CN112707509B - Method for removing heavy metals in water body by using marine microalgae - Google Patents
Method for removing heavy metals in water body by using marine microalgae Download PDFInfo
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- 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
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
- C02F3/322—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
Abstract
The invention provides a method for removing heavy metals in a water body by using marine microalgae, which relates to the technical field of environmental protection and comprises the following steps: preparing biochar-based microalgae particles; and adding the biochar-based microalgae particles into the water body polluted by the heavy metal for adsorption and purification. The biochar-based microalgae particles comprise a biochar matrix and microalgae; pre-culturing, domesticating and pre-treating the microalgae seeds, mixing, and forming immobilized particles with biochar; the microalgae include Chlorella vulgaris, Chlorella pyrenoidosa, Chlorella ellipsoidea, and Cyclotella minitans. According to the method provided by the invention, the microalgae and the biochar matrix are solidified to form particles, and the concentration and the quantity of the phycoprotein secreted by the phycosomes are increased by improving the expression abundance of the phycoprotein in the microalgae, so that the adsorption capacity and the adsorption efficiency of the microalgae to heavy metal ions are improved, the adsorption capacity and the service life of the biochar-based microalgae particles are prolonged, and the purposes of efficiently removing heavy metals and easily recovering the phycosomes are achieved.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a method for removing heavy metals in a water body by using marine microalgae.
Background
The rapid development of social economy and the huge consumption of energy cause the industries such as mining, ferrous metallurgy, mechanical processing and the like to rise rapidly, so that the situation that the mining and utilization of heavy metal substances are expanded continuously is caused, and more potential safety hazards are brought along. Heavy metal (metal elements with specific gravity of more than 5 and relative atomic mass of 63.5-200.6) discharged from industry pollutes wastewater and has serious harm and causes permanent damage to the environment and the health of life bodies. The industrial wastewater usually contains heavy metal elements such As Pb, Hg, Ni, Cr, Cd, As, Zn, Ti, etc.
As an indispensable substance for living of organisms, water is the best medium for heavy metal pollution. Heavy metals are extremely difficult to degrade, are continuously enriched in organisms, and can cause various diseases such as central nervous system, kidney, liver injury and the like after being ingested by human bodies, so that the removal or reduction of heavy metal ion pollution is one of the main problems facing the current society. Therefore, China has definite discharge standards for various heavy metal-containing wastewater. However, a large amount of wastewater containing heavy metals still enters the water body due to the current water treatment technology and the like. In addition, even if the heavy metal wastewater reaches the standard and is discharged, the accumulative pollution caused by the chemical stability of the heavy metal wastewater cannot be ignored.
The traditional method for treating the heavy metal polluted water mainly comprises physical, chemical and biological methods, including a precipitation method, a chelating resin method, a high-molecular trapping agent method, a natural zeolite adsorption method, a membrane technology, an activated carbon adsorption process, an ion exchange method and the like. However, the traditional methods of ion exchange, membrane filtration, chemical precipitation, electrolysis, reverse osmosis and the like are adopted to remove heavy metal ions in water, and the ion exchange resin used by the ion exchange method has poor heat resistance and poor cycle regeneration; the membrane filtration method has the defect of overhigh later maintenance cost; the chemical precipitation method can generate a large amount of sludge in the treatment process to cause secondary pollution; the electrolysis method has large power consumption and high cost, and is not suitable for treating low-concentration heavy metal ion wastewater; the reverse osmosis method has high energy consumption and high cost.
Research shows that the algae has excellent adsorption and enrichment capacity on heavy metals. In the 20 th century, algae have been applied to the environmental field, and compared with traditional physical and chemical methods, the method for repairing heavy metals by using microalgae has the following advantages: (1) the adsorption effect is fast, the retention time is short, and the energy consumption is saved; (2) microalgae can obtain a carbon source and energy by photosynthesis, the growth of the microalgae is ensured without additionally providing a carbon source, the cost is low, and continuous organic matter supply is not needed; (3) the recovered heavy metal is easy to elute, and can be desorbed and reused by using a simple chemical reagent; (4) the sewage is rich in nitrogen and phosphorus, so that good inorganic nutrition is provided for microalgae propagation, the microalgae is high in growth speed, and the source is rich; (5) the environment is protected, and no waste is generated; (6) the surface-to-volume ratio is large, and the adsorption efficiency is high; (7) has good removal effect under high heavy metal concentration and low heavy metal concentration. Therefore, the natural algae is used as the biological adsorbent to treat and repair the heavy metal polluted wastewater, and has good application value and prospect.
However, although many microalgae have a certain heavy metal ion adsorption capacity, the adsorption efficiency of the existing natural microalgae to the heavy metal ions is limited, and many microalgae have poor tolerance to the heavy metal ions, and also have the disadvantages of low mechanical properties, poor chemical stability and the like, which greatly limits the practical application of the microalgae. Therefore, there is a need to research new microalgae capable of efficiently adsorbing heavy metal ions and a method for removing heavy metals from water by using marine microalgae.
Disclosure of Invention
One of the purposes of the invention is to provide the biochar-based microalgae particles which have high adsorption capacity, long service life, high heavy metal removal efficiency and easy algae recovery.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a biochar-based microalgae particle comprises a biochar matrix and microalgae;
pre-culturing, domesticating and pre-treating the microalgae seeds, mixing, and forming immobilized particles with biochar;
the acclimatization is carried out in a metal ion mixed solution with the ion concentration not more than 0.3 mg/L;
the microalgae include Chlorella vulgaris, Chlorella pyrenoidosa, Chlorella ellipsoidea, and Cyclotella minitans.
Through the technical scheme, the method can obtain the biochar-based microalgae particles which have the advantages of high adsorption capacity, long service life, high heavy metal removal efficiency and easy recovery of algae by adsorbing and complexing heavy metal ions by utilizing the microalgae and the algae protein secreted by the algae and simultaneously utilizing the adsorption effect of the biochar matrix on the heavy metal.
According to the invention, Fe is contained in the metal ion mixed solution2+、Fe3+、Al3+、Zn2+The weight ratio of the ions is 0.5:0.5-1:1-2: 1. The stress acclimation of the microalgae is carried out by adopting the low-concentration heavy metal ion solution, the microalgae can adapt to the heavy metal ion environment in advance, the environment can be quickly adapted after the microalgae enters the polluted water body, the heavy metal ions are adsorbed and purified, and the capability of removing the heavy metal ions from the microalgae is beneficially improved.
According to the invention, the domestication conditions are as follows: the pH value is 7-8, the illumination intensity is 4000-.
Preferably, Chlorella vulgaris and Chlorella ellipsoidea are cultured in HB111 medium, Cyclotella metini is cultured in D1 medium, and Chlorella pyrenoidosa is cultured in BG11 medium. More preferably, the pre-culture is performed under the same culture conditions as the acclimatized culture for 2-5 days.
Preferably, the pretreatment step is: collecting algae after acclimation, mixing the algae according to the weight ratio of 1:1:1:1-3, putting the mixture into 0.05-0.15mol/L hydrochloric acid solution, stirring and soaking for 30-60min, washing residual chloride ions with distilled water, and collecting mixed microalgae for later use. The hydrochloric acid can wash away metal ions and part of soluble substances adsorbed by the algae in the domestication process, can purify and increase adsorption points of the algae, and is beneficial to subsequent adsorption of heavy metal ions in the water body.
The invention also provides the application of the biochar-based microalgae particles in wastewater treatment, wherein the wastewater is industrial wastewater, agricultural wastewater or domestic wastewater; the treatment effect of the biochar-based microalgae particles is to remove nitrogen, phosphorus and heavy metals in wastewater.
Another objective of the present invention is to provide a method for preparing biochar-based microalgae particles, which can increase the expression abundance of algal proteins of microalgae, increase the concentration and quantity of algal proteins secreted by the algal cells, and increase the adsorption capacity and adsorption efficiency of heavy metal ions by microalgae, the method comprising:
pre-culturing, domesticating and pre-treating the microalgae seeds, and mixing to obtain mixed microalgae; the domestication is carried out in a metal ion mixed solution with the ion concentration of 0.2-0.3 mg/L;
the preparation of the above-mentioned biochar, and,
mixing the mixed microalgae with the biochar, and adding CaCl into sodium alginate solution2Curing and forming;
the microalgae species include Chlorella vulgaris, Chlorella pyrenoidosa, Chlorella ellipsoidea and Cyclotella merrina, and the above algae species are mixed at a weight ratio of 1:1:1: 1-3.
Through the technical scheme, the microalgae is fully adhered to the surface of the biochar and the pores of the biochar, and then is further solidified into particles, when heavy metals are removed from a polluted water body, the biochar and the microalgae can absorb a large amount of heavy metals in a solution, meanwhile, the existence of the activated carbon also enables microalgae cells to keep activity in a relatively low heavy metal solution, and heavy metal ions are adsorbed by metabolic products such as algal proteins and the like secreted by the algal bodies, so that the adsorption capacity and the service life of the biochar-based microalgae particles are improved, and the method has the advantages of high heavy metal removal rate, easiness in algal body recovery and the like.
According to the invention, the biochar is obtained by pre-baking the agricultural and forestry waste at the temperature of 100-150 ℃ and carbonizing the agricultural and forestry waste for 2-6h at the temperature of 400-500 ℃. Preferably, the prebaking time is 12-16h, after the prebaking is finished, the prebaked product is crushed to the particle size of 0.2-5mm, and then carbonization is carried out. The agricultural and forestry waste is prebaked in advance, so that the porosity of the agricultural and forestry waste can be further enlarged, the contact area of the biochar and the heavy metal is increased, and the adsorption effect and the storage amount of the heavy metal are improved. The biochar has various functional groups, such as amino, phosphate, carboxyl, organic hydroxyl and the like, and can chelate heavy metals in a water body, a large amount of negative charges and adsorption sites on the surface of the biochar are favorable for adsorbing heavy metal ions with positive charges, and the removal effect of the heavy metals can be further improved.
According to the invention, the metal ion mixed solution also contains 0.02-0.04mg/L of 3-mercaptopropionic acid and 0.01-0.05mg/L of sodium methallyl sulfonate. The 3-mercaptopropionic acid and the sodium methallylsulfonate are matched with heavy metal ions to carry out the collaborative domestication culture on the microalgae, the algae are probably stimulated to maintain the balance state of algae cells in a stress environment by adjusting the protein metabolism level, the expression abundance of algae proteins is effectively improved after the microalgae are subjected to the collaborative domestication process, the concentration and the quantity of the algae proteins secreted by the algae are increased, the algae proteins secreted by the microalgae have a good adsorption effect on the heavy metals, and therefore the adsorption quantity and the adsorption efficiency of the microalgae on the heavy metal ions can be further improved.
According to the invention, the curing and forming steps are as follows: the biochar and the mixed microalgae are vibrated and mixed for 12 to 24 hours under the conditions that the rotating speed is 200-2Solidifying the solution for 1-2h, washing with deionized water to obtain biochar-based microalgae particles, and drying in an oven at 40-60 ℃ to constant weight.
Further setting the weight ratio of the biochar to the mixed microalgae to be 1:1-3, the weight ratio of the mixture of the mixed microalgae and the biochar to the sodium alginate solution to be 20-35%, and the sodium alginate solution and CaCl2The weight ratio of the solution is 1: 0.8-1.5.
Preferably, the agricultural and forestry waste comprises wood chips, straws, fruit shells, barks and the like.
Most importantly, in order to achieve the formation of granules by solidification of the microalgae and biochar matrix; the method increases the concentration and the quantity of the phycobioproteins secreted by the phycobionts and improves the adsorption capacity and the adsorption efficiency of the microalgae on heavy metal ions by improving the expression abundance of the phycobioproteins in the microalgae, thereby improving the adsorption capacity and the service life of biochar-based microalgae particles, and finally achieving the purposes of efficiently removing heavy metals and easily recovering the phycobionts.
Preparing the biochar-based microalgae particles according to the preparation method; and the combination of (a) and (b),
adding the biochar-based microalgae particles into a water body polluted by heavy metal for adsorption and purification;
the using amount of the biochar-based microalgae particles in a water body is not less than 0.3 g/L. The method combines the characteristics of low consumption, stability and reusability of the biochar with the characteristic of high-efficiency enrichment of nitrogen, phosphorus and heavy metals in the microalgae, improves the removal efficiency of heavy metal pollutants, realizes removal and resource recycling of heavy metal ions in the wastewater, and can consume nutrient-rich substances such as nitrogen, phosphorus and the like in the wastewater through growth and metabolism of the microalgae while quickly removing the heavy metals in the biochar, the microalgae and microalgae secretions to achieve the effect of deeply purifying the water body.
Test results show that the biochar-based microalgae particles have strong adsorption effects on lead, copper, zinc, iron, cadmium, barium, aluminum, chromium and nickel ions, have different adsorption effects on different metal ions, and have adsorption capacity of over 350mg/g, wherein the adsorption capacity on the zinc, the iron and the aluminum can be over 500 mg/g.
The invention adopts microalgae and biochar matrix to form particles by solidification, and is used for removing heavy metals in polluted water bodies, thereby having the following beneficial effects: 1) the biochar-based microalgae particles have the advantages of high adsorption capacity, long service life, high heavy metal removal efficiency and easiness in algae recovery; 2) the stress acclimation is carried out on the microalgae by mutually matching the low-concentration heavy metal ion solution, the 3-mercaptopropionic acid and the sodium methallylsulfonate, so that the microalgae can be favorably adapted to the heavy metal ion environment in advance, the expression abundance of the algal protein of the microalgae can be improved, the concentration and the quantity of the algal protein secreted by the microalgae can be increased, and the adsorption quantity and the adsorption efficiency of the microalgae on the heavy metal ions can be improved; 3) the biochar-based microalgae particles are used in heavy metal polluted water, biochar and microalgae can absorb a large amount of heavy metals in a solution, meanwhile, the existence of activated carbon enables microalgae cells to keep activity in a relatively low heavy metal solution, and rich nutrients such as nitrogen and phosphorus in wastewater are consumed through the growth and metabolism of microalgae, so that the effect of deeply purifying the water is achieved.
Drawings
FIG. 1 is a schematic diagram showing the change of protein concentration of microalgae obtained from different embodiments of acclimatization step;
FIG. 2 shows the results of measuring the adsorption capacity of mixed microalgae obtained in different examples;
fig. 3 shows the mechanical strength test results of the biochar-based microalgae particles prepared by different methods under different acid-base conditions.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
in a specific implementation scenario, Chlorella vulgaris, Chlorella pyrenoidosa, Chlorella ellipsoidea, and Chlorella minutissima are purchased from Shanghai plain Biotechnology Ltd.
In a specific implementation scene, the chlorella vulgaris and the chlorella ellipsoidea adopt HB111 culture medium, the Cyclotella metini adopts D1 culture medium, and the chlorella pyrenoidosa adopts BG11 culture medium.
In a specific implementation scenario, in the step of solidification and molding, sodium alginate is added into deionized water at 80-90 ℃ to prepare a solution with the concentration of 1.5-2wt%, after cooling, the mixture of the mixed microalgae and the biochar is added into the sodium alginate solution, and the solidification is completed after uniform stirring.
In a specific implementation scene, when the concentration of heavy metals in the polluted water body is lower than 100mg/L, the using amount of the biochar-based microalgae particles in the water body is 0.3-0.5 g/L; when the concentration of the heavy metal in the polluted water body is 100-500mg/L, the usage amount of the biochar-based microalgae particles in the water body is 0.5-0.8 g/L; when the concentration of heavy metal in the polluted water body is higher than 500mg/L, the using amount of the biochar-based microalgae particles in the water body is not lower than 0.8 g/L.
As an improvement of the proposal, in the step of solidification and forming, CaCl is added2The solution is also added with 0.01 to 0.1 weight percent of uracil-5-carboxylic acid and 0.01 to 0.5 weight percent of m-aminoacetanilide. In the solidification process, the biochar, sodium alginate and microalgae are combined with each other to form a stable solid structure, the intervention of uracil-5-carboxylic acid and m-aminoacetanilide provides a new group and an active adsorption site, and simultaneously, the mechanical strength and the acid and alkali resistance of product particles can be improved, so that the biochar-based microalgae particles oscillate in an acid-base solution for more than 48 hours, the stability and the recoverability of the biochar-based microalgae particles in a water body are improved, in addition, the desorption rate of adsorbed heavy metals in the particles can be reduced, the fixed binding capacity of heavy metal ions in the particles is enhanced, the purpose of fixing the heavy metals without easy desorption is achieved, and the desorption and secondary pollution caused by the change of the water body environment can be avoided.
The present invention and the conventional techniques in the embodiments are known to those skilled in the art and will not be described in detail herein.
It is to be understood that the foregoing description is to be considered illustrative or exemplary and not restrictive, and that changes and modifications may be made by those skilled in the art within the scope and spirit of the appended claims. In particular, the present invention covers other embodiments having any combination of features from the different embodiments described above and below, without the scope of the invention being limited to the specific examples below.
Example 1:
the method for removing the heavy metals in the water body by using the marine microalgae comprises the following steps:
1) pre-culturing: selecting biological algae species of common chlorella, chlorella pyrenoidosa, chlorella ellipsoidea and chlorella intermedia, respectively inoculating the biological algae species into a culture medium subjected to high-pressure sterilization for pre-culture, wherein the culture conditions are as follows: pH of 7.5, light intensity of 4500Lx, light dark period of 14h:10h, temperature of 28 deg.C, and culture time of 5D, wherein the above Chlorella vulgaris and Chlorella ellipsoidea adopt HB111 culture medium, Cyclotella metschnikowii adopts D1 culture medium, and Chlorella pyrenoidosa adopts BG11 culture medium;
2) domestication: respectively adding a metal ion mixed solution with the concentration of 0.2mg/L into the pre-cultured algae and the culture medium thereof for acclimatization culture, wherein the culture conditions are as follows: the pH value is 7.5, the illumination intensity is 4500Lx, the light dark period is 14h:10h, the temperature is 28 ℃, the time is 4d, and Fe in the metal ion mixed solution2+、Fe3+、Al3+、Zn2+The weight ratio of ions is 0.5:0.75:1.25: 1; the metal ion mixed solution also contains 0.02mg/L of 3-mercaptopropionic acid and 0.04mg/L of sodium methallyl sulfonate;
3) pretreatment: after the acclimatization is finished, centrifuging and collecting algae seeds, then mixing the algae seeds according to the weight ratio of 1:1:1:2.5, then placing the mixture into 0.1mol/L hydrochloric acid solution, stirring and soaking for 60min, washing residual chloride ions by using distilled water, and collecting mixed microalgae for later use;
4) collecting agricultural and forestry wastes, prebaking the agricultural and forestry wastes in an oven at the temperature of 130 ℃ for 12 hours, then crushing the agricultural and forestry wastes until the particle size is less than 3mm, and then carbonizing the agricultural and forestry wastes for 4 hours at the temperature of 500 ℃ to obtain biochar; the agricultural and forestry waste is straws and barks in a weight ratio of 1: 1;
5) curing and forming: shaking and mixing biochar and mixed microalgae at rotation speed of 200rpm and illumination intensity of 3000Lx for 16h, adding sodium alginate into 80 deg.C deionized water to obtain 2wt% solution, cooling, adding the mixture of mixed microalgae and biochar into sodium alginate solution, stirring, and dripping 2wt% CaCl2Solidifying the solution for 2 hours, washing the solution with deionized water to obtain biochar-based microalgae particles, and drying the biochar-based microalgae particles in an oven at 50 ℃ to constant weight; the weight ratio of the biochar to the mixed microalgae is 1:2.5, the weight ratio of the mixture of the mixed microalgae and the biochar in the sodium alginate solution is 30 percent, and the sodium alginate solution and CaCl are added2The weight ratio of the solution is 1: 1.5;
6) adding the obtained biochar-based microalgae particles into a water body polluted by heavy metal for adsorption and purification; the using amount of the biochar-based microalgae particles in a water body is not less than 0.3 g/L.
Example 2:
the method for removing the heavy metals in the water body by using the marine microalgae is different from the method in the embodiment 1 only in the following steps:
step 5) in solidification forming, the biochar and the mixed microalgae are vibrated and mixed for 16 hours under the conditions that the rotating speed is 200rpm and the illumination intensity is 3000Lx, sodium alginate is added into deionized water at 80 ℃ to prepare a solution with the concentration of 2wt%, after cooling, the mixture of the mixed microalgae and the biochar is added into the sodium alginate solution, after even stirring, CaCl with the concentration of 2wt% is dripped in2Solidifying the solution for 2 hours, washing the solution with deionized water to obtain biochar-based microalgae particles, and drying the biochar-based microalgae particles in an oven at 50 ℃ to constant weight; above CaCl20.05 wt% of uracil-5-carboxylic acid and 0.015 wt% of m-aminoacetanilide are also added into the solution; the weight ratio of the biochar to the mixed microalgae is 1:2.5, the weight ratio of the mixture of the mixed microalgae and the biochar in the sodium alginate solution is 30 percent, and the sodium alginate solution and CaCl are added2The weight ratio of the solution was 1: 1.5.
Example 3:
the method for removing the heavy metals in the water body by using the marine microalgae is different from the method in the embodiment 1 only in the following steps:
step 2) domestication: respectively adding a metal ion mixed solution with the concentration of 0.2mg/L into the pre-cultured algae and the culture medium thereof for acclimatization culture, wherein the culture conditions are as follows: the pH value is 7.5, the illumination intensity is 4500Lx, the light dark period is 14h:10h, the temperature is 28 ℃, the time is 4d, and Fe in the metal ion mixed solution2+、Fe3+、Al3+、Zn2+The weight ratio of ions is 0.5:0.75:1.25: 1; the metal ion mixed solution also contains 0.02mg/L of 3-mercaptopropionic acid, and sodium methallyl sulfonate is not added.
Example 4:
the method for removing the heavy metals in the water body by using the marine microalgae is different from the method in the embodiment 1 only in the following steps:
step 2) domestication: respectively adding a metal ion mixed solution with the concentration of 0.2mg/L into the pre-cultured algae and the culture medium thereof for acclimatization culture, wherein the culture conditions are as follows: the pH value is 7.5, the illumination intensity is 4500Lx, the light dark period is 14h:10h, the temperature is 28 ℃, the time is 4d, and Fe in the metal ion mixed solution2+、Fe3+、Al3+、Zn2+The weight ratio of ions is 0.5:0.75:1.25: 1; the metal ion mixed solution also contains 0.04mg/L sodium methallyl sulfonate, and 3-mercaptopropionic acid is not added.
Example 5:
the method for removing the heavy metals in the water body by using the marine microalgae is different from the method in the embodiment 1 only in the following steps:
step 2) domestication: respectively adding a metal ion mixed solution with the concentration of 0.2mg/L into the pre-cultured algae and the culture medium thereof for acclimatization culture, wherein the culture conditions are as follows: the pH value is 7.5, the illumination intensity is 4500Lx, the light dark period is 14h:10h, the temperature is 28 ℃, the time is 4d, and Fe in the metal ion mixed solution2+、Fe3+、Al3+、Zn2+The weight ratio of ions was 0.5:0.75:1.25: 1.
Example 6:
the method for removing the heavy metals in the water body by using the marine microalgae is different from the method in the embodiment 1 only in the following steps:
step 2) domestication: respectively adding a solution containing 0.02mg/L of 3-mercaptopropionic acid and 0.04mg/L of sodium methallyl sulfonate into the pre-cultured algae and the culture medium thereof for acclimatization culture, wherein the culture conditions are as follows: the pH value is 7.5, the illumination intensity is 4500Lx, the light dark period is 14h:10h, the temperature is 28 ℃, and the time is 4 d; namely, the mixed solution of metal ions is not added in the acclimatization process.
Example 7:
the method for removing the heavy metals in the water body by using the marine microalgae is different from the method in the embodiment 2 only in that:
step 5) in solidification forming, the biochar and the mixed microalgae are vibrated and mixed for 16 hours under the conditions that the rotating speed is 200rpm and the illumination intensity is 3000Lx, sodium alginate is added into deionized water at 80 ℃ to prepare a solution with the concentration of 2wt%, after cooling, the mixture of the mixed microalgae and the biochar is added into the sodium alginate solution, after even stirring, CaCl with the concentration of 2wt% is dripped in2Solidifying the solution for 2 hours, washing the solution with deionized water to obtain biochar-based microalgae particles, and drying the biochar-based microalgae particles in an oven at 50 ℃ to constant weight; above CaCl20.05 wt% of uracil-5-carboxylic acid and 0.0 wt% of m-aminoacetanilide are also added into the solution; the weight ratio of the biochar to the mixed microalgae is 1:2.5, the weight ratio of the mixture of the mixed microalgae and the biochar in the sodium alginate solution is 30 percent, and the sodium alginate solution and CaCl are added2The weight ratio of the solution was 1: 1.5.
Example 8:
the method for removing the heavy metals in the water body by using the marine microalgae is different from the method in the embodiment 2 only in that:
step 5) in solidification forming, the biochar and the mixed microalgae are vibrated and mixed for 16 hours under the conditions that the rotating speed is 200rpm and the illumination intensity is 3000Lx, sodium alginate is added into deionized water at 80 ℃ to prepare a solution with the concentration of 2wt%, after cooling, the mixture of the mixed microalgae and the biochar is added into the sodium alginate solution, after even stirring, CaCl with the concentration of 2wt% is dripped in2Solidifying in the solution for 2h, washing with deionized water to obtain biochar-based microalgae particles, and placing in an oven at 50 deg.CDrying at the temperature of DEG C to constant weight; above CaCl20.0 wt% of uracil-5-carboxylic acid and 0.015 wt% of m-aminoacetanilide are also added into the solution; the weight ratio of the biochar to the mixed microalgae is 1:2.5, the weight ratio of the mixture of the mixed microalgae and the biochar in the sodium alginate solution is 30 percent, and the sodium alginate solution and CaCl are added2The weight ratio of the solution was 1: 1.5.
Example 9:
the method for removing the heavy metals in the water body by using the marine microalgae is different from the method in the embodiment 1 only in the following steps:
and 3) directly curing and forming the mixed microalgae after obtaining the mixed microalgae, namely fixing the microalgae without a biochar matrix, and specifically comprising the following steps: adding sodium alginate into 80 deg.C deionized water to obtain 2wt% solution, cooling, adding mixed microalgae into sodium alginate solution, stirring, and adding 2wt% CaCl2Solidifying the solution for 2 hours, washing the solution with deionized water to obtain microalgae particles, and drying the microalgae particles in an oven at 50 ℃ to constant weight; the weight ratio of the mixed microalgae in the sodium alginate solution is 30 percent, and the sodium alginate solution and CaCl are mixed2The weight ratio of the solution is 1: 1.5;
example 10:
the method for removing the heavy metals in the water body by using the marine microalgae is not used during working, and only biochar is used for directly carrying out solidification molding, and the specific steps comprise the steps 4), 5) and 6) in the embodiment 1, and are only different from the embodiment 1 in that:
step 5) in the solidification forming, sodium alginate is added into deionized water at 80 ℃ to prepare a solution with the concentration of 2wt%, after cooling, biochar is added into the sodium alginate solution, and after stirring uniformly, CaCl with the concentration of 2wt% is dripped in2Solidifying the solution for 2 hours, washing the solution with deionized water to obtain biochar particles, and drying the biochar particles in an oven at 50 ℃ to constant weight; the weight ratio of the biochar in the sodium alginate solution is 30 percent, and the sodium alginate solution and CaCl are mixed2The weight ratio of the solution was 1: 1.5.
Example 11:
use of marine microalgae for removingThe process for removing heavy metals from water, when working, differs from example 1 only in that: the biochar and the mixed microalgae are not subjected to solidification forming, and the method comprises the following specific steps: step 5) in the solidification molding, the biochar and the mixed microalgae are subjected to oscillation mixing for 16 hours under the conditions that the rotating speed is 200rpm and the illumination intensity is 3000Lx, and then the mixture is dried in an oven at 50 ℃ to constant weight, so that the biochar matrix microalgae particles are obtained; above CaCl20.0 wt% of uracil-5-carboxylic acid and 0.015 wt% of m-aminoacetanilide are also added into the solution; the weight ratio of the biochar to the mixed microalgae is 1:2.5, the weight ratio of the mixture of the mixed microalgae and the biochar in the sodium alginate solution is 30 percent, and the sodium alginate solution and CaCl are added2The weight ratio of the solution was 1: 1.5.
Experimental example 1:
adsorption capacity test of different methods for removing heavy metals in water body
The experimental method comprises the following steps: preparing biochar-based microalgae particles according to the methods of examples 1, 2 and 9-11 respectively, and then preparing 1L of lead, copper, zinc, iron, cadmium, barium, aluminum, chromium and nickel ion solutions containing 750mg/L respectively; and then adding the biochar-based microalgae particles prepared in different embodiments into the metal ion solution in an amount of 1g/L, adsorbing for 24 hours, testing the metal ion concentration in the adsorbed liquid, and calculating the adsorption quantity of different metal ions by using an atomic absorption spectrum testing instrument. The adsorption amount is (Co-Ce) × V/M, Co (mg/L) is the initial concentration of the heavy metal solution before adsorption, Ce (mg/L) is the concentration of the remaining heavy metal in the solution when adsorption reaches equilibrium, V (L) is the volume of the heavy metal solution, and M (g) is the mass of the charcoal-based microalgae particles. The results are shown in Table 1.
TABLE 1 adsorption capacity in mg/g for different methods for removing heavy metals from water
| Lead (II) | Copper (Cu) | Zinc | Iron | Cadmium (Cd) | Barium salt | Aluminium | Chromium (III) | Nickel (II) | |
| Example 1 | 405.2 | 455.4 | 516.3 | 621.4 | 413.1 | 406.8 | 572.1 | 436.5 | 439.9 |
| Example 2 | 432.5 | 458.6 | 579.4 | 662.1 | 452.9 | 415.2 | 601.3 | 462.7 | 496.1 |
| Example 9 | 302.5 | 366.4 | 395.7 | 401.3 | 322.1 | 304.8 | 326.5 | 284.2 | 334.6 |
| Example 10 | 212.4 | 235.8 | 301.7 | 355.7 | 267.4 | 234.5 | 352.7 | 205.8 | 224.8 |
| Example 11 | 384.5 | 401.8 | 446.8 | 487.6 | 357.6 | 348.7 | 428.6 | 328.1 | 350.8 |
Test results show that the biochar-based microalgae particles in examples 1 and 2 have the best effect of removing heavy metal ions, wherein the biochar-based microalgae particles have stronger adsorption effect on lead, copper, zinc, iron, cadmium, barium, aluminum, chromium and nickel ions, have different adsorption effects on different metal ions, and have adsorption capacity of over 400mg/g, particularly over 500 mg/g.
The results show that the adsorption capacity of the biochar-based microalgae particles of example 1 and examples 9-11 is significantly different, which indicates that the invention makes the microalgae sufficiently adhere to the surface of the biochar and the pores thereof, and then utilizes sodium alginate and CaCl2The further solidification is graininess, when getting rid of heavy metal in the polluted water body, biochar and little algae can both absorb a large amount of heavy metal in the solution, and the existence of active carbon also makes little algae cell keep the activity in relatively lower heavy metal solution simultaneously to adsorb heavy metal ion through metabolic products such as alga body self and alga body protein of secreting to improve the adsorption capacity and the life of biochar base little algae granule, have advantages such as heavy metal clearance height, alga body recovery are easy.
Experimental example 2:
effect of different methods on algal body proteins and adsorption Capacity of microalgae
The experimental method comprises the following steps: biochar-based microalgae particles were prepared according to the methods of examples 1, 3-6, respectively, and the microalgae therein were subjected to measurement of algal proteins, with the microalgae obtained by pre-culture as a blank group. The microalgae obtained in the acclimatization steps of different embodiments are taken as experimental samples, protein is extracted by adopting a phenol extraction method, and the protein concentration is measured according to a Bradford protein measurement method. Meanwhile, the adsorption capacity and the adsorption rate of the mixed microalgae obtained in each embodiment are measured, the sample solution is 1L of copper ion solution with the concentration of 500mg/L, then the microalgae obtained in the acclimation step prepared in different embodiments are added into the metal ion solution in an amount of 0.7g/L, after 24 hours of adsorption, the metal ion concentration in the adsorbed liquid is tested, and the test instrument is an atomic absorption spectrum, and the adsorption capacity of different metal ions is calculated. The adsorption amount (mg/g) ═ Co-Ce × V/M, the adsorption rate% ((Co-Ce)/Co × 100), Co (mg/L) is the initial concentration of the heavy metal solution before adsorption, Ce (mg/L) is the concentration of the remaining heavy metal in the solution when adsorption reaches equilibrium, V (L) is the volume of the heavy metal solution, and M (g) is the mass of the mixed microalgae. The results are shown in FIGS. 1 and 2.
FIG. 1 is a schematic diagram of the change of protein concentration of microalgae obtained from different embodiments of acclimatization steps. As shown in fig. 1, the protein concentration of the same algal species under the acclimated culture conditions of the examples was significantly different, and compared with the blank group, the protein concentrations of the algal proteins of the microalgae in example 4 of example 1 all showed a significant increase trend, and it is clear that the expression abundance of the algal proteins of the microalgae in example 1 is the highest, and the number of protein spots in the sample is also the highest. The results of comparative examples 1 and 3-6 show that in example 1, the cooperative acclimation culture of microalgae by using 3-mercaptopropionic acid and sodium methallylsulfonate in combination with heavy metal ions may stimulate the algae to maintain the balance state of algae cells in a stress environment by adjusting the level of protein metabolism, and after the microalgae is subjected to the cooperative acclimation process, the expression abundance of algae proteins is effectively increased, so that the concentration and the amount of algae proteins secreted by the algae are increased.
FIG. 2 shows the results of the adsorption capacity measurement of the mixed microalgae obtained in the different examples. The results also show that the highest adsorption capacity and adsorption rate of the copper ions are obtained in example 1, because the cooperative acclimation culture mode of the microalgae by using the 3-mercaptopropionic acid and the sodium methallyl sulfonate to cooperate with the heavy metal ions is adopted in example 1, the amount of the phycobiont protein secreted by the microalgae is increased, and the phycobiont protein has the binding capacity to the heavy metal ions, so that the adsorption capacity and adsorption rate of the microalgae to the heavy metal ions can be further improved.
Experimental example 3:
mechanical strength and acid and alkali resistance test of biochar-based microalgae particles prepared by different methods
The experimental method comprises the following steps: preparing biochar-based microalgae particles according to the methods of examples 1, 2, 7, 8 and 11, preparing acid-base solutions with pH values of 5, 7, 9 and 11 by using sulfuric acid and sodium hydroxide solutions, dividing into 5 parts, respectively adding 1g of biochar-based microalgae particles prepared in different examples, placing the solutions in a constant-temperature shaking table (30 ℃, 200r/s) for oscillation timing, recording oscillation time when the biochar-based microalgae particles break, namely biochar carbon powder appears in the solutions, ending the oscillation, and counting the mechanical strength of the biochar-based microalgae particles by using the oscillation time when the biochar-based microalgae particles break. The results are shown in FIG. 3.
Fig. 3 shows the results of mechanical strength tests of biochar-based microalgae particles prepared by different methods under different acid-base conditions. The results show that the biochar-based microalgae particles have better stability in acid-base solutions with different pH values, wherein the oscillation time of the embodiment 2 is longest, and the oscillation time of the embodiment 11 is shortest, which indicates that the preparation method of the embodiment 2 can improve the mechanical strength and the acid and alkali resistance of the biochar-based microalgae particles, so that the biochar-based microalgae particles oscillate in the acid-base solution for more than 48 hours, thereby improving the stability and the recoverability of the biochar-based microalgae particles in a water body, ensuring that the particles are not easy to break and break in the water body, causing no secondary pollution to the environment, and being beneficial to operation and recovery.
Experimental example 4:
desorption rate determination method of biochar-based microalgae particles prepared by different methods
The experimental method comprises the following steps: biochar-based microalgae particles were prepared according to the methods of examples 1, 2, 7, 8, and 11, 0.05g of biochar-based microalgae particles were weighed and added with 100mL and 100mg/L Cr, respectively6+The solution was adsorbed by shaking at 25 ℃ and pH 7.5 for 12 hours, and then taken out and filtered to measure the metal ion concentration (see the method of Experimental example 1) to obtain Cr6+The amount of adsorption of (2). Drying the filtered biochar-based microalgae particles to constant weight, and respectively adding the dried biochar-based microalgae particles to 100mL and 0.01mol of CaCl2In the solution, oscillating and analyzing for 4h, taking out, filtering, measuring, and calculating Cr6+The amount of desorption and desorption rate. Desorption amount (mg/g) ═ Ce × V/M, desorption rate% ═ desorption amount/adsorption amount × 100, Ce (mg/L) is the concentration of heavy metal ions in the desorption solution, V (L) is the volume of the desorption solution, and M (g) is the mass of the biochar-based microalgae particles. The results are shown in Table 2.
Table 2 shows the results of measuring the adsorption and desorption capacities of the biochar-based microalgae particles prepared by different methods
| Adsorption amount mg/g | Desorption amount mg/g | Desorption rate% | |
| Example 1 | 116.5 | 13.2 | 11.3 |
| Example 2 | 123.4 | 4.2 | 3.4 |
| Example 7 | 115.5 | 13.4 | 11.6 |
| Example 8 | 119.1 | 11.3 | 9.5 |
| Example 11 | 86.5 | 17.8 | 20.6 |
The results show that the desorption amount and desorption rate of each example are obviously different, wherein the desorption rate of example 2 is the smallest, and the desorption rate of example 11 is the highest. The preparation method in example 2 can enhance the fixing and binding ability of heavy metal ions in the particles, and reduce the desorption rate of the heavy metal adsorbed in the particles, thereby achieving the purpose of fixing the heavy metal without easy desorption, and avoiding desorption and secondary pollution caused by the change of water environment.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above embodiments are merely illustrative, and not restrictive, of the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (6)
1. A biochar-based microalgae particle comprises a biochar matrix and microalgae;
pre-culturing, domesticating and pre-treating the microalgae seeds, mixing, and forming immobilized particles with biochar;
the domestication is carried out in a metal ion mixed solution with the ion concentration not more than 0.3 mg/L;
the microalgae comprise Chlorella vulgaris, Chlorella pyrenoidosa, Chlorella ellipsoidea and Chlorella quintocida;
wherein, the metal ion mixed solution contains Fe2+、Fe3+、Al3+、Zn2+The weight ratio of ions is 0.5:0.5-1:1-2:1, and the metal ion mixed solution also contains 0.02-0.04mg/L of 3-mercaptopropionic acid and 0.01-0.05mg/L of sodium methallyl sulfonate.
2. The biochar-based microalgae particles as claimed in claim 1, which are characterized in that: the domestication conditions are as follows: the pH value is 7-8, the illumination intensity is 4000-.
3. Use of the biochar-based microalgae particles according to claim 1 in the treatment of wastewater, which is industrial wastewater, agricultural wastewater or domestic wastewater; the treatment effect of the biochar-based microalgae particles is to remove nitrogen, phosphorus and heavy metals in the wastewater.
4. A method for preparing the biochar-based microalgae particles of claim 1, comprising:
pre-culturing, domesticating and pre-treating microalgae seeds, and mixing to obtain mixed microalgae; the domestication is carried out in a metal ion mixed solution with the ion concentration of 0.2-0.3mg/L, and Fe in the metal ion mixed solution2+、Fe3+、Al3+、Zn2+The weight ratio of ions is 0.5:0.5-1:1-2:1, and the metal ion mixed solution also contains 0.02-0.04mg/L of 3-mercaptopropionic acid and 0.01-0.05mg/L of sodium methallyl sulfonate;
the preparation of the biochar, and,
mixing the mixed microalgae with the biochar, and then adding CaCl into sodium alginate solution2Curing and forming;
the microalgae species comprise chlorella vulgaris, chlorella pyrenoidosa, chlorella ellipsoidea and armillaria mellea, and the microalgae species are mixed in a weight ratio of 1:1:1: 1-3;
the curing and forming steps are as follows: oscillating and mixing the biochar and the mixed microalgae for 12-24h under the conditions that the rotation speed is 200-300rpm and the illumination intensity is 3000-4000Lx, adding the mixture into a sodium alginate solution with the concentration of 1.5-2wt%, uniformly stirring, and dripping CaCl with the concentration of 1-2wt%2Solidifying the solution for 1-2h, washing with deionized water to obtain biochar-based microalgae particles, and drying in an oven at 40-60 ℃ to constant weight;
the weight ratio of the biochar to the mixed microalgae is 1:1-3, and the microalgae and the biochar are mixedThe weight ratio of the mixture in the sodium alginate solution is 20-35%, the sodium alginate solution and CaCl2The weight ratio of the solution is 1: 0.8-1.5.
5. The method for preparing biochar-based microalgae particles as claimed in claim 4, which is characterized in that: the biochar is obtained by pre-baking the agricultural and forestry wastes at the temperature of 100-150 ℃ and carbonizing the agricultural and forestry wastes for 2-6 hours at the temperature of 400-500 ℃.
6. The method for removing the heavy metals in the water body by using the biochar-based microalgae particles comprises the following steps:
the biochar-based microalgae particles are prepared by the preparation method according to claim 4; and the combination of (a) and (b),
adding the biochar-based microalgae particles into a water body polluted by heavy metal for adsorption and purification;
the using amount of the biochar-based microalgae particles in a water body is not less than 0.3 g/L.
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