CN112427018A - Heavy metal wastewater biomass adsorbent and preparation method thereof - Google Patents
Heavy metal wastewater biomass adsorbent and preparation method thereof Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a heavy metal wastewater biomass adsorbent and a preparation method thereof, belonging to the technical field of wastewater treatment. The heavy metal wastewater biomass adsorbent disclosed by the invention is wide in raw material source, low in cost and good in environmental compatibility, and the adsorbent prepared by modification has the advantages of strong selectivity, high removal rate, simplicity in operation, high adsorption capacity and good adsorption effect, and is wide in application prospect.
Description
Technical Field
The invention relates to a heavy metal wastewater biomass adsorbent and a preparation method thereof, belonging to the technical field of wastewater treatment.
Background
At present, biomass has the characteristics of wide raw material sources, low cost, good environmental compatibility and the like, and the adsorbent prepared by modification has the advantages of strong selectivity, high removal rate, simplicity in operation and the like, and is an environment-friendly material. Biomass is the most extensive and most abundant substance on earth, and the most extensive research at present is the lignin fibers such as loofah sponge, straw, trees and the like; agricultural and forestry wastes such as corncobs, sawdust, husks and cotton fibers; algae, fungi, and livestock manure and waste during animal production. With the gradual depletion of mineral resources and petroleum resources, the polymeric adsorbent material and the inorganic adsorbent material face serious threats of raw material shortage and price rise. Therefore, the adsorbent is expected to replace traditional adsorbing materials such as resin, activated carbon and the like, and is applied to the removal of heavy metal ions in wastewater in a large scale. However, the adsorption performance of the currently common biomass adsorbent is poor.
In view of the above-mentioned defects, the present designer actively makes research and innovation to create a heavy metal wastewater biomass adsorbent and a preparation method thereof, so that the adsorbent has industrial utilization value.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a heavy metal wastewater biomass adsorbent and a preparation method thereof.
The invention relates to a heavy metal wastewater biomass adsorbent, which is prepared by culturing and reacting a membrane-covered loofah sponge and an Aspergillus oryzae bacterium suspension in the presence of tryptone, a yeast extract, sodium chloride and deionized water;
the film-coated loofah sponge is prepared by microwave reaction of a pre-modified loofah sponge and a dopamine solution;
the pre-modified loofah sponge is prepared by mixing pre-treated loofah sponge and grafting liquid and then carrying out ultraviolet light initiated reaction;
the pretreated loofah sponge is prepared by carrying benzophenone ethanol solution on loofah sponge after alkaline leaching;
the grafting solution is prepared by mixing water, ethanol and acrylic acid.
A preparation method of a heavy metal wastewater biomass adsorbent comprises the following specific preparation steps:
(1) selecting loofah sponge, cutting into blocks, repeatedly washing, mixing the washed blocks with a sodium hydroxide solution, and soaking to obtain alkaline-leaching loofah sponge;
(2) mixing the alkali-soaked loofah sponge and a benzophenone ethanol solution, soaking and drying to obtain pretreated loofah sponge;
(3) mixing water, ethanol and acrylic acid to obtain a grafting solution, mixing the grafting solution with the pretreated loofah sponge, adding methyl hydroquinone, and stirring to obtain a reaction base solution;
(4) transferring the reaction base solution into a test tube, discharging oxygen, sealing, transferring into an ultraviolet light grafting reaction device, performing irradiation reaction, repeatedly washing after the reaction is finished, extracting with acetone, washing with water, and drying to obtain pre-modified loofah sponge;
(5) mixing the pre-modified loofah sponge fibers with the dopamine solution, carrying out microwave reaction, taking out the pre-modified loofah sponge after reaction, and naturally airing to obtain the film-coated loofah sponge;
(6) weighing tryptone, a yeast extract, sodium chloride, deionized water and a film-coated loofah sponge, uniformly mixing to obtain a substrate, adding an aspergillus oryzae bacterial suspension into the substrate, carrying out constant-temperature shaking culture, filtering and separating to obtain filter residues after the culture is finished, repeatedly washing with the deionized water, and naturally drying to obtain the heavy metal wastewater biomass adsorbent.
Further, the preparation method comprises the following specific steps:
(1) peeling and seed removing mature loofah sponge, cutting into blocks with the size of 1cm multiplied by 1cm, repeatedly washing with deionized water and boiling water for 3-5 times in sequence, mixing the washed blocks of loofah sponge with a sodium hydroxide solution with the mass fraction of 6%, standing and soaking for 3-5 hours to obtain alkali-soaked loofah sponge;
(2) mixing the alkali-dipped loofah sponge and 0.4 mass percent benzophenone ethanol solution according to a mass ratio of 1:8, putting the mixture into an ultrasonic oscillator, carrying out oscillation dipping, taking out the loofah sponge after dipping, putting the loofah sponge into an oven, and drying the loofah sponge at 105-110 ℃ for 1-2 hours to obtain pretreated loofah sponge;
(3) mixing water, ethanol and acrylic acid to obtain a grafting solution, mixing the grafting solution and the pretreated loofah sponge to obtain a mixed solution, adding methyl hydroquinone with the mass of 0.5% of that of the grafting solution into the mixed solution, and stirring for 10-15 min to obtain a reaction base solution;
(4) transferring the reaction base solution into a test tube, introducing nitrogen for 10min, discharging all oxygen in the test tube, sealing, transferring into an ultraviolet light grafting reaction device, carrying out irradiation reaction, taking out a reaction product after the reaction is finished, repeatedly washing the reaction product for 3-5 times by using boiling water and ethanol, extracting for 24 hours by using acetone to remove residual homopolymer on the surface of the reaction product, finally washing by using water, putting into an oven, and drying for 1-2 hours at 45 ℃ to obtain the pre-modified loofah sponge;
(5) mixing the pre-modified loofah sponge fibers with a dopamine solution with the mass concentration of 10mg/L, placing the mixture into a microwave reactor for microwave reaction, taking out the pre-modified loofah sponge after the microwave reaction is finished, and naturally drying the pre-modified loofah sponge to obtain the film-coated loofah sponge;
(6) weighing tryptone, a yeast extract, sodium chloride, deionized water and a film-coated loofah sponge, uniformly mixing to obtain a substrate, adding an aspergillus oryzae bacterial suspension with the concentration of 0.01g/mL and the mass of 5% of the substrate into the substrate, carrying out constant-temperature oscillation culture for 2-3 days at 25-30 ℃, filtering and separating to obtain filter residues after the culture is finished, repeatedly washing for 3-5 times by using the deionized water, and naturally airing to obtain the heavy metal wastewater biomass adsorbent.
Further, the mass ratio of the blocky loofah sponge washed in the step (1) to the sodium hydroxide solution with the mass fraction of 6% is 1: 10.
Further, the frequency of the oscillation dipping in the step (2) is 30-40 kHz, and the time of the oscillation dipping is 1-2 hours.
Further, the mass ratio of the water, the ethanol and the acrylic acid in the step (3) is 15:5:2, and the mass ratio of the grafting solution to the pretreated loofah sponge is 12: 1.
Further, the ultraviolet light power during the irradiation reaction in the step (4) is 15W, and the irradiation reaction time is 2-3 h.
Further, the power of the microwave reaction in the step (5) is 100-200W, and the time of the microwave reaction is 10-12 h.
Further, in the step (6), by weight, 10-15 parts of tryptone, 5-10 parts of yeast extract, 10-15 parts of sodium chloride, 900-1000 parts of deionized water and 200-300 parts of coated loofah sponge.
By the scheme, the invention at least has the following advantages:
the heavy metal wastewater biomass adsorbent disclosed by the invention is wide in raw material source, low in cost and good in environmental compatibility, and the adsorbent prepared by modification has the advantages of strong selectivity, high removal rate, simplicity in operation, high adsorption capacity and good adsorption effect, and is wide in application prospect.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate a certain embodiment of the present invention, and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a scanning electron microscope image of original retinervus Luffae fructus;
FIG. 2 is a scanning electron microscope image of retinervus Luffae fructus and acrylic acid polymerized and modified;
FIG. 3 is an overall cluster scanning electron microscope image of pre-modified loofah sponge fibers before microbial modification;
FIG. 4 is an electron microscope image of the whole bundle scanning of the modified loofah sponge fiber modified by the microorganism;
FIG. 5 is a Fourier infrared spectrum of the whole bundle of the pre-modified loofah sponge fiber after being modified by the microorganism.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
(1) Peeling and seed removing mature loofah sponge, cutting into blocks with the size of 1cm multiplied by 1cm, repeatedly washing for 3-5 times by using deionized water and boiling water in sequence, mixing the washed blocks of loofah sponge with a sodium hydroxide solution with the mass fraction of 6% according to the mass ratio of 1:10, standing and soaking for 3-5 hours to obtain alkali-soaked loofah sponge; through alkaline leaching treatment, the alkali liquor enters the interior of the loofah sponge fiber, and part of crystalline regions are converted into amorphous regions, so that the diameter of the loofah sponge is swelled, the surface is curled, the surface microstructure of the loofah sponge is improved, the specific surface area of the loofah sponge is increased, and the adsorption performance of the loofah sponge is initially improved;
(2) mixing the alkali-dipped loofah sponge and 0.4 mass percent benzophenone ethanol solution according to a mass ratio of 1:8, placing the mixture into an ultrasonic oscillator, carrying out oscillation dipping for 1-2 h at a frequency of 30-40 kHz, taking out the loofah sponge after dipping, placing the loofah sponge into an oven, and drying for 1-2 h at a temperature of 105-110 ℃ to obtain pretreated loofah sponge; adsorbing and immobilizing the oily arone photosensitizer on the surface of the loofah sponge through ultrasonic immersion;
(3) mixing water, ethanol and acrylic acid according to a mass ratio of 15:5:2 to obtain a grafting solution, mixing the grafting solution and the pretreated loofah sponge according to a mass ratio of 12:1 to obtain a mixed solution, adding methyl hydroquinone accounting for 0.5% of the mass of the grafting solution into the mixed solution, and stirring for 10-15 min to obtain a reaction base solution; mixing the grafting solution, the pretreated loofah sponge and a polymerization inhibitor to prepare a reaction base solution;
(4) transferring the reaction base solution into a test tube, introducing nitrogen for 10min, discharging all oxygen in the test tube, sealing, transferring into an ultraviolet light grafting reaction device, carrying out irradiation reaction for 2-3 h under the condition that the ultraviolet light power is 15W, taking out a reaction product after the reaction is finished, repeatedly washing the reaction product for 3-5 times by using boiling water and ethanol, extracting by using acetone for 24h to remove residual homopolymer on the surface of the reaction product, finally washing by using water, putting into an oven, and drying for 1-2 h at 45 ℃ to obtain pre-modified loofah sponge; the method comprises the following steps of capturing hydrogen on the surface of a loofah sponge base material by utilizing a photosensitizer under the irradiation of ultraviolet light to form macromolecular free radicals, further initiating a grafting reaction with acrylic acid, wherein the ultraviolet light catalyzed grafting reaction can uniformly graft polyacrylic acid on a natural three-dimensional spongy structure skeleton of the loofah sponge, so that the acrylic acid is respectively arranged on the surfaces of loofah sponge fibers in a large intestine villous shape, and pore channels between fiber bundles can be opened to a certain extent, compared with the original loofah sponge base material, the surface of the pre-modified loofah sponge becomes rough, the section of the loofah sponge is loose and porous, the specific surface area is remarkably increased, and the adsorption performance is greatly improved; as can be seen from the scanning electron micrographs in fig. 3 and fig. 4, the surface of the loofah sponge in fig. 3 is relatively smooth, while the surface of the modified sample in fig. 4 becomes relatively rough and has a villous shape in large intestine, and it can be clearly seen that the polymer layer is uniformly grafted to the surface of the loofah sponge;
(5) mixing the pre-modified loofah sponge fibers with a dopamine solution with the mass concentration of 10mg/L, placing the mixture into a microwave reactor, carrying out microwave reaction for 10-12 hours at the power of 100-200W, taking out the pre-modified loofah sponge after the microwave reaction is finished, and naturally drying the pre-modified loofah sponge to obtain the film-coated loofah sponge; a layer of sticky polydopamine film layer is loaded on the surface of the pre-modified loofah sponge through the oxidation auto-polymerization reaction of dopamine, so that the subsequent microorganism loading is facilitated;
(6) weighing 10-15 parts of tryptone, 5-10 parts of yeast extract, 10-15 parts of sodium chloride, 900-1000 parts of deionized water and 200-300 parts of the film-coated loofah sponge, uniformly mixing to obtain a substrate, adding an aspergillus oryzae bacterial suspension with the concentration of 0.01g/mL and the mass of the substrate being 5% to the substrate, carrying out constant-temperature shaking culture at 25-30 ℃ for 2-3 days, filtering and separating to obtain filter residues after the culture is finished, repeatedly washing with the deionized water for 3-5 times, and naturally drying to obtain the heavy metal wastewater biomass adsorbent. The biomass substrate is subjected to microbial modification, so that the adsorption pores of the biomass adsorption material are enlarged, the adsorbability of the biomass adsorption material is improved, strains are attached to the surface of the adsorption material through microbial modification to form a new pore structure, a large number of active functional groups such as amino, carboxyl, hydroxyl, carbonyl and the like are introduced into the biomass substrate, and the adsorption effect of the adsorption material on heavy metal ions is further improved by utilizing the chelation and electric adsorption characteristics of the active functional groups and the physical adsorbability of a newly added pore structure; as can be seen from the scanning electron micrographs in FIGS. 1 and 2, the surface of the raw material (b1) presents a columnar, smooth and non-porous compact structure, after the microorganism is compounded (b2), the surface morphology of the material is obviously changed, the columnar structure is decomposed by the microorganism, the surface of the material is rough and uneven, a small amount of pore structures appear, and the surface can be observedA layer of microbial colonies is observed to be attached, the surface roughness of the microbial colonies is improved, meanwhile, as can be seen from a Fourier infrared spectrogram (b2) after the microbial colonies are loaded in the graph shown in FIG. 5, the spectrogram has more absorption peaks, the obvious and wide absorption peak in the range of 3750-3200/cm is a cross stretching vibration peak of hydroxyl and amino, and the peak of 2950-2700/cm is from CH and CH2The asymmetric stretching vibration peak of C-H bond in (3) is a C ═ O stretching vibration peak in fatty acid R-COOH, a stretching vibration peak of C ═ O on carboxyl, ester group or aldehyde group between 1700 and 1600/cm and a C ═ C stretching vibration peak of aromatic ring, a peak near 1540/cm is a bending vibration peak of N-H in amine group, a peak between 1700 and 1600/cm is a bending vibration peak of O-H, a peak at 1050/cm is a C-O bond stretching vibration peak, and a peak at 770/cm is a vibration peak of heterocyclic compound ring of pyridine and furan.
Example 1
Selecting mature loofah sponge, peeling and removing seeds, cutting the loofah sponge into blocks with the size of 1cm multiplied by 1cm, repeatedly washing the blocks with deionized water and boiling water for 3 times in sequence, mixing the washed block loofah sponge with a sodium hydroxide solution with the mass fraction of 6% according to the mass ratio of 1:10, standing and soaking for 3 hours to obtain alkali-soaked loofah sponge; mixing the alkali-dipped loofah sponge with 0.4 mass percent benzophenone ethanol solution according to the mass ratio of 1:8, putting the mixture into an ultrasonic oscillator, oscillating and dipping the mixture for 1h at the frequency of 30kHz, taking out the loofah sponge after dipping, putting the loofah sponge into an oven, and drying the loofah sponge for 1h at 105 ℃ to obtain pretreated loofah sponge; mixing water, ethanol and acrylic acid according to a mass ratio of 15:5:2 to obtain a grafting solution, mixing the grafting solution and the pretreated loofah sponge according to a mass ratio of 12:1 to obtain a mixed solution, adding methyl hydroquinone accounting for 0.5% of the mass of the grafting solution into the mixed solution, and stirring for 10min to obtain a reaction base solution; transferring the reaction base solution into a test tube, introducing nitrogen for 10min, discharging all oxygen in the test tube, sealing, transferring into an ultraviolet light grafting reaction device, carrying out irradiation reaction for 2h under the condition that the ultraviolet light power is 15W, taking out a reaction product after the reaction is finished, repeatedly washing the reaction product for 3 times by using boiling water and ethanol, extracting by using acetone for 24h to remove residual homopolymer on the surface of the reaction product, finally washing by using water, putting into an oven, and drying for 1h at 45 ℃ to obtain the pre-modified loofah sponge; mixing the pre-modified loofah sponge fibers with a dopamine solution with the mass concentration of 10mg/L, placing the mixture into a microwave reactor, carrying out microwave reaction for 10 hours at the power of 100W, taking out the pre-modified loofah sponge after the microwave reaction is finished, and naturally drying the pre-modified loofah sponge to obtain the film-coated loofah sponge; weighing 10 parts of tryptone, 5 parts of yeast extract, 10 parts of sodium chloride, 900 parts of deionized water and 200 parts of the membrane-coated loofah sponge, uniformly mixing to obtain a substrate, adding an aspergillus oryzae bacterial suspension with the concentration of 0.01g/mL and the mass of the substrate being 5% of that of the substrate into the substrate, carrying out constant-temperature oscillation culture for 2 days at 25 ℃, filtering and separating to obtain filter residues after the culture is finished, repeatedly washing the filter residues for 3 times by using the deionized water, and naturally drying the filter residues to obtain the heavy metal wastewater biomass adsorbent.
Example 2
Selecting mature loofah sponge, peeling and removing seeds, cutting the loofah sponge into blocks with the size of 1cm multiplied by 1cm, repeatedly washing the blocks with deionized water and boiling water for 4 times in sequence, mixing the washed blocks with 6% of sodium hydroxide solution according to the mass ratio of 1:10, standing and soaking for 4 hours to obtain alkali-soaked loofah sponge; mixing the alkali-dipped loofah sponge with 0.4 mass percent benzophenone ethanol solution according to the mass ratio of 1:8, putting the mixture into an ultrasonic oscillator, oscillating and dipping the mixture for 2 hours at the frequency of 35kHz, taking out the loofah sponge after dipping, putting the loofah sponge into an oven, and drying the loofah sponge for 1 hour at 108 ℃ to obtain pretreated loofah sponge; mixing water, ethanol and acrylic acid according to a mass ratio of 15:5:2 to obtain a grafting solution, mixing the grafting solution and the pretreated loofah sponge according to a mass ratio of 12:1 to obtain a mixed solution, adding methyl hydroquinone accounting for 0.5% of the mass of the grafting solution into the mixed solution, and stirring for 13min to obtain a reaction base solution; transferring the reaction base solution into a test tube, introducing nitrogen for 10min, discharging all oxygen in the test tube, sealing, transferring into an ultraviolet light grafting reaction device, carrying out irradiation reaction for 2h under the condition that the ultraviolet light power is 15W, taking out a reaction product after the reaction is finished, repeatedly washing the reaction product for 4 times by using boiling water and ethanol, extracting by using acetone for 24h to remove residual homopolymer on the surface of the reaction product, finally washing by using water, putting into an oven, and drying for 2h at 45 ℃ to obtain the pre-modified loofah sponge; mixing the pre-modified loofah sponge fibers with a dopamine solution with the mass concentration of 10mg/L, putting the mixture into a microwave reactor, carrying out microwave reaction for 11 hours at the power of 150W, taking out the pre-modified loofah sponge after the microwave reaction is finished, and naturally drying the pre-modified loofah sponge to obtain the film-coated loofah sponge; weighing 13 parts of tryptone, 8 parts of yeast extract, 13 parts of sodium chloride, 950 parts of deionized water and 250 parts of the membrane-coated loofah sponge, uniformly mixing to obtain a substrate, adding an aspergillus oryzae bacterial suspension with the concentration of 0.01g/mL and the mass of the substrate being 5% of that of the substrate into the substrate, carrying out constant-temperature oscillation culture at 28 ℃ for 2 days, filtering and separating to obtain filter residues after the culture is finished, repeatedly washing the filter residues for 4 times by using deionized water, and naturally drying the filter residues to obtain the heavy metal wastewater biomass adsorbent.
Example 3
Selecting mature loofah sponge, peeling and removing seeds, cutting the loofah sponge into blocks with the size of 1cm multiplied by 1cm, repeatedly washing the blocks with deionized water and boiling water for 5 times in sequence, mixing the washed block loofah sponge with a sodium hydroxide solution with the mass fraction of 6% according to the mass ratio of 1:10, standing and soaking for 5 hours to obtain alkali-soaked loofah sponge; mixing the alkali-dipped loofah sponge with 0.4 mass percent benzophenone ethanol solution according to the mass ratio of 1:8, putting the mixture into an ultrasonic oscillator, oscillating and dipping the mixture for 2 hours at the frequency of 40kHz, taking out the loofah sponge after dipping, putting the loofah sponge into an oven, and drying the loofah sponge for 2 hours at the temperature of 110 ℃ to obtain pretreated loofah sponge; mixing water, ethanol and acrylic acid according to a mass ratio of 15:5:2 to obtain a grafting solution, mixing the grafting solution and the pretreated loofah sponge according to a mass ratio of 12:1 to obtain a mixed solution, adding methyl hydroquinone accounting for 0.5% of the mass of the grafting solution into the mixed solution, and stirring for 15min to obtain a reaction base solution; transferring the reaction base solution into a test tube, introducing nitrogen for 10min, discharging all oxygen in the test tube, sealing, transferring into an ultraviolet light grafting reaction device, carrying out irradiation reaction for 3h under the condition that the ultraviolet light power is 15W, taking out a reaction product after the reaction is finished, repeatedly washing the reaction product for 5 times by using boiling water and ethanol, extracting by using acetone for 24h to remove residual homopolymer on the surface of the reaction product, finally washing by using water, putting into an oven, and drying for 2h at 45 ℃ to obtain the pre-modified loofah sponge; mixing the pre-modified loofah sponge fibers with a dopamine solution with the mass concentration of 10mg/L, putting the mixture into a microwave reactor, carrying out microwave reaction for 12 hours at the power of 200W, taking out the pre-modified loofah sponge after the microwave reaction is finished, and naturally drying the pre-modified loofah sponge to obtain the film-coated loofah sponge; weighing 15 parts of tryptone, 10 parts of yeast extract, 15 parts of sodium chloride, 1000 parts of deionized water and 300 parts of the film-coated loofah sponge, uniformly mixing to obtain a substrate, adding an aspergillus oryzae bacterial suspension with the concentration of 0.01g/mL and the mass of the substrate being 5% of that of the substrate into the substrate, carrying out constant-temperature oscillation culture for 3 days at 30 ℃, filtering and separating to obtain filter residues after the culture is finished, repeatedly washing the filter residues for 5 times by using deionized water, and naturally drying the filter residues to obtain the heavy metal wastewater biomass adsorbent.
Comparative example 1: the preparation method is basically the same as that of the example 1 of the invention, except that the original loofah sponge is used for replacing the pre-modified loofah sponge of the invention, and the biomass adsorbent is also prepared;
comparative example 2: the preparation method is basically the same as that of example 1 of the present invention, except that the pre-modified loofah sponge is not subjected to microbial modification, but is directly used as a biomass adsorbent;
the performance of examples 1 to 3 of the present invention and comparative examples 1 and 2 were measured, respectively, and the results are shown in table 1:
the detection method comprises the following steps:
the adsorbent obtained in the above example and the adsorbent of the comparative example are respectively added into heavy metal wastewater according to the adding amount of 10mg/L, after the adding is finished, the mixture is stirred for 40min and kept stand, the supernatant obtained by separation is the treated heavy metal wastewater, then the content of heavy metal ions in the treated heavy metal wastewater is detected, and the specific detection results are shown in Table 1:
TABLE 1 Performance test results
As can be seen from the detection data in the above table, in comparative example 1 of the present invention, the original loofah sponge is used to replace the pre-modified loofah sponge of the present invention, and the biomass adsorbent is also prepared, so that the adsorption capacity and the heavy metal removal rate of the final adsorbent are both significantly reduced, and therefore, the polymer modification performed on the loofah sponge of the present invention indeed improves the adsorption performance of the adsorbent, and in comparative example 2, the pre-modified loofah sponge is not subjected to the microbial modification, but is directly used as the biomass adsorbent, so that the adsorption capacity and the heavy metal removal rate of the final adsorbent are both significantly reduced, and thus, the microbial modification performed on the pre-modified loofah sponge of the present invention indeed improves the adsorption performance of the adsorbent, and has a broad application prospect.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The heavy metal wastewater biomass adsorbent is characterized in that: is prepared by culturing and reacting a coated loofah sponge and an aspergillus oryzae bacterium suspension in the presence of tryptone, a yeast extract, sodium chloride and deionized water;
the film-coated loofah sponge is prepared by microwave reaction of a pre-modified loofah sponge and a dopamine solution;
the pre-modified loofah sponge is prepared by mixing pre-treated loofah sponge and grafting liquid and then carrying out ultraviolet light initiated reaction;
the pretreated loofah sponge is prepared by carrying benzophenone ethanol solution on loofah sponge after alkaline leaching;
the grafting solution is prepared by mixing water, ethanol and acrylic acid.
2. A preparation method of a heavy metal wastewater biomass adsorbent is characterized by comprising the following steps: the preparation method comprises the following specific steps:
(1) selecting loofah sponge, cutting into blocks, repeatedly washing, mixing the washed blocks with a sodium hydroxide solution, and soaking to obtain alkaline-leaching loofah sponge;
(2) mixing the alkali-soaked loofah sponge and a benzophenone ethanol solution, soaking and drying to obtain pretreated loofah sponge;
(3) mixing water, ethanol and acrylic acid to obtain a grafting solution, mixing the grafting solution with the pretreated loofah sponge, adding methyl hydroquinone, and stirring to obtain a reaction base solution;
(4) transferring the reaction base solution into a test tube, discharging oxygen, sealing, transferring into an ultraviolet light grafting reaction device, performing irradiation reaction, repeatedly washing after the reaction is finished, extracting with acetone, washing with water, and drying to obtain pre-modified loofah sponge;
(5) mixing the pre-modified loofah sponge fibers with the dopamine solution, carrying out microwave reaction, taking out the pre-modified loofah sponge after reaction, and naturally airing to obtain the film-coated loofah sponge;
(6) weighing tryptone, a yeast extract, sodium chloride, deionized water and a film-coated loofah sponge, uniformly mixing to obtain a substrate, adding an aspergillus oryzae bacterial suspension into the substrate, carrying out constant-temperature shaking culture, filtering and separating to obtain filter residues after the culture is finished, repeatedly washing with the deionized water, and naturally drying to obtain the heavy metal wastewater biomass adsorbent.
3. The preparation method of the heavy metal wastewater biomass adsorbent according to claim 2, characterized by comprising the following specific preparation steps:
(1) peeling and seed removing mature loofah sponge, cutting into blocks with the size of 1cm multiplied by 1cm, repeatedly washing with deionized water and boiling water for 3-5 times in sequence, mixing the washed blocks of loofah sponge with a sodium hydroxide solution with the mass fraction of 6%, standing and soaking for 3-5 hours to obtain alkali-soaked loofah sponge;
(2) mixing the alkali-dipped loofah sponge and 0.4 mass percent benzophenone ethanol solution according to a mass ratio of 1:8, putting the mixture into an ultrasonic oscillator, carrying out oscillation dipping, taking out the loofah sponge after dipping, putting the loofah sponge into an oven, and drying the loofah sponge at 105-110 ℃ for 1-2 hours to obtain pretreated loofah sponge;
(3) mixing water, ethanol and acrylic acid to obtain a grafting solution, mixing the grafting solution and the pretreated loofah sponge to obtain a mixed solution, adding methyl hydroquinone with the mass of 0.5% of that of the grafting solution into the mixed solution, and stirring for 10-15 min to obtain a reaction base solution;
(4) transferring the reaction base solution into a test tube, introducing nitrogen for 10min, discharging all oxygen in the test tube, sealing, transferring into an ultraviolet light grafting reaction device, carrying out irradiation reaction, taking out a reaction product after the reaction is finished, repeatedly washing the reaction product for 3-5 times by using boiling water and ethanol, extracting for 24 hours by using acetone to remove residual homopolymer on the surface of the reaction product, finally washing by using water, putting into an oven, and drying for 1-2 hours at 45 ℃ to obtain the pre-modified loofah sponge;
(5) mixing the pre-modified loofah sponge fibers with a dopamine solution with the mass concentration of 10mg/L, placing the mixture into a microwave reactor for microwave reaction, taking out the pre-modified loofah sponge after the microwave reaction is finished, and naturally drying the pre-modified loofah sponge to obtain the film-coated loofah sponge;
(6) weighing tryptone, a yeast extract, sodium chloride, deionized water and a film-coated loofah sponge, uniformly mixing to obtain a substrate, adding an aspergillus oryzae bacterial suspension with the concentration of 0.01g/mL and the mass of 5% of the substrate into the substrate, carrying out constant-temperature oscillation culture for 2-3 days at 25-30 ℃, filtering and separating to obtain filter residues after the culture is finished, repeatedly washing for 3-5 times by using the deionized water, and naturally airing to obtain the heavy metal wastewater biomass adsorbent.
4. The preparation method of the heavy metal wastewater biomass adsorbent according to claim 2 or 3, characterized in that: the mass ratio of the blocky loofah sponge washed in the step (1) to the sodium hydroxide solution with the mass fraction of 6% is 1: 10.
5. The preparation method of the heavy metal wastewater biomass adsorbent according to claim 2 or 3, characterized in that: in the step (2), the frequency of the vibration dipping is 30-40 kHz, and the time of the vibration dipping is 1-2 h.
6. The preparation method of the heavy metal wastewater biomass adsorbent according to claim 2 or 3, characterized in that: the mass ratio of the water, the ethanol and the acrylic acid in the step (3) is 15:5:2, and the mass ratio of the grafting solution to the pretreated loofah sponge is 12: 1.
7. The preparation method of the heavy metal wastewater biomass adsorbent according to claim 2 or 3, characterized in that: the ultraviolet light power during the irradiation reaction in the step (4) is 15W, and the irradiation reaction time is 2-3 h.
8. The preparation method of the heavy metal wastewater biomass adsorbent according to claim 2 or 3, characterized in that: the microwave reaction power in the step (5) is 100-200W, and the microwave reaction time is 10-12 h.
9. The preparation method of the heavy metal wastewater biomass adsorbent according to claim 2 or 3, characterized in that: in the step (6), by weight, 10-15 parts of tryptone, 5-10 parts of yeast extract, 10-15 parts of sodium chloride, 900-1000 parts of deionized water and 200-300 parts of film-coated loofah sponge.
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