/mL;
optionally, the culturing time is 20-30h, the illumination intensity of the culturing is 1000-3000lx, and the culturing temperature is 29-30 ℃.
4. The method according to claim 3, wherein the light culturing is performed by membrane culturing in a light-culturing shaker, the membrane culturing is performed under water flow, and the rotation speed of the shaker is 120-180 r/min.
5. The method according to any one of claims 1 to 4, wherein the seed culture of the photosynthetic bacteria is inoculated into the first liquid culture medium and cultured under the conditions of oxygen deficiency, illumination intensity of 1000-;
inoculating the seed culture solution according to the inoculation amount with the mass fraction of 5-15% to perform amplification culture in a second liquid culture medium, and culturing for 3-4 days under the conditions of oxygen deficiency, illumination intensity of 1000-.
6. The method according to claim 5, wherein the first liquid culture medium and the second liquid culture medium are each prepared by a method comprising:
mixing 0.8-1.2g/L ammonium chloride, 0.8-1.2g/L sodium bicarbonate, 2.5-3.5g/L sodium acetate, 1.5-2.5g/L sodium chloride, 0.1-0.3g/L dipotassium hydrogen phosphate, 0.1-0.3g/L magnesium sulfate heptahydrate, 0.05-0.15g/L yeast extract, 8-12mL growth factor and 8-12mL microelement solution, adjusting pH value to 6.8-7.2, and sterilizing.
7. A microbial composite material produced by the production method according to any one of claims 1 to 6.
8. Use of the microbial composite according to claim 7 for adsorbing heavy metal ions in wastewater.
9. The use according to claim 8, wherein the heavy metal ions are zinc ions or copper ions, and the concentration of the heavy metal ions in the wastewater is 80-150 mg/L.
10. The use according to claim 8, wherein the method for adsorbing the heavy metal ions in wastewater comprises: placing the microbial composite material in a solution containing the heavy metal ions for anoxic adsorption;
wherein the solid-to-liquid ratio of the microbial composite material to the solution is 30-50mg/mL, the adsorption temperature is 29-30 ℃, and the adsorption is carried out for 20-30h under the condition of oscillation.
CN202010740710.3A 2020-07-28 2020-07-28 Microbial composite material and preparation method and application thereof Pending CN113998787A (en)

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