CN107893064B - Preparation method and application of biochar-polyvinyl alcohol combined immobilized microalgae pellets - Google Patents
Preparation method and application of biochar-polyvinyl alcohol combined immobilized microalgae pellets Download PDFInfo
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- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention belongs to the technical field of microbial treatment of industrial wastewater, and particularly relates to a preparation method and application of micro-algae pellets jointly immobilized by biochar-polyvinyl alcohol. The method comprises the steps of crushing and sieving desert hyphomycetes algae slices obtained by artificial large-scale culture and air drying to obtain algae powder; then, the method for preparing the microalgae pellets jointly fixed by the biochar and the polyvinyl alcohol is established by taking the algae powder, the biochar and the polyvinyl alcohol as raw materials, the preparation process is simple, the used materials are cheap and easy to obtain, the production cost is low, and the industrial scale production is easy to realize. The invention also discloses application of the microalgae pellets in the aspect of adsorbing heavy metal ions, the heavy metal ion content in the industrial wastewater polluted by heavy metals can be reduced, the adsorption rate is higher, and the granular pellets are easy to separate from the solution, are convenient to recover and can be recycled.
Description
Technical Field
The invention belongs to the technical field of microbial treatment of industrial wastewater, and particularly relates to a preparation method and application of micro-algae pellets jointly immobilized by biochar-polyvinyl alcohol.
Background
In recent years, heavy metal pollution caused by unreasonable treatment and discharge of industrial heavy metal wastewater causes serious negative effects on the life and ecological environment of people. Therefore, the removal of heavy metal ions in wastewater is a troublesome problem to be solved. The traditional physical and chemical methods such as activated carbon adsorption method, chemical precipitation method zeolite molecular sieve adsorption method and the like are used for treating wastewater, the adsorption capacity is low, the removal is incomplete, the required cost is high, and secondary pollution is easily caused, so that the search for a new adsorbent with low cost and good adsorption effect becomes the target for treating heavy metal wastewater at present.
In the 60 s of the 20 th century, along with the development of microalgae bioengineering technology in the world, the microalgae biosorption method has attracted extensive attention for treating heavy metal wastewater, and has the advantages of large adsorption capacity, low cost, no secondary pollution and the like.
Compared with free algae, the immobilized algae has the advantages of high algae cell density, high reaction speed, stable adsorption performance, less algae cell loss, easy separation from waste water and the like, and has wider application prospect in waste water treatment. The algae system formed by utilizing the immobilization technology is an effective way for overcoming the defects of long retention time, large occupied area and the like of the traditional algae sewage treatment system.
The biochar is a novel environment functional material which is stable and highly aromatic and contains carbon and is obtained by thermally cracking biomass under the anoxic or anaerobic condition, and has great application potential in the aspect of repairing heavy metal polluted environment. The natural porous structure of the biochar has stronger adsorption force on toxic heavy metals, and toxic substances are fixed on the surfaces of micropores of the biochar through the adsorption and fixation effects, so that the chemical activity and toxicity of the pollutants in the soil are reduced, and the aim of repairing the polluted soil for a long time is fulfilled.
Compared with biochar, microalgae is another type of biological adsorbent commonly used at present, and the heavy metal remediation by utilizing microalgae has the following advantages: (1) the adsorption effect is fast, the retention time is short, and the energy consumption is saved; (2) 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 growth speed is high, 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.
The surface pores of the biochar can provide habitat for the microalgae, and the surface functional groups of the biochar can neutralize the negative charges on the surface of the microalgae, reduce the repulsive force between the algae cells and the carrier, promote the secretion of extracellular polymers and further promote the stability of the fixed algae cells. In addition, the growth of microalgae can also cause the physical and chemical properties of the surface of the biochar to change. Microalgae and biochar have various advantages in the aspect of heavy metal remediation, and from the perspective of immobilizing microalgae, biochar is undoubtedly the best adsorption carrier. The biochar is used as a carrier, algae cells are fixed on the surface of the biochar to form a mixed adsorbent, and the adsorption rate and the recovery rate of the carbon-based immobilized microalgae adsorbent are further improved. For example, patent publication No. CN 106076278A discloses a method for removing heavy metals by using a biochar-based microalgae complex adsorbent, which uses biochar as a substrate material, and fixes microalgae on a biochar carrier to form a complex adsorbent, thereby removing heavy metals. However, the biochar and the algae powder are both powder, and are difficult to separate from heavy metals after adsorption, and difficult to recycle.
Disclosure of Invention
The invention aims to provide a preparation method of a micro-algae pellet jointly fixed by biochar and polyvinyl alcohol, which has the advantages of simple preparation process, cheap and easily-obtained materials, low production cost and easy realization of industrial mass production.
The invention also aims to provide the application of the biochar-polyvinyl alcohol combined immobilized microalgae beads in the aspect of adsorbing heavy metal ions, the heavy metal ion content in the industrial wastewater polluted by heavy metals can be reduced, the adsorption rate is high, the granular beads are easy to separate from the solution, the recovery is convenient, and the reutilization can be realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a micro-algae pellet jointly fixed by biochar and polyvinyl alcohol, which comprises the following steps:
step 1: pulverizing and sieving the desert hyphomycete algae pieces obtained by artificial large-scale culture and air drying to obtain desert hyphomycete algae powder with fineness of 80-100 meshes;
step 2: mixing the desert algae powder with ultrapure water, magnetically stirring for 5-10 min, and grinding by using a glass grinder to obtain a uniform desert algae suspension;
and step 3: adding biochar into the desert algae suspension, and uniformly mixing for 2h by oscillation to obtain a first mixed solution; the mass ratio of the desert algae powder to the biochar is 1: (1-3);
and 4, step 4: mixing the first mixed solution in the step 3 with a polyvinyl alcohol solution according to a volume ratio of 1: 1, adding the first mixed solution into a polyvinyl alcohol solution cooled to room temperature to obtain a second mixed solution, magnetically stirring until no bubbles exist, dripping the second mixed solution into a saturated boric acid solution, solidifying at room temperature for 6-12 hours to obtain immobilized microalgae pellets, and cleaning the microalgae pellets with ultrapure water until a cleaning solution is neutral;
and 5: and (4) placing the cleaned microalgae pellets in a culture dish, and air-drying at room temperature for later use.
Further, the desert algae in step 1 is Microcoleus vaginatus.
Further, the particle size of the biochar in the step 3 is 100 meshes.
Further, in the step 4, when the second mixed solution is dripped into the saturated boric acid solution, the height of the operating instrument from the liquid level of the saturated boric acid solution is not less than 10 cm.
Further, the saturated boric acid solution in the step 4 contains polyoxyethylene octyl phenol ether with the concentration of 50mmol/L, and the pH value of the saturated boric acid solution is 6.7.
The invention also provides application of the biochar-polyvinyl alcohol jointly immobilized microalgae beads prepared by the biochar-polyvinyl alcohol jointly immobilized microalgae bead preparation method in the aspect of heavy metal ion adsorption.
Further, the above application comprises the steps of: adding microalgae pellets into the artificially simulated heavy metal ion solution, and placing the solution in a shaking table for 1-24 hours; the adding mass of the microalgae pellets is 1-4.5% of the volume of the artificially simulated heavy metal ion solution.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention utilizes the biochar-polyvinyl alcohol to jointly fix the microalgae, combines the biochar and the desert algae which both have adsorbability together to prepare granular microalgae pellets, and enhances the mechanical property and the adsorption property of the immobilized material.
2. The invention relates to a micro-algae pellet jointly fixed by biochar and polyvinyl alcohol and Cu in heavy metal ion solution2+、Pb2+、Cr6+And Cd2+The adsorption effect is obvious, compared with single-component microalgae powder, biological carbon powder or a mixture of the microalgae powder and the biological carbon powder, the adsorption rate is obviously improved, and after the heavy metal ion solution is adsorbed, the granular globules are easy to separate from the heavy metal ion solution, are convenient to recover and can be recycled.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The test methods in the following examples are conventional methods unless otherwise specified.
The biochar is a solid substance which is insoluble, stable, highly aromatic and rich in carbon and is prepared by pyrolyzing wheat straws or peanut shells at 450-700 ℃ under the anoxic condition. And after the preparation of the biochar is finished, air-drying, filtering by a 100-mesh sieve, and storing in a ventilated and dry place for later use.
The desert algae is Microcoleus vaginatus, but the preparation method of the invention, which utilizes the combination of biochar and polyvinyl alcohol to fix microalgae to obtain microalgae pellets, is not limited to fixing Microcoleus vaginatus, and is also suitable for other desert algae. The Microcoleus vaginatus is one of desert algae species which are most widely distributed in desert soil, the biomass of the Microcoleus vaginatus is sometimes more than 95% of the total amount of soil microorganisms, and the Microcoleus vaginatus has growth advantages and adsorption characteristics, such as developed phycofilaments and large extracellular polysaccharide secretion amount. Firstly, carrying out artificial large-scale culture of the desert algae. Adopting BG-11 liquid culture medium as culture medium, respectively culturing the desert algae by stage I, II and III algae, transferring the expanded three-stage algae to photobioreactor or raceway-type circulation pool, and culturing in large scale. In the above each stage of culturing of the desert algae, the culturing conditions are as follows: continuously culturing for 15-30 days at 28-35 deg.C and 3000Lux-4000Lux under aeration, detecting to obtain chlorophyll a content of 8-10 μ g/mL, collecting algae, naturally air drying to obtain desert hyphomycete sheet, and storing.
The BG-11 liquid medium had the following composition (per liter for example): 1.5g of sodium nitrate, 0.04g of dipotassium hydrogen phosphate trihydrate, 0.07g of magnesium sulfate heptahydrate, 0.036g of calcium chloride dihydrate, 0.006g of citric acid, 0.006g of ferric ammonium citrate, 0.001g of disodium ethylenediamine tetraacetic acid (EDTA), 0.02g of sodium carbonate and 1mL of trace element A5 liquid; wherein the A5 liquid component (taking each liter as an example): 2.86g of boric acid, 0.039g of sodium molybdate dihydrate, 0.222g of zinc sulfate heptahydrate, 0.074g of copper sulfate pentahydrate, 1.18g of manganese chloride monohydrate, and 0.049g of cobalt nitrate hexahydrate.
The syringe needles used in the following examples were 18G (inner diameter 0.86mm, outer diameter 1.26mm), 20G (inner diameter 0.6mm, outer diameter 0.9mm) and disposable needles (20 ml).
Example one
A preparation method of a biochar-polyvinyl alcohol combined immobilized microalgae pellet comprises the following steps:
step 1: pulverizing and sieving the desert hypnea algae pieces obtained by artificial large-scale culture and air drying to obtain desert hypnea algae powder with fineness of 80 mesh.
Step 2: mixing 0.5g of Aphanizomenon desert algae powder with 50ml of ultrapure water, magnetically stirring for 5min, and grinding with a glass grinder to obtain uniform Aphanizomenon desert algae suspension. During grinding, single desert algae cell is obtained as much as possible, and more binding sites are exposed, so that the relative surface area of the desert algae cell is increased.
And step 3: adding 1.5g of charcoal into 50ml of the desert algae suspension, and shaking and mixing uniformly for 2h to fully fix the desert algae cells on the charcoal, thereby obtaining a first mixed solution.
And 4, step 4: before the polyvinyl alcohol is heated and melted, the polyvinyl alcohol is ground by a dry mill to make the polyvinyl alcohol melt relatively easily. 6g of polyvinyl alcohol was added to 50ml of ultrapure water, heated in an infrared heating furnace, and the polyvinyl alcohol was melted to obtain a polyvinyl alcohol solution, which was cooled to room temperature. The saturated boric acid solution is prepared to contain polyoxyethylene octyl phenol ether (OP-10) with the concentration of 50mmol/L, and the pH value of the saturated boric acid solution is 6.7.
Adding 50ml of the first mixed solution into 50ml of the polyvinyl alcohol solution cooled to room temperature to obtain a second mixed solution, wherein the concentration of the polyvinyl alcohol is 6%, and magnetically stirring until no bubbles exist.
And (3) dripping the second mixed solution into 400ml of saturated boric acid solution by using a syringe with the needle head model of 20G, solidifying for 6 hours at room temperature when the height of the needle point of the syringe from the liquid level of the saturated boric acid solution is 12cm during operation to obtain immobilized microalgae pellets with the particle size of 2mm, and cleaning the microalgae pellets by using ultrapure water until a cleaning solution is neutral so as to separate the microalgae pellets from the saturated boric acid solution.
And 5: and (4) placing the cleaned microalgae pellets in a culture dish, and air-drying at room temperature for later use.
Example two
A preparation method of a biochar-polyvinyl alcohol combined immobilized microalgae pellet comprises the following steps:
step 1: pulverizing and sieving the desert hypnea algae pieces obtained by artificial large-scale culture and air drying to obtain desert hypnea algae powder with fineness of 100 meshes.
Step 2: mixing 1g of Aphanizomenon desert algae powder with 50ml of ultrapure water, magnetically stirring for 8min, and grinding with a glass grinder to obtain a uniform Aphanizomenon desert algae suspension. During grinding, single desert algae cell is obtained as much as possible, and more binding sites are exposed, so that the relative surface area of the desert algae cell is increased.
And step 3: adding 3g of charcoal into 50ml of the desert algae suspension, and shaking and mixing uniformly for 2h to fully fix desert algae cells on the charcoal, thereby obtaining a first mixed solution.
And 4, step 4: before the polyvinyl alcohol is heated and melted, the polyvinyl alcohol is ground by a dry mill to make the polyvinyl alcohol melt relatively easily. 7g of polyvinyl alcohol was added to 50ml of ultrapure water, heated in an infrared heating furnace, and the polyvinyl alcohol was melted to obtain a polyvinyl alcohol solution, which was cooled to room temperature. The saturated boric acid solution is prepared to contain polyoxyethylene octyl phenol ether (OP-10) with the concentration of 50mmol/L, and the pH value of the saturated boric acid solution is 6.7.
Adding 50ml of the first mixed solution into 50ml of the polyvinyl alcohol solution cooled to room temperature to obtain a second mixed solution, wherein the concentration of the polyvinyl alcohol is 7%, and magnetically stirring until no bubbles exist.
And (3) dripping the second mixed solution into 400ml of saturated boric acid solution by using an injector with the model number of 18G, solidifying for 8 hours at room temperature when the height of the needle point of the injector from the liquid level of the saturated boric acid solution is 12cm during operation to obtain immobilized microalgae pellets with the grain diameter of 3mm, and cleaning the microalgae pellets by using ultrapure water until a cleaning solution is neutral so as to separate the microalgae pellets from the saturated boric acid solution.
And 5: and (4) placing the cleaned microalgae pellets in a culture dish, and air-drying at room temperature for later use.
EXAMPLE III
A preparation method of a biochar-polyvinyl alcohol combined immobilized microalgae pellet comprises the following steps:
step 1: pulverizing and sieving the desert hypnea algae pieces obtained by artificial large-scale culture and air drying to obtain desert hypnea algae powder with fineness of 80 mesh.
Step 2: mixing 2g of Aphanizomenon desert algae powder with 50ml of ultrapure water, magnetically stirring for 10min, and grinding with a glass grinder to obtain a uniform Aphanizomenon desert algae suspension. During grinding, single desert algae cell is obtained as much as possible, and more binding sites are exposed, so that the relative surface area of the desert algae cell is increased.
And step 3: adding 6g of charcoal into 50ml of the desert algae suspension, and shaking and mixing uniformly for 2h to fully fix desert algae cells on the charcoal, thereby obtaining a first mixed solution.
And 4, step 4: before the polyvinyl alcohol is heated and melted, the polyvinyl alcohol is ground by a dry mill to make the polyvinyl alcohol melt relatively easily. 8g of polyvinyl alcohol was added to 50ml of ultrapure water, heated in an infrared heating furnace, and the polyvinyl alcohol was melted to obtain a polyvinyl alcohol solution, which was cooled to room temperature. The saturated boric acid solution is prepared to contain polyoxyethylene octyl phenol ether (OP-10) with the concentration of 50mmol/L, and the pH value of the saturated boric acid solution is 6.7.
Adding 50ml of the first mixed solution into 50ml of the polyvinyl alcohol solution cooled to room temperature to obtain a second mixed solution, wherein the concentration of the polyvinyl alcohol is 8%, and magnetically stirring until no bubbles exist.
And (3) dripping the second mixed solution into 400ml of saturated boric acid solution by using a disposable needle tube (20ml), solidifying for 12 hours at room temperature when the height of the needle point of the injector from the liquid level of the saturated boric acid solution is 15cm, obtaining immobilized microalgae beads with the particle size of 4mm, and cleaning the microalgae beads by using ultrapure water until the cleaning solution is neutral, so as to separate the microalgae beads from the saturated boric acid solution.
And 5: and (4) placing the cleaned microalgae pellets in a culture dish, and air-drying at room temperature for later use.
Example four
A preparation method of a biochar-polyvinyl alcohol combined immobilized microalgae pellet comprises the following steps:
step 1: pulverizing and sieving the desert hypnea algae pieces obtained by artificial large-scale culture and air drying to obtain desert hypnea algae powder with fineness of 80 mesh.
Step 2: mixing 3g of Aphanizomenon desert algae powder with 50ml of ultrapure water, magnetically stirring for 10min, and grinding with a glass grinder to obtain a uniform Aphanizomenon desert algae suspension. During grinding, single desert algae cell is obtained as much as possible, and more binding sites are exposed, so that the relative surface area of the desert algae cell is increased.
And step 3: adding 3g of charcoal into 50ml of the desert algae suspension, and shaking and mixing uniformly for 2h to fully fix desert algae cells on the charcoal, thereby obtaining a first mixed solution.
And 4, step 4: before the polyvinyl alcohol is heated and melted, the polyvinyl alcohol is ground by a dry mill to make the polyvinyl alcohol melt relatively easily. 7g of polyvinyl alcohol was added to 50ml of ultrapure water, heated in an infrared heating furnace, and the polyvinyl alcohol was melted to obtain a polyvinyl alcohol solution, which was cooled to room temperature. The saturated boric acid solution is prepared to contain polyoxyethylene octyl phenol ether (OP-10) with the concentration of 50mmol/L, and the pH value of the saturated boric acid solution is 6.7.
Adding 50ml of the first mixed solution into 50ml of the polyvinyl alcohol solution cooled to room temperature to obtain a second mixed solution, wherein the concentration of the polyvinyl alcohol is 7%, and magnetically stirring until no bubbles exist.
And (3) dripping the second mixed solution into 400ml of saturated boric acid solution by using an injector with the model number of 18G, solidifying for 8 hours at room temperature when the height of the needle point of the injector from the liquid level of the saturated boric acid solution is 15cm, obtaining immobilized microalgae pellets with the grain diameter of 3mm, and cleaning the microalgae pellets by using ultrapure water until the cleaning solution is neutral so as to separate the microalgae pellets from the saturated boric acid solution.
And 5: and (4) placing the cleaned microalgae pellets in a culture dish, and air-drying at room temperature for later use.
EXAMPLE five
Preparing an artificial simulated heavy metal ion solution with the concentration of 300mg/L, wherein 1L of the artificial simulated heavy metal ion solution contains 1.17g of copper sulfate pentahydrate, 0.55g of lead acetate, 1.7g of potassium dichromate and 0.61g of chromium chloride, so that the Cu in the artificial simulated heavy metal ion solution is2+、Pb2+、Cr6+And Cd2+The initial concentrations of (A) were all 0.3 g/L.
The air-dried microalgae pellets with the particle size of 4mm prepared in example three are adopted, 0.6g of microalgae pellets are added into 20mL of artificial simulated heavy metal ion solution, and the mixture is placed in a shaking table for 6 hours. The adsorption rates were averaged for 3 replicates each time. Microalgae pellet pair Cu2+、Pb2+、Cr6+、Cd2+The adsorption of four heavy metal ions was performed, and compared with the adsorption effect of heavy metal ions of conventional microalgae powder, bio-carbon powder, and a mixture of microalgae powder and bio-carbon powder (the amount of microalgae powder or bio-carbon contained in 0.6g of microalgae pellet was 0.08g), the final concentrations of four heavy metals in the adsorbed heavy metal ion solution were measured with an a3 type atomic absorption spectrophotometer, and the adsorption rate was calculated, with the results shown in table 1.
TABLE 1 adsorption rates of conventional microalgae powders, charcoal powders and microalgae beads for heavy metal ions
As can be seen from table 1, compared with single-component microalgae powder, bio-carbon powder or a mixture of the microalgae powder and the bio-carbon powder, the adsorption effect of the microalgae beads jointly immobilized by bio-carbon-polyvinyl alcohol on heavy metal ions is obviously better, and the separation of the microalgae beads from the heavy metal ion solution after the adsorption is finished is simple and easy to operate.
EXAMPLE six
This embodiment is substantially the same as the fifth embodiment, except that: the air-dried microalgae pellets with the particle size of 2mm prepared in the first example are added into 20mL of artificial simulated heavy metal ion solution by 0.4g of microalgae pellets and placed in a shaking table for 3 hours. Measuring the final concentrations of four heavy metals in the adsorbed heavy metal ion solution by using an A3 type atomic absorption spectrophotometer, calculating the adsorption rate, and carrying out microalgae pellet on Cu2+、Pb2+、Cr6+、Cd2+The adsorption rates of the four heavy metal ions are 89.16%, 92.7%, 91.34% and 78.29% respectively.
EXAMPLE seven
This embodiment is substantially the same as the fifth embodiment, except that: and (3) adding 0.4g of the air-dried microalgae pellets with the particle size of 3mm prepared in the fourth example into 20mL of the artificial simulated heavy metal ion solution, and placing the mixture in a shaking table for 5 hours. Measuring the final concentrations of four heavy metals in the adsorbed heavy metal ion solution by using an A3 type atomic absorption spectrophotometer, calculating the adsorption rate, and carrying out microalgae pellet on Cu2+、Pb2+、Cr6+、Cd2+The adsorption rates of the four heavy metal ions are respectively 98.97%, 95.35%, 92.78% and 83.78%.
Example eight
This embodiment is substantially the same as the fifth embodiment, except that: by using the air-dried microalgae pellets with the particle size of 4mm prepared in the third embodiment, 0.2g, 0.4g, 0.5g, 0.6g, 0.8g and 0.9g of microalgae pellets are respectively added into 20mL of the artificial simulated heavy metal ion solution and placed in a shaking table for 6 hours. The adsorption rates were averaged for 3 replicates each time. Microalgae pellet pair Cu2+、Pb2 +、Cr6+、Cd2+Four heavy metal ions were adsorbed, and the final concentrations of the four heavy metals in the adsorbed heavy metal ion solution were measured with an a3 type atomic absorption spectrophotometer, and the adsorption rates were calculated, with the results shown in table 2.
TABLE 2 adsorption rates of heavy metal ions by microalgae beads at different dosages
As can be seen from table 2, the adsorption rates of the microalgae spheres to the four heavy metal ions are all enhanced with the increase of the added amount, because the total amount of the functional groups of the adsorbent is less and the microalgae spheres cannot provide enough adsorption sites under the condition of less added amount of the adsorbent, so that the adsorption rates to the four heavy metal ions are all low. However, as the amount of the catalyst to be added increases, the total amount of the functional groups increases, and the adsorption rate increases accordingly. However, as the addition amount of the microalgae beads continues to increase, the adsorption rate increases slowly, because the heavy metal ions are prevented from being combined with the adsorption sites due to the electrostatic interaction and the mutual interference between the reaction groups, so that the adsorption rate of the immobilized beads to the heavy metals increases slowly.
Example nine
This embodiment is substantially the same as the fifth embodiment, except that: and (3) adding 0.6g of the air-dried microalgae pellets with the particle size of 4mm prepared in the third embodiment into 20mL of the artificial simulated heavy metal ion solution, and placing the solution in a shaking table to shake for 5min, 15min, 30min, 1h, 2h, 4h, 6h, 8h, 12h and 24h respectively. The adsorption rates were averaged for 3 replicates each time. Microalgae pellet pair Cu2+、Pb2+、Cr6+、Cd2+Four heavy metal ions were adsorbed, and the final concentrations of the four heavy metals in the adsorbed heavy metal ion solution were measured with an a3 type atomic absorption spectrophotometer, and the adsorption rates were calculated, and the results are shown in table 3.
TABLE 3 adsorption rate of heavy metal ions by microalgae beads at different adsorption times
As can be seen from table 3, the adsorption process of the microalgae beads to heavy metal ions is divided into 2 stages: the first stage is physical adsorption to Cu2+、Pb2+、Cd2+The adsorption is rapidly carried out in the first 8 hours, and the adsorption rates respectively reach 90.74%, 96.55% and 82.3%; for Cr6+The adsorption of (2) is rapidly carried out in the first 6h, and the adsorption rate reaches 89.71%. This is because the presence of the adsorbent in solution provides a large number of adsorption sites for the heavy metals, enhancing the ion exchange effect. The second stage is a chemical adsorption process, and Cu is treated within 8-24h2+、Pb2+、Cd2+And 6-24h for Cr6+The adsorption rate of (A) slowly increases with the passage of time, and the phase is mainly a process in which metal ions adsorbed on the surfaces of algae cells are further transferred to the insides of the cells, and the process is slow.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which are merely illustrative and not restrictive, and it should be understood that other embodiments may be easily implemented by those skilled in the art by means of replacement or modification according to the technical contents disclosed in the specification, and therefore, all changes and modifications that come within the spirit and technical conditions of the present invention should be included in the claims of the present invention.
Claims (3)
1. The application of the micro-algae pellets jointly immobilized by the biochar and the polyvinyl alcohol in the aspect of adsorbing heavy metal ions is characterized in that the using method comprises the following steps: adding microalgae pellets into the artificially simulated heavy metal ion solution, and placing the solution in a shaking table for 1-24 hours; the adding mass of the microalgae pellets is 1-4.5% of the volume of the artificially simulated heavy metal ion solution;
the preparation method of the microalgae pellets comprises the following steps:
step 1: pulverizing and sieving the desert hyphomycete algae pieces obtained by artificial large-scale culture and air drying to obtain desert hyphomycete algae powder with fineness of 80-100 meshes; the desert algae is Microcoleus vaginatus;
step 2: mixing the desert algae powder with ultrapure water, magnetically stirring for 5-10 min, and grinding by using a glass grinder to obtain a uniform desert algae suspension;
and step 3: adding biochar into the desert algae suspension, and uniformly mixing for 2h by oscillation to obtain a first mixed solution; the mass ratio of the desert algae powder to the biochar is 1: (1-3);
and 4, step 4: mixing the first mixed solution in the step 3 with a polyvinyl alcohol solution according to a volume ratio of 1: 1, adding the first mixed solution into a polyvinyl alcohol solution cooled to room temperature to obtain a second mixed solution, magnetically stirring until no bubbles exist, dripping the second mixed solution into a saturated boric acid solution, solidifying at room temperature for 6-12 hours to obtain immobilized microalgae pellets, and cleaning the microalgae pellets with ultrapure water until a cleaning solution is neutral; the saturated boric acid solution contains polyoxyethylene octyl phenol ether with the concentration of 50mmol/L, and the pH value of the saturated boric acid solution is 6.7;
and 5: and (4) placing the cleaned microalgae pellets in a culture dish, and air-drying at room temperature for later use.
2. The application of the biochar-polyvinyl alcohol combined immobilized microalgae beads in the aspect of adsorbing heavy metal ions as claimed in claim 1, wherein the particle size of the biochar in the step 3 is 100 meshes.
3. The application of the biochar-polyvinyl alcohol jointly immobilized microalgae beads in adsorbing heavy metal ions as claimed in claim 1, wherein when the second mixed solution is dripped into the saturated boric acid solution in the step 4, the height of an operating instrument from the liquid level of the saturated boric acid solution is not less than 10 cm.
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