CN111206027B - Magnetic biochar suitable for loading bacillus and preparation method and application thereof - Google Patents
Magnetic biochar suitable for loading bacillus and preparation method and application thereof Download PDFInfo
- Publication number
- CN111206027B CN111206027B CN202010093313.1A CN202010093313A CN111206027B CN 111206027 B CN111206027 B CN 111206027B CN 202010093313 A CN202010093313 A CN 202010093313A CN 111206027 B CN111206027 B CN 111206027B
- Authority
- CN
- China
- Prior art keywords
- biochar
- magnetic biochar
- bacillus
- magnetic
- corncob
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
- C02F2103/325—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters from processes relating to the production of wine products
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Inorganic Chemistry (AREA)
- Zoology (AREA)
- Genetics & Genomics (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Biotechnology (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention discloses a preparation method of magnetic biochar suitable for loading bacillus, which comprises the following steps: (1) Adding corncob into the mixed solution, oscillating on a shaking table at 40-70 ℃ to perform structural penetration, and performing hydrothermal carbonization on the dried modified corncob to obtain biochar for later use; (2) Mixing biochar with soluble ferric salt solution, oscillating at room temperature on a shaking table to perform structural penetration, and roasting the dried modified biochar at high temperature under a weak oxidizing atmosphere to obtain the magnetic biochar. According to the invention, corncobs are used as raw materials, mixed solution containing multiple microelements is subjected to low-temperature mixed permeation and then subjected to high-temperature hydrothermal carbonization, the porous structure of the biochar is rich by utilizing power provided by volatilization of moisture twice, the microelements permeate into pores to be reserved, the obtained biochar with rich porous structure and rich nutrient elements is permeated by soluble ferric salt, and the magnetic biochar is obtained by roasting in protective atmosphere.
Description
Technical Field
The invention belongs to the technical field of biochar preparation and environmental protection, and relates to magnetic biochar suitable for loading bacillus, a preparation method thereof and application thereof in wastewater purification.
Background
In China, about 10% of waste water from agricultural and sideline product processing industry, food processing industry and beverage production manufacturing industry is consumed, along with national economic adjustment, enterprise structures are developed towards energy conservation and high efficiency, the discharge amount of the industrial waste water is large and has a continuous increasing trend, and the waste water discharged into rivers can pollute water bodies, cause serious eutrophication of the water bodies, and cause red tide and other phenomena. The microbial treatment method is to utilize the cultured and domesticated wastewater degradation bacteria under proper degradation conditions to carry out a high-efficiency degradation process on harmful substances in the wastewater, so that the content of COD, BOD and the like in the wastewater is reduced, but the microbial treatment still has the problems of low microbial activity and adaptability and difficulty in playing a role in severe environment pollution; immobilized microbial remediation is one type of microbial remediation, and is a biotechnology that uses physical or chemical means to immobilize free microorganisms in a region and maintain a high degree of enrichment and activity to meet the application. The application number CN20160555834.8 proposes a preparation method of the activated carbon loaded with the microorganisms, wherein 80% of the microorganisms are loaded on the surface of the activated carbon, but the microorganisms are loaded on the surface of the activated carbon, so that the mechanical strength is poor, the recovery is difficult, and the secondary utilization is not facilitated; the application number CN20101082869.3 proposes a filler for bearing microorganisms, but the preparation cost of the microbial carrier filler is higher, and the filler can cause secondary pollution to the environment; the pH value of the wastewater is low, the COD is high but the phosphorus concentration is low in the range of 3-4, and the N, P content in the wastewater is low, so that the C, N, P proportion for maintaining the biological effect is deregulated, and when the wastewater is treated by adopting a biochemical process, the normal operation of the process is generally maintained by adding nutritive salt to ensure the C, N, P proportion required by general microorganisms. However, this method not only increases the running cost, but also has poor treatment effect if the addition amount is insufficient, and increases the phosphorus content of the effluent if the addition amount is excessive. Therefore, there is a need to solve the above problems by creating a new biological treatment process with little or no addition of nutrient elements.
Disclosure of Invention
In order to solve the defects existing in the prior art, the invention aims to provide a preparation method of magnetic biochar suitable for loading bacillus, which takes corncobs as raw materials, carries out low-temperature mixed permeation on the corncobs by using mixed solution containing various microelements, and then carries out hydrothermal carbonization, the power provided by volatilization of moisture twice is utilized to ensure that the pore structure of the biochar is rich, microelements permeate into pores to remain and provide the power required by microorganism growth, and the rich pores are beneficial to oxygen bubbling, more charged oxygen-containing functional groups such as amido, carboxyl and the like are formed, the adhesion and proliferation of microorganisms are beneficial, and the obtained biochar with rich pore structures and rich in nutrient elements is subjected to soluble ferric salt permeation and protective atmosphere roasting to obtain the magnetic biochar.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of magnetic biochar suitable for loading bacillus comprises the following steps:
(1) Adding corncob into the mixed solution, oscillating on a shaking table at 40-70 ℃ to perform structural penetration, and performing hydrothermal carbonization on the dried modified corncob to obtain biochar for later use;
the solute of the mixed solution comprises the following components: 15-25.0mg of magnesium sulfate, 2.0-2.5g of disodium hydrogen phosphate, 1.0-1.5g of monopotassium phosphate and 0.5-1.0g of ammonium nitrate, wherein the total mass fraction of the mixed solution is 15% -20%;
(2) Mixing biochar with soluble ferric salt solution, oscillating at room temperature on a shaking table to perform structural penetration, and roasting the dried modified biochar at high temperature under a weak oxidizing atmosphere to obtain the magnetic biochar.
According to the invention, the corncob and the mixed solution are subjected to low-temperature mixed permeation at 40-70 ℃ in advance, slow transpiration of moisture provides power to pore the material, and the porosity of the material is improved; meanwhile, various microelements in the mixed solution penetrate into the formed corncob pores, then the corncob pores are carbonized through high-temperature hydrothermal, and the materials are porous again by utilizing the power provided by water volatilization, so that the formed biochar has a rich pore structure, the rich pores are favorable for the bubbling of oxygen, more charged oxygen-containing functional groups such as amido, carboxyl and the like are formed, the adhesion and proliferation of microorganisms are favorable, and the microelements which penetrate into the corncob pores are reserved in the pores after carbonization, so that the biochar with a rich pore structure and rich in nutrient elements is obtained; and then performing permeation modification in a soluble ferric salt solution, roasting and forming at high temperature, and generating ferroferric oxide and ferric oxide by ferric salt in a high-temperature weak oxidizing atmosphere to obtain the magnetic biochar.
Preferably, in the step (1), the corncob is firstly cut into 1-1.5cm blocky structures, and then added into the mixed solution according to the mass-volume ratio of 1:3-4 g/mL.
Preferably, in step (1), the oscillation time is 18-24 hours.
Preferably, in the step (1), the concentration of the modified corncob is 0.36-0.66g/mL, the temperature is 180-250 ℃ and the time is 4-6h during hydrothermal carbonization.
Preferably, in the step (2), the mass-volume ratio of the biochar to the soluble ferric salt solution is 1g:30-40mL, and the mass fraction of the soluble ferric salt solution is 50%.
Preferably, in step (2), the soluble iron salt is ferric chloride, ferric sulfate or ferric nitrate.
Preferably, in step (2), the oscillation time is 4 to 5 hours.
Preferably, in the step (2), the weakly oxidizing atmosphere is a mixed atmosphere of 5% by volume of oxygen and 95% by volume of nitrogen, and the high-temperature roasting temperature is 400-700 ℃ for 2-3 hours.
Preferably, in the step (2), the magnetic biochar is washed with water and then washed with acid or alkali until the pH is 7.2-7.4.
The invention also provides the magnetic biochar prepared by the preparation method, which has rich pore structure, is rich in charged oxygen-containing functional groups such as amido, carboxyl and the like and various trace nutrient elements, and is very suitable for the growth of microorganisms such as bacillus and the like.
The invention also provides application of the magnetic biochar, and the magnetic biochar is used for purifying wastewater after bacillus is loaded.
Preferably, the specific process of the bacillus supported by the magnetic biochar is as follows: inoculating the bacillus agent into a container filled with LB liquid culture medium according to the inoculum size of 1-5% by volume, culturing for 2-8 hours in an oscillating incubator with the rotation speed of 120-150r/min at 20-35 ℃, adding a magnetic biochar carrier according to 3-5% by weight of the LB liquid culture medium, uniformly mixing the magnetic biochar with bacterial liquid, placing the mixture in a shaking table with the temperature of 35 ℃ and the rotation speed of 90-130r/min for fixing for 1-2 days, taking out the mixture, centrifuging the mixture on a high-speed centrifuge with the rotation speed of 5000-8000r/min after the fixing is finished, removing the culture medium, washing the mixture with 0.85% physiological saline, and carrying out solid-liquid separation to obtain the magnetic biochar loaded with bacillus.
Compared with the prior art, the invention has the advantages that:
(1) Compared with the existing carrier, the corncob is used as the raw material for preparing the biochar, and has a rich pore structure, so that microorganisms can enter the pores, the corncob is suitable for the inhabitation of the microorganisms, the damage of high-concentration pollutants to the microorganisms is avoided, the activity and the quantity of the microorganisms in a polluted environment are improved, and the corncob is more suitable for being used as a microbial carrier.
(2) According to the invention, the corncob is subjected to low-temperature mixed permeation by adopting the mixed solution at 40-70 ℃, slow transpiration of moisture provides power to pore the material, and the porosity of the material is improved; the prepared biochar contains N, P, mg, S and other microelements, so that the microelements required by microorganism growth can be provided, the method is more suitable for microorganism growth and propagation, the quantity of microorganisms in pollutants is increased, and the degradation efficiency is improved. On the other hand, the addition of the elements also improves the electrochemical performance of the biochar and accelerates the action of microorganisms through the biochar and pollutants.
(3) The prepared corncob charcoal is subjected to permeation modification in a soluble ferric salt solution, is baked and formed at a high temperature of 400-700 ℃, and the soluble ferric salt reacts with oxygen at a high temperature to generate ferroferric oxide and ferric oxide, so that the magnetic charcoal material is obtained, has magnetism, can be recycled after treatment, and does not pollute the environment.
(4) According to the invention, bacillus is loaded by the magnetic biochar to degrade organic matters in the pollutants in the brewing wastewater, and the magnetic biochar is favorable for survival of microorganisms so as to achieve the aim of effectively degrading the pollutants. The degradation process does not damage the environment, does not bring secondary pollution, is environment-friendly, and realizes green degradation.
Drawings
FIG. 1 is a graph showing the specific surface area adsorption/desorption curve and pore size distribution of the magnetic biochar material prepared in example 1;
FIG. 2 is an X-ray diffraction chart of the magnetic biochar material prepared in example 1;
FIG. 3 is an infrared spectrum of the magnetic biochar materials prepared in comparative example 3 and example 1;
FIG. 4 is an EDS diagram of the magnetic biochar material prepared in example 1;
FIG. 5 is a scanning electron microscope image of the magnetic biochar material prepared in example 1 before and after loading bacillus, wherein the left image is before loading, and the right image is after loading;
FIG. 6 is a photograph of the magnetic biochar prepared in example 1;
FIG. 7 is a graph showing the specific surface area adsorption and desorption curves and pore size distribution of the magnetic biochar material prepared in comparative example 1;
FIG. 8 is a photograph of the magnetic biochar prepared in comparative example 2.
Detailed Description
The present invention will be further described in detail by way of examples, which are not intended to limit the scope of the present invention. It will be understood by those skilled in the art that equivalent substitutions and corresponding modifications of technical features of the present disclosure are still within the scope of the present disclosure.
Example 1
Collecting corncob, cutting the corncob into a sheet structure with a knife about 1cm, adding the corncob into a prepared 20mL mixed solution (the solute of the mixed solution comprises the following components of 20.0mg of magnesium sulfate, 2.0g of disodium hydrogen phosphate, 1.2g of monopotassium phosphate and 0.8g of ammonium nitrate) according to the mass volume ratio of 1:3g/mL, oscillating for 24 hours at 40 ℃ on a shaking table, performing low-temperature structure permeation, and drying after oscillation to obtain the modified corncob; adding water into modified corncob to prepare 0.5g/mL concentration, putting the mixture into a hydrothermal reaction kettle, carrying out hydrothermal carbonization for 5 hours at 180 ℃ in an oven to prepare biochar, washing the biochar to be neutral by distilled water, then drying the biochar, adding the biochar into 50wt% ferric chloride solution according to a mass-volume ratio of 1:30mL, carrying out activation treatment, oscillating the mixture on a shaking table at room temperature for 24 hours, carrying out structural infiltration, drying the oscillated mixture, putting the oscillated mixture into a tubular furnace, and firing the tubular furnace at 500 ℃ for 2 hours under a mixed atmosphere of oxygen with a volume fraction of 5% and nitrogen with a volume fraction of 95% to prepare the magnetic biochar; washing the magnetic biochar with water, washing with acid or alkali until the pH value is 7.2, and drying for later use;
1ml of bacillus agent is inoculated into a container filled with 50ml of LB liquid culture medium, after the bacillus agent is cultured for 5 hours in an oscillation incubator with the rotating speed of 150r/min at room temperature, 2g of magnetic biochar carrier is added, the magnetic biochar and bacterial liquid are uniformly mixed, the mixture is taken out after being fixed for 2 days by a shaking table with the rotating speed of 130r/min at the temperature of 35 ℃, after the fixation is finished, the culture medium is removed by centrifugation on a high-speed centrifuge with the rotating speed of 6000r/min, and the magnetic biochar loaded with bacillus is obtained after washing with 0.85% normal saline and solid-liquid separation.
As shown in FIG. 1, it was confirmed that the magnetic biochar prepared in example 1 contained a large specific surface area (specific surface area: 464.7808 m) 2 Per gram of average pore diameter: 3.2249 nm) can provide more active sites and a larger colonization environment for microorganisms.
As shown in FIG. 2, the magnetic biochar prepared in example 1 was confirmed to have magnetism by an X-ray diffraction pattern, and was recovered after use without secondary pollution.
As shown in FIG. 3, the infrared spectrogram can prove that the magnetic biochar prepared in the embodiment 1 is rich in oxygen-containing functional groups and is implanted with multi-electron nitrogen-containing functional groups, electrons can be provided for microorganisms, inter-species electron transfer is promoted, microbial activity is improved, and degradation of organic matters is accelerated.
As shown in FIG. 4, the X-ray energy spectrum further proves that the magnetic biochar prepared by the method in the example 1 is successfully doped with N, O, mg, P and other elements, so that nutrients can be provided for the survival of microorganisms, and the adhesion and proliferation of the microorganisms are facilitated.
As shown in FIG. 5, it was found by a scanning electron microscope that the bacillus-loaded magnetic biochar prepared in example 1 was successfully loaded with a large amount of bacillus.
As shown in FIG. 6, the magnetic biochar prepared in example 1 has compact macroscopic structure and complete morphology.
Example 2
Collecting corncob, cutting the corncob into a sheet structure with a knife about 1cm, adding the corncob into a prepared 20mL mixed solution (the solute of the mixed solution comprises 25.0mg of magnesium sulfate, 2.5g of disodium hydrogen phosphate, 1.5g of potassium dihydrogen phosphate and 1.0g of ammonium nitrate) according to the mass volume ratio of 1:4g/mL, oscillating for 20 hours at 70 ℃ on a shaking table, performing low-temperature structure permeation, and drying after oscillation to obtain the modified corncob; adding water into modified corncob to prepare 0.5g/mL concentration, putting the mixture into a hydrothermal reaction kettle, carrying out hydrothermal carbonization for 5 hours at 250 ℃ in an oven to prepare biochar, washing the biochar to be neutral by distilled water, then drying the biochar, adding the biochar into 50wt% ferric chloride solution according to a mass-volume ratio of 1:40mL, carrying out activation treatment, oscillating the mixture on a shaking table at room temperature for 24 hours, carrying out structural infiltration, drying the mixture after oscillation, and putting the mixture into a tubular furnace to be fired for 2 hours at 700 ℃ under a mixed atmosphere of oxygen with a volume fraction of 5% and nitrogen with a volume fraction of 95%, thus preparing the magnetic biochar; washing the magnetic biochar with water, washing with acid or alkali until the pH value is 7.2, and drying for later use;
1ml of bacillus agent is inoculated into a container filled with 50ml of LB liquid culture medium, after the bacillus agent is cultured for 5 hours in an oscillation incubator with the rotating speed of 150r/min at room temperature, 2g of magnetic biochar carrier is added, the magnetic biochar and bacterial liquid are uniformly mixed, the mixture is taken out after being fixed for 2 days by a shaking table with the rotating speed of 130r/min at the temperature of 35 ℃, after the fixation is finished, the culture medium is removed by centrifugation on a high-speed centrifuge with the rotating speed of 6000r/min, and the magnetic biochar loaded with bacillus is obtained after washing with 0.85% normal saline and solid-liquid separation.
Comparative example 1
Collecting corncob, cutting the corncob into a sheet structure with a knife about 1cm, adding the corncob into a prepared 20mL mixed solution (the solute of the mixed solution comprises the following components of 20.0mg of magnesium sulfate, 2.0g of disodium hydrogen phosphate, 1.2g of potassium dihydrogen phosphate and 0.8g of ammonium nitrate) according to the mass-to-volume ratio of 1:3g/mL, uniformly mixing and drying to obtain a modified corncob; adding water into modified corncob to prepare 0.5g/mL concentration, putting the mixture into a hydrothermal reaction kettle, carrying out hydrothermal carbonization for 5 hours at 180 ℃ in an oven to prepare biochar, washing the biochar to be neutral by distilled water, then drying the biochar, adding the biochar into 50wt% ferric chloride solution according to a mass-volume ratio of 1:30mL, carrying out activation treatment, oscillating the mixture on a shaking table at room temperature for 24 hours, carrying out structural infiltration, drying the oscillated mixture, putting the oscillated mixture into a tubular furnace, and firing the tubular furnace at 500 ℃ for 2 hours under a mixed atmosphere of oxygen with a volume fraction of 5% and nitrogen with a volume fraction of 95% to prepare the magnetic biochar; washing the magnetic biochar with water, washing with acid or alkali until the pH value is 7.2, and drying for later use;
1ml of bacillus agent is inoculated into a container filled with 50ml of LB liquid culture medium, after the bacillus agent is cultured for 5 hours in an oscillation incubator with the rotating speed of 150r/min at room temperature, 2g of magnetic biochar carrier is added, the magnetic biochar and bacterial liquid are uniformly mixed, the mixture is taken out after being fixed for 2 days by a shaking table with the rotating speed of 130r/min at the temperature of 35 ℃, after the fixation is finished, the culture medium is removed by centrifugation on a high-speed centrifuge with the rotating speed of 6000r/min, and the magnetic biochar loaded with bacillus is obtained after washing with 0.85% normal saline and solid-liquid separation.
As shown in FIG. 7, the mixed solution does not swell into biomass and only contacts the outer surface of the material without low-temperature permeation, chemical reaction, degradation and conversion are carried out at high temperature, and the prepared magnetic biochar sample has small specific surface area (specific surface area: 259.696 m) 2 /g, average pore diameter: 3.719 nm). The invention makes the material swell and porous through the slow transpiration of water at 40-70 ℃ in the previous stage, and the elements such as N, mg, S and the like are fully swelled into the biomass structure in the reaction process, and then the biomass structure is carbonized by high temperature water, and the power provided by the volatilization of water is utilizedAnd the material is subjected to pore forming again, so that the material has rich specific surface area.
Comparative example 2
Collecting corncob, cutting the corncob into a sheet structure with a knife about 1cm, adding the corncob into a prepared 20mL mixed solution (the solute of the mixed solution comprises the following components of 20.0mg of magnesium sulfate, 2.0g of disodium hydrogen phosphate, 1.2g of monopotassium phosphate and 0.8g of ammonium nitrate) according to the mass-volume ratio of 1:3g/mL, oscillating for 24 hours at 100 ℃ on a shaking table, performing low-temperature structure permeation, and drying after oscillation to obtain the modified corncob; adding water into modified corncob to prepare 0.5g/mL concentration, putting the mixture into a hydrothermal reaction kettle, carrying out hydrothermal carbonization for 5 hours at 180 ℃ in an oven to prepare biochar, washing the biochar to be neutral by distilled water, then drying the biochar, adding the biochar into 50wt% ferric chloride solution according to a mass-volume ratio of 1:30mL, carrying out activation treatment, oscillating the mixture on a shaking table at room temperature for 24 hours, carrying out structural infiltration, drying the oscillated mixture, putting the oscillated mixture into a tubular furnace, and firing the tubular furnace at 500 ℃ for 2 hours under a mixed atmosphere of oxygen with a volume fraction of 5% and nitrogen with a volume fraction of 95% to prepare the magnetic biochar; washing the magnetic biochar with water, washing with acid or alkali until the pH value is 7.2, and drying for later use;
1ml of bacillus agent is inoculated into a container filled with 50ml of LB liquid culture medium, after the bacillus agent is cultured for 5 hours in an oscillation incubator with the rotating speed of 150r/min at room temperature, 2g of magnetic biochar carrier is added, the magnetic biochar and bacterial liquid are uniformly mixed, the mixture is taken out after being fixed for 2 days by a shaking table with the rotating speed of 130r/min at the temperature of 35 ℃, after the fixation is finished, the culture medium is removed by centrifugation on a high-speed centrifuge with the rotating speed of 6000r/min, and the magnetic biochar loaded with bacillus is obtained after washing with 0.85% normal saline and solid-liquid separation.
As shown in fig. 8, the structure permeation was performed at 100 ℃, the steam was rapidly volatilized, and the impact force was strong. The mixed solution and the biomass powder undergo preliminary chemical reaction, and under the condition of later-stage pyrolysis, the prepared magnetic biochar is loose and unstable in structure, fragile and not provided with an integral structure.
Comparative example 3
Collecting corncob, cutting the corncob into a sheet structure with a knife, adding water to prepare a concentration of 0.5g/mL, putting the sheet structure into a hydrothermal reaction kettle, carrying out hydrothermal carbonization for 5 hours at 180 ℃ in an oven to prepare biochar, washing the biochar to be neutral with distilled water, drying the biochar, adding the biochar into a 50wt% ferric chloride solution according to a mass-volume ratio of 1:30mL, carrying out activation treatment, oscillating the mixture on a shaking table at room temperature for 24 hours, carrying out structural permeation, drying the mixture after oscillation, putting the mixture into a tubular furnace, and firing the tubular furnace at 500 ℃ for 2 hours under a mixed atmosphere of oxygen with a volume fraction of 5% and nitrogen with a volume fraction of 95%, thus preparing the magnetic biochar; washing the magnetic biochar with water, washing with acid or alkali until the pH value is 7.2, and drying for later use;
1ml of bacillus agent is inoculated into a container filled with 50ml of LB liquid culture medium, after the bacillus agent is cultured for 5 hours in an oscillation incubator with the rotating speed of 150r/min at room temperature, 2g of magnetic biochar carrier is added, the magnetic biochar and bacterial liquid are uniformly mixed, the mixture is taken out after being fixed for 2 days by a shaking table with the rotating speed of 130r/min at the temperature of 35 ℃, after the fixation is finished, the culture medium is removed by centrifugation on a high-speed centrifuge with the rotating speed of 6000r/min, and the magnetic biochar loaded with bacillus is obtained after washing with 0.85% normal saline and solid-liquid separation.
As shown in figure 3, the prepared magnetic biochar has relatively few oxygen-containing functional groups without adding mixed solution modification treatment, and the prepared biochar has small nutrient element content due to the fact that various microelements are not added, so that microorganisms adsorbed on the surface of the biochar are few, the capability of the biochar for adsorbing organic matters is reduced, the efficiency of bacteria loaded on the surface of the biochar for adsorbing and absorbing the organic matters is low, and the pollutant removal efficiency is relatively low.
2g of the bacillus-loaded magnetic biochar samples prepared in examples 1-2 and comparative examples 1-3 were added to 100mL of a brewing wastewater water sample (the original COD of the water sample is 1287mg/L, BOD is 864mg/L, total nitrogen is 42mg/L, total phosphorus is 7.5mg/L, pH value is 3.75), placed in a shaker, and shaken at 35 ℃ for 5 days at a rotational speed of 130r/min to detect COD, total nitrogen and total phosphorus data of the water, and the results are shown in Table 1:
table 1 comparison of the wastewater samples before and after treatment
Note that: the blank is that only 1ml of bacillus agent is directly added into a water sample of the brewing wastewater.
Claims (8)
1. The preparation method of the magnetic biochar suitable for loading bacillus is characterized by comprising the following steps of: (1) Adding corncob into the mixed solution, oscillating on a shaking table at 40-70 ℃ to perform structural penetration, and performing hydrothermal carbonization on the dried modified corncob to obtain biochar for later use; the volume of the mixed solution is 20mL;
the solute of the mixed solution comprises the following components: 15-25.0mg of magnesium sulfate, 2.0-2.5g of disodium hydrogen phosphate, 1.0-1.5g of monopotassium phosphate and 0.5-1.0g of ammonium nitrate, wherein the total mass fraction of the mixed solution is 15% -20%;
(2) Mixing biochar with a soluble ferric salt solution, oscillating at room temperature on a shaking table to perform structural penetration, drying, and roasting at high temperature in a weak oxidizing atmosphere to obtain magnetic biochar;
in the step (1), the corncob is firstly cut into a block structure with the mass-volume ratio of 1:3-4g/mL, and then the block structure is added into the mixed solution; the oscillation time is 18-24h.
2. The method for preparing the magnetic biochar suitable for loading bacillus according to claim 1, wherein the method comprises the following steps: in the step (1), the concentration of the modified corncob is 0.36-0.66g/mL, the temperature is 180-250 ℃ and the time is 4-6h during hydrothermal carbonization.
3. The method for preparing the magnetic biochar suitable for loading bacillus according to claim 1, wherein the method comprises the following steps: in the step (2), the mass-volume ratio of the biochar to the soluble ferric salt solution is 1g:30-40mL, and the mass fraction of the soluble ferric salt solution is 50%; the soluble ferric salt is ferric chloride, ferric sulfate or ferric nitrate; the oscillation time is 4-5h.
4. The method for preparing the magnetic biochar suitable for loading bacillus according to claim 1, wherein the method comprises the following steps: in the step (2), the weak oxidizing atmosphere is a mixed atmosphere of 5% of oxygen and 95% of nitrogen by volume, and the high-temperature roasting temperature is 400-700 ℃ and the time is 2-3h.
5. The method for preparing the magnetic biochar suitable for loading bacillus according to claim 1, wherein the method comprises the following steps: in the step (2), the magnetic biochar is washed by water and then washed by acid or alkali until the pH value is 7.2-7.4.
6. A magnetic biochar produced by the production method of any one of claims 1 to 5.
7. Use of the magnetic biochar according to claim 6, wherein: and after the bacillus is loaded by the magnetic biochar, the magnetic biochar is used for purifying wastewater.
8. The use of magnetic biochar according to claim 7, wherein: the specific process of the magnetic biochar loaded bacillus is as follows: inoculating the bacillus agent into a container filled with LB liquid culture medium according to the inoculum size of 1-5% by volume, culturing for 2-8 hours in an oscillating incubator with the rotation speed of 120-150r/min at 20-35 ℃, adding a magnetic biochar carrier according to 3-5% by weight of the LB liquid culture medium, uniformly mixing the magnetic biochar with bacterial liquid, placing the mixture in a shaking table with the temperature of 35 ℃ and the rotation speed of 90-130r/min for fixing for 1-2 days, taking out the mixture, centrifuging the mixture on a high-speed centrifuge with the rotation speed of 5000-8000r/min after the fixing is finished, removing the culture medium, washing the mixture with 0.85% physiological saline, and carrying out solid-liquid separation to obtain the magnetic biochar loaded with bacillus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010093313.1A CN111206027B (en) | 2020-02-14 | 2020-02-14 | Magnetic biochar suitable for loading bacillus and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010093313.1A CN111206027B (en) | 2020-02-14 | 2020-02-14 | Magnetic biochar suitable for loading bacillus and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111206027A CN111206027A (en) | 2020-05-29 |
| CN111206027B true CN111206027B (en) | 2023-09-29 |
Family
ID=70780878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010093313.1A Active CN111206027B (en) | 2020-02-14 | 2020-02-14 | Magnetic biochar suitable for loading bacillus and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111206027B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113293157A (en) * | 2021-06-18 | 2021-08-24 | 华东理工大学 | Ferroferric oxide modified charcoal immobilized polycyclic aromatic hydrocarbon degrading microbial inoculum and preparation and application thereof |
| CN115228433A (en) * | 2022-07-19 | 2022-10-25 | 安徽省农业科学院植物保护与农产品质量安全研究所 | Preparation method and application of nitrogen-doped modified biochar loaded with microorganisms |
Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648707A (en) * | 2009-08-27 | 2010-02-17 | 南京林业大学 | Preparation method of activated carbon with high pore volume |
| CN102515914A (en) * | 2011-11-28 | 2012-06-27 | 北京师范大学 | Preparation method and use method of biomass carbon fertilizer |
| CN103406099A (en) * | 2013-08-14 | 2013-11-27 | 中国农业大学 | Calcium-magnesium mineralized biocarbon, and preparation method and application thereof |
| CN103566883A (en) * | 2013-10-17 | 2014-02-12 | 复旦大学 | Preparation method of hydrothermal liquefied biochar-based porous carbon and magnetic carbon material and applications of porous carbon and magnetic carbon material |
| CN105001887A (en) * | 2015-07-11 | 2015-10-28 | 全椒盛源生物质能源有限公司 | Processing method for preparing biological carbon from biomass raw material |
| CN105384171A (en) * | 2015-12-18 | 2016-03-09 | 齐鲁工业大学 | Method for preparing active carbon by using corn straw waste residue obtained from xylitol preparation process |
| CN105536700A (en) * | 2015-12-22 | 2016-05-04 | 国家海洋局天津海水淡化与综合利用研究所 | Method for preparing magnetic biochar from straw |
| CN105854799A (en) * | 2016-04-26 | 2016-08-17 | 复旦大学 | Method for preparing magnetic carbon material by activating hydrothermal liquified biochar through CO2 and application of method |
| CN106115938A (en) * | 2016-07-29 | 2016-11-16 | 江苏省农业科学院 | The preparation method of magnetic bio charcoal load photosynthetic bacteria material and sewage water treatment method |
| CN106179222A (en) * | 2016-08-11 | 2016-12-07 | 华中科技大学 | A kind of magnetic green material is burnt and preparation method thereof |
| CN106378100A (en) * | 2016-09-09 | 2017-02-08 | 广西大学 | Impregnated silkworm litter porous charcoal MOFs (Metal organic Framework) composite material, and preparation method and application thereof |
| CN107523561A (en) * | 2017-09-04 | 2017-12-29 | 西南石油大学 | A kind of high temperature alkalization modification biological charcoal base carrier preparation method and application |
| CN107583612A (en) * | 2017-09-28 | 2018-01-16 | 青岛农业大学 | Charcoal preparation method and preparation system and mercury absorbent based on corncob |
| CN107840728A (en) * | 2017-12-20 | 2018-03-27 | 大连工业大学 | A kind of biological carbon-based potash fertilizer synergist and preparation method thereof |
| CN108636356A (en) * | 2018-06-05 | 2018-10-12 | 吉林农业大学 | A kind of cornstalk biological charcoal and restorative procedure that can repair nitrogen phosphorus pollution of area source |
| CN109231204A (en) * | 2018-09-29 | 2019-01-18 | 华中科技大学 | A kind of method of biomass substep activation preparation porous charcoal |
| CN109499538A (en) * | 2018-12-28 | 2019-03-22 | 天津大学 | A kind of iron modified peanut magnetic bio charcoal and its preparation method and application |
| CN110270310A (en) * | 2019-07-25 | 2019-09-24 | 安徽农业大学 | A kind of synchronous high-efficiency recycles the preparation method and applications of the rich magnesium charcoal of nitrogen and phosphorus nutrient in farm's waste liquid |
| CN110559998A (en) * | 2019-10-18 | 2019-12-13 | 清华大学 | Loaded biochar functional material for adsorbing heavy metal ions as well as preparation and application thereof |
| CN110756166A (en) * | 2019-12-03 | 2020-02-07 | 四川农业大学 | Corncob-loaded magnesium-modified adsorption material and preparation method and application thereof |
-
2020
- 2020-02-14 CN CN202010093313.1A patent/CN111206027B/en active Active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648707A (en) * | 2009-08-27 | 2010-02-17 | 南京林业大学 | Preparation method of activated carbon with high pore volume |
| CN102515914A (en) * | 2011-11-28 | 2012-06-27 | 北京师范大学 | Preparation method and use method of biomass carbon fertilizer |
| CN103406099A (en) * | 2013-08-14 | 2013-11-27 | 中国农业大学 | Calcium-magnesium mineralized biocarbon, and preparation method and application thereof |
| CN103566883A (en) * | 2013-10-17 | 2014-02-12 | 复旦大学 | Preparation method of hydrothermal liquefied biochar-based porous carbon and magnetic carbon material and applications of porous carbon and magnetic carbon material |
| CN105001887A (en) * | 2015-07-11 | 2015-10-28 | 全椒盛源生物质能源有限公司 | Processing method for preparing biological carbon from biomass raw material |
| CN105384171A (en) * | 2015-12-18 | 2016-03-09 | 齐鲁工业大学 | Method for preparing active carbon by using corn straw waste residue obtained from xylitol preparation process |
| CN105536700A (en) * | 2015-12-22 | 2016-05-04 | 国家海洋局天津海水淡化与综合利用研究所 | Method for preparing magnetic biochar from straw |
| CN105854799A (en) * | 2016-04-26 | 2016-08-17 | 复旦大学 | Method for preparing magnetic carbon material by activating hydrothermal liquified biochar through CO2 and application of method |
| CN106115938A (en) * | 2016-07-29 | 2016-11-16 | 江苏省农业科学院 | The preparation method of magnetic bio charcoal load photosynthetic bacteria material and sewage water treatment method |
| CN106179222A (en) * | 2016-08-11 | 2016-12-07 | 华中科技大学 | A kind of magnetic green material is burnt and preparation method thereof |
| CN106378100A (en) * | 2016-09-09 | 2017-02-08 | 广西大学 | Impregnated silkworm litter porous charcoal MOFs (Metal organic Framework) composite material, and preparation method and application thereof |
| CN107523561A (en) * | 2017-09-04 | 2017-12-29 | 西南石油大学 | A kind of high temperature alkalization modification biological charcoal base carrier preparation method and application |
| CN107583612A (en) * | 2017-09-28 | 2018-01-16 | 青岛农业大学 | Charcoal preparation method and preparation system and mercury absorbent based on corncob |
| CN107840728A (en) * | 2017-12-20 | 2018-03-27 | 大连工业大学 | A kind of biological carbon-based potash fertilizer synergist and preparation method thereof |
| CN108636356A (en) * | 2018-06-05 | 2018-10-12 | 吉林农业大学 | A kind of cornstalk biological charcoal and restorative procedure that can repair nitrogen phosphorus pollution of area source |
| CN109231204A (en) * | 2018-09-29 | 2019-01-18 | 华中科技大学 | A kind of method of biomass substep activation preparation porous charcoal |
| CN109499538A (en) * | 2018-12-28 | 2019-03-22 | 天津大学 | A kind of iron modified peanut magnetic bio charcoal and its preparation method and application |
| CN110270310A (en) * | 2019-07-25 | 2019-09-24 | 安徽农业大学 | A kind of synchronous high-efficiency recycles the preparation method and applications of the rich magnesium charcoal of nitrogen and phosphorus nutrient in farm's waste liquid |
| CN110559998A (en) * | 2019-10-18 | 2019-12-13 | 清华大学 | Loaded biochar functional material for adsorbing heavy metal ions as well as preparation and application thereof |
| CN110756166A (en) * | 2019-12-03 | 2020-02-07 | 四川农业大学 | Corncob-loaded magnesium-modified adsorption material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 玉米秸秆和玉米芯生物炭对水溶液中无机氮的吸附性能;武丽君;王朝旭;张峰;崔建国;;中国环境科学(01);第74-81页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111206027A (en) | 2020-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109628353B (en) | Biochar-based immobilized microbial agent as well as preparation method and application thereof | |
| CN110127972B (en) | Method for improving anaerobic digestion efficiency of sludge and simultaneously reducing heavy metal ecotoxicity | |
| CN109536173B (en) | Composite material for simultaneously repairing heavy metal and glyphosate and preparation method thereof | |
| CN109734199A (en) | Immobilized microorganism structural body and preparation method thereof | |
| CN111389367A (en) | Metal sludge-based biochar, preparation method and application in removing nitrogen and phosphorus in water body | |
| CN111206027B (en) | Magnetic biochar suitable for loading bacillus and preparation method and application thereof | |
| CN110078332B (en) | Method for promoting anaerobic fermentation of excess sludge to produce acid by using modified steel slag | |
| CN113731363A (en) | Adsorbent and preparation method and application thereof | |
| CN106479935A (en) | A kind of preparation method of use in waste water treatment denitrification denitrogenation microbial inoculum | |
| CN110614078A (en) | Preparation of potassium permanganate modified heavy metal cadmium adsorbent | |
| CN109225187B (en) | Preparation method and application of sludge-based ceramic-based catalyst | |
| CN110922010A (en) | Benthic microorganism ecological restoration agent for black and odorous water body sediment and preparation method thereof | |
| CN114308037A (en) | Adsorption and catalysis double-effect material and preparation method and application thereof | |
| CN109052650B (en) | Preparation of immobilized microalgae water quality control agent | |
| CN114645041A (en) | Bottom sediment-improved composite microbial inoculum and preparation method thereof | |
| CN115771951A (en) | Method for removing nitrogen and phosphorus from aquaculture wastewater | |
| CN112391375B (en) | Preparation method and application of biochar immobilized denitrifying bacteria for rapidly removing nitrate in water body | |
| CN113372602B (en) | Preparation method of biomass aerogel and magnetic microbial ball | |
| CN101392245B (en) | Preparation and application of flocculating alcaligenes faecalis fixed pellet | |
| CN115121239A (en) | Preparation method and application of biochar catalyst | |
| CN111676151B (en) | Low-temperature-resistant phosphorus accumulating bacterium and application thereof | |
| CN109896703B (en) | Light-enzyme composite catalytic function microorganism water purifying agent for culturing anaerobic sewage | |
| CN111995063A (en) | Powdered activated carbon carrier and preparation method and application thereof | |
| CN110818180A (en) | Method for digesting black and odorous river channel by using microbial preparation | |
| CN112708613B (en) | Preparation method of biological denitrification agent based on multifunctional carrier immobilization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |