CN114873699B - Magnetic cationized biological flocculant and preparation method thereof - Google Patents
Magnetic cationized biological flocculant and preparation method thereof Download PDFInfo
- Publication number
- CN114873699B CN114873699B CN202210631290.4A CN202210631290A CN114873699B CN 114873699 B CN114873699 B CN 114873699B CN 202210631290 A CN202210631290 A CN 202210631290A CN 114873699 B CN114873699 B CN 114873699B
- Authority
- CN
- China
- Prior art keywords
- flocculant
- cationized
- magnetic
- glycoprotein
- bioflocculant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a magnetic cationization bioflocculant and a preparation method thereof, comprising the following steps: adding a cationized bioflocculant to FeCl 3 In the solution, uniformly stirring, and reacting the nano magnetic powder to obtain a glycoprotein flocculant-Fe compound; adding the glycoprotein flocculant-Fe complex into an absolute ethyl alcohol solution containing a cross-linking agent, and performing a cross-linking reaction to obtain the magnetic cationic biological flocculant. The flocculant prepared by the invention has magnetic separation performance and adsorption and flocculation performance of protein macromolecules, and the interior of the flocculant is of a porous structure, so that the flocculant has more action sites beneficial to adsorption, and can realize high-efficiency separation and rapid sedimentation on the premise of ensuring flocculation effect.
Description
Technical Field
The invention belongs to the technical field of water treatment, and relates to a magnetic cationized bioflocculant and a preparation method thereof.
Background
Microbial flocculants are a class of metabolites produced by microorganisms that have flocculating activity. The advantages of high efficiency, no toxicity, no secondary pollution, wide application and the like are used as research hot spots. The substances secreted by microorganisms and having flocculation activity are negatively charged, and Ca is usually required 2+ 、Mg 2+ Plasma or polyaluminium chloride and the like are used as coagulant aids to improve the efficiency and activity of water treatment. This will result in a settled sludge and a higher residual Ca in the treated water sample 2+ 、Mg 2+ Or Al 3+ Secondary pollution is easy to cause, and the coagulant aid are added respectively during application, so that the operation steps are complicated. Cationic modification of microbial flocculants is one approach to solve this problem. At present, biomacromolecule cationization research is mainly focused on polysaccharide natural products such as starch, cellulose, chitosan and the like. The functional groups and the space structures in the molecule of glycoprotein or protein are complex and easy to change, and no related report of cationization of glycoprotein flocculant is currently seen.
In recent years, as an emerging water treatment technology, a magnetic flocculation technology has been rapidly developed in water supply treatment and various sewage and wastewater treatments, and has been applied to engineering practice. The magnetic flocculation technology mainly realizes the effective combination of tiny suspended matters or insoluble pollutants in water and small-particle-diameter magnetic particles through the functions of adsorption, coagulation and bridging, thereby increasing the volume and density of the flocs, further accelerating the sedimentation speed of the flocs, and further effectively reducing the hydraulic retention time of a flocculation sedimentation tank and increasing the surface load of the flocculation sedimentation tank. The conventional magnetic flocculation process mainly comprises the steps of respectively adding flocculant and magnetic powder, removing pollutants through the combined action of the flocculant and the magnetic powder, wherein the direct addition of unmodified magnetic powder in a water sample can cause the problems of large addition amount of the magnetic powder, low utilization efficiency, high economic cost, limited application range and the like.
Disclosure of Invention
The invention aims to provide a magnetic cationized bioflocculant and a preparation method thereof, wherein the bioflocculant integrates magnetism and flocculation characteristics and has the effect of efficiently removing suspended matters in water.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a magnetic cationized bioflocculant, comprising the following steps:
1) Adding a cationized bioflocculant to FeCl 3 In the solution, uniformly stirring, and reacting the nano magnetic powder to obtain a glycoprotein flocculant-Fe compound;
2) Adding the glycoprotein flocculant-Fe complex into an absolute ethyl alcohol solution containing a cross-linking agent, and performing a cross-linking reaction to obtain the magnetic cationic biological flocculant.
A further improvement of the invention is that per 15g of the cationic glycoprotein flocculant corresponding FeCl 3 The dosage of (2) is 0.01-0.02 mol; feCl 3 The concentration of the solution is 0.1-0.2mol/L.
The invention is further improved in that the cationized bioflocculant is prepared by the following steps:
uniformly mixing the epoxypropyl trimethyl ammonium chloride with the NaOH solution, adding the biological flocculant, uniformly mixing, and reacting for 2-4 hours at 80-90 ℃ to obtain the cationized glycoprotein microbial flocculant.
The invention is further improved in that the molar ratio of the epoxypropyl trimethyl ammonium chloride to the NaOH is 1 (1-1.6).
The invention is further improved in that the concentration of NaOH solution is 1mol/L, and the dosage of epoxypropyl trimethyl ammonium chloride corresponding to each 10g glycoprotein microbial flocculant is 0.01-0.03 mol.
The invention is further improved in that the nano magnetic powder is nano Fe 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The reaction time in the step 1) is 1-2 h, and the reaction time in the step 2) is 2-4 h.
The invention is further improved in that the mass ratio of the cationized bioflocculant to the magnetic powder is 1:0.6 to 0.9.
The invention is further improved in that the cross-linking agent is glutaraldehyde or succinaldehyde.
The invention is further improved in that the amount of the crosslinking agent corresponding to 10g of the cationized glycoprotein flocculant-Fe complex is 0.01-0.03 mol.
A magnetic cationized bioflocculant prepared according to the method described above.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes cationic biological flocculant as raw material, introduces nano magnetic powder, and uses aldehyde groups at two ends of the cross-linking agent to respectively act on Fe 3 O 4 And carrying out crosslinking reaction with amino groups of the glycoprotein flocculant to obtain the magnetic cationic bioflocculant. The flocculant prepared by the invention has magnetic separation performance and adsorption and flocculation performance of protein macromolecules, and the interior of the flocculant is of a porous structure, so that the flocculant has more action sites beneficial to adsorption, and can realize high-efficiency separation and rapid sedimentation on the premise of ensuring flocculation effect. The microbial flocculant prepared by the invention has positively charged molecules and magnetism, and can dispense with coagulant addition in the use process. The flocculant is independently used, and can efficiently remove suspended solids in water, so that the use flow of the flocculant is simplified, the purpose of simplifying the flocculation process is finally achieved, the coagulant adding cost is saved, the content of inorganic coagulant in settled sludge is reduced, and secondary pollution of the settled sludge to the environment is reduced.
Furthermore, the cationic quaternary ammonium salt epoxypropyl trimethyl ammonium chloride can effectively cationize the negatively charged microbial flocculant, and the Zeta potential of the microbial flocculant can reach +13mv from-49.7 mv, which is favorable for enhancing the electric neutralization adsorption capacity of the flocculant and provides a foundation for adsorption bridging and net cloth rolling.
Further, the mass ratio of the cationized bioflocculant to the nano magnetic powder ferroferric oxide is 1: the microbial flocculant prepared by the invention has the magnetic separation performance of magnetic nano particles and the adsorption and trapping performance of protein macromolecules at the same time by 0.6-0.9 composite magnetism. And the internal structure of the flocculant after magnetization is of a porous structure, so that more adsorption-facilitated action sites are provided, and high-efficiency separation and rapid sedimentation can be realized on the premise of ensuring flocculation effect, thereby increasing surface load and reducing hydraulic retention time.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The biological flocculant used in the invention is glycoprotein microbial flocculant, and specifically adopts the following patent: 201510582265.1, a glycoprotein-based microbial flocculant.
The preparation method of the magnetic cationized bioflocculant comprises the following steps:
uniformly mixing the epoxypropyl trimethyl ammonium chloride with the NaOH solution, reacting for 10min, adding a biological flocculant (glycoprotein type microbial flocculant), and rapidly stirring for 1.5-2 h at room temperature, wherein the rotating speed is about 80r/min, so that the uniform mixing is realized. Then, after reacting for 2-4 hours at 80-90 ℃, adding water into the mixture after the reaction is completed until the mixture is completely dissolved, and then adding absolute ethyl alcohol for extraction, wherein the volume ratio of the absolute ethyl alcohol extraction is 1:3-5. Separating out precipitate, centrifuging, discarding supernatant, and drying the precipitate to obtain the cationized glycoprotein microbial flocculant.
Wherein, the mol ratio of the epoxypropyl trimethyl ammonium chloride to the NaOH is 1 (1-1.6), and the concentration of the NaOH solution is 1mol/L. The glycoprotein microbial flocculant is 0.01 to 0.03mol per 10g of corresponding epoxypropyl trimethyl ammonium chloride.
Adding 100mL of 0.1-0.2mol/L FeCl into the cationized bioflocculant which is quantitatively crushed into powder 3 Stirring the solution at room temperature for 20 to 30 minutes, and then adding magnetic nano powder Fe under the condition of intense stirring 3 O 4 Fully mixing and reacting for 1-2 h to obtain glycoprotein flocculant-Fe complex, adding absolute ethyl alcohol, extracting glycoprotein flocculant-Fe complex, volatilizing alcohol, drying, grinding, adding into absolute ethyl alcohol solution containing quantitative cross-linking agent glutaraldehyde, using absolute ethyl alcohol to completely dissolve all reactants, cross-linking at room temperature for 2-4 h, and using aldehyde groups of glutaraldehyde to act on Fe respectively 3 O 4 And (3) carrying out a crosslinking reaction with amino groups of the glycoprotein flocculant, wherein the crosslinking agent glutaraldehyde can be replaced by succinaldehyde. Finally, the chemically crosslinked product is separated by magnetic fieldObtaining the magnetic cationized bioflocculant. Wherein the cationized bioflocculant and the magnetic nanometer Fe 3 O 4 The mass ratio of the powder is 1:0.6 to 0.9.
Wherein, the dosage of glutaraldehyde or glyoxal corresponding to each 10g of cationized glycoprotein flocculant-Fe complex is 0.01-0.03 mol. FeCl corresponding to each 15g of cationized glycoprotein flocculant 3 The amount of (C) is 0.01-0.02 mol.
The internal structure of the magnetic cationized biological flocculant prepared by the invention is of a porous structure, and has more action sites which are favorable for adsorption, and flocculated products can be separated magnetically.
Example 1
Step one, cationizing modification of glycoprotein microbial flocculant:
0.015mol of epoxypropyl trimethyl ammonium chloride and NaOH solution with the concentration of 1mol/L are mixed according to the mol ratio of the epoxypropyl trimethyl ammonium chloride to the NaOH of 1:1.2, stirring for 10min to fully mix and react, and adding 10g of glycoprotein microbial flocculant pure product. And (3) stirring the mixture at room temperature at the rotating speed of 80 r/mm for 2 hours, fully and uniformly mixing, and putting the mixture into a constant temperature box to react for 3 hours at the temperature of 80 ℃ to obtain the mixture of the cationized glycoprotein microbial flocculant.
Purifying the cationized glycoprotein microbial flocculant:
and (3) completely dissolving the mixture obtained in the step in 10mL of deionized water, adding 30mL of absolute ethyl alcohol to separate out a precipitate, filtering, repeatedly washing the precipitate for three times, discarding supernatant, retaining the precipitate, centrifuging at 10000r/min at 4 ℃ for 1min, and drying to obtain the purified cationized glycoprotein microbial flocculant.
Step three, magnetization of the cationized glycoprotein microbial flocculant:
1.5g of the cationized glycoprotein microbial flocculant was dissolved in 100mL of 0.1mol/L FeCl 3 After stirring the solution at room temperature for 0.5h, 1.2g of magnetic powder Fe was added with vigorous stirring 3 O 4 Stirring until completely dispersed. Adding absolute ethanol, precipitatingGlycoprotein flocculant-Fe complex and then washing off excess FeCl with absolute ethanol 3 The supernatant was discarded. Drying, grinding to obtain a dark brown solid, immersing the dark brown solid in 100mL absolute ethanol (glutaraldehyde mass concentration 3%) solution at room temperature for 3h, and allowing the aldehyde groups at both ends to act on Fe respectively 3 O 4 And amino groups of glycoprotein flocculant to carry out crosslinking reaction. Finally, the chemical crosslinking product is subjected to magnetic separation, ultra-pure water washing and drying to obtain the magnetic cationized bioflocculant.
Application example 1
This application example shows a method for removing suspended matter from river water using the magnetic cationized bioflocculant prepared in example 1.
2mL of the magnetic cationized bioflocculant (4 g/L) and the glycoprotein microbial flocculant pure product (4 g/L) are respectively added into 250mL of a certain river water suspension (pH 7.5) with the suspension concentration of about 2g/L, the mixture is stirred for 1min at a high speed, stirred for 2min at a low speed, and kept stand for 5min, and the absorbance of the supernatant at 550nm is measured. And calculating the flocculation rate of the sample.
Flocculation rate (%) = [ (a-B)/a ] ×100%, wherein:
a is absorbance of the sample before flocculation at 550 nm;
b is absorbance of supernatant at 550nm after flocculation.
Results test characterization:
the Zeta potential of the glycoprotein-based microbial flocculant pure product before modification in comparative example 1 is-49.7 mv, while the Zeta potential of the magnetic cationized biological flocculant modified by the method of the invention is +13mv; the flocculation rate of the glycoprotein-based microbial flocculant before modification was 60.2%, while the flocculation rate of the magnetic cationized biological flocculant after cationization in application example 1 was 89.3%. The result shows that the modified microbial flocculant can effectively cationize the negatively charged microbial flocculant, enhance the electric neutralization adsorption capacity of the flocculant and greatly improve the flocculation capacity of the flocculant.
Application example 2
Experiment group one: 1mL of coagulant Fe with concentration of 1mol/LCl 3 The solution was added to 250mL of a certain river water suspension (pH 7.5) having a suspension concentration of about 2g/L, followed by rapid stirring for 1min, then 2mL of a magnetic cationized bioflocculant (4 g/L), slow stirring for 2min, standing for 5min, and the absorbance of the supernatant at 550nm was measured. The flocculation rate of the sample was calculated.
Experimental group two: 2mL of a magnetic cationized bioflocculant (4 g/L) was added to 250mL of a certain river suspension (pH 7.5) with a suspension concentration of 2g/L, stirred rapidly for 1min, stirred slowly for 2min, left to stand for 5min, and the absorbance of the supernatant at 550nm was measured. And calculating the flocculation rate of the sample.
Results test characterization:
in the two experiments in the comparative example 2, the flocculation rate of the modified magnetic cationized biological flocculant in the second experiment group is 89.9%, and the flocculation rate of the magnetic cationized biological flocculant modified by the coagulant is 92.3%, so that the flocculation rate is improved by 2.4%, and the use process of the modified magnetic cationized biological flocculant does not need to add the coagulant on the premise of meeting the requirement of effluent quality.
Application example 3
And verifying the flocculation removal effect of the magnetic cationization bioflocculant on algae in the high algae water. Simultaneously adding magnetic cationization biological flocculant (40 mg/L) and glycoprotein microorganism flocculant pure product (40 mg/L) into the same 2 parts of 250mL water sample of certain lake water (algae cell concentration is about 5x 10) 7 Fast stirring for 1min, slow stirring for 2min, then standing for 5min, and sampling at 3cm below the liquid surface. The concentration of algae before and after flocculation was measured by an algae analyzer (flow cytometer), and the flocculation rate was calculated.
The flocculation rate calculation formula is: flocculation rate (%) = [ (A1-A2)/A1 ] ×100%
Wherein A1 is the concentration of algae cells in a water sample before adding a flocculating agent; a2 is the concentration of algae cells in the supernatant after the flocculation reaction is finished.
Results test characterization:
the removal rate of the glycoprotein microbial flocculant before modification is 28%, the removal effect is not obvious, the removal rate of the modified magnetic cationized biological flocculant on algae cells is 98%, the effect is good, and the flocculation and sedimentation separation capacities of the magnetic cationized biological flocculant after magnetism and cationization on algae cells are obviously improved.
Example 2
Step one, cationizing modification of glycoprotein microbial flocculant:
0.01mol of epoxypropyl trimethyl ammonium chloride and NaOH solution with the concentration of 1mol/L are mixed according to the mol ratio of the epoxypropyl trimethyl ammonium chloride to the NaOH of 1:1, stirring for 10min to fully mix and react, and adding 10g of glycoprotein microbial flocculant. And (3) stirring the mixture at room temperature at the rotating speed of 80 r/mm for 2 hours, fully and uniformly mixing, and putting the mixture into a constant temperature box to react at the temperature of 90 ℃ for 2 hours to obtain the mixture of the cationized glycoprotein microbial flocculant.
Purifying the cationized glycoprotein microbial flocculant:
and (3) completely dissolving the mixture obtained in the step in 10mL of deionized water, adding 30mL of absolute ethyl alcohol to separate out a precipitate, filtering, repeatedly washing the precipitate for three times, discarding supernatant, retaining the precipitate, centrifuging at 10000r/min at 4 ℃ for 1min, and drying to obtain the purified cationized glycoprotein microbial flocculant.
Step three, magnetization of the cationized glycoprotein microbial flocculant:
1.5g of the cationized glycoprotein microbial flocculant was dissolved in 100mL of 0.1mol/L FeCl 3 Stirring the solution at room temperature for 25min, and then adding 0.9g of magnetic nano powder Fe under the condition of intense stirring 3 O 4 Stir for 1h until completely dispersed. Adding absolute ethanol again to precipitate solid, and washing off excessive FeCl with absolute ethanol 3 The supernatant was discarded. Drying and grinding to obtain a black brown solid, namely glycoprotein flocculant-Fe compound, immersing the black brown solid in 100mL of glutaraldehyde absolute ethanol solution (the mass concentration of glutaraldehyde is 3%) for 3h at room temperature, and carrying out crosslinking reaction. The amount of glutaraldehyde corresponding to each 10g of cationized glycoprotein flocculant-Fe complex was 0.01mol. Finally, the chemically crosslinked product is subjected to magnetic separation and ultra-pure water washingAnd drying to obtain the magnetic cationized bioflocculant.
Example 3
Step one, cationizing modification of glycoprotein microbial flocculant:
0.03mol of epoxypropyl trimethyl ammonium chloride and NaOH solution with the concentration of 1mol/L are mixed according to the mol ratio of the epoxypropyl trimethyl ammonium chloride to the NaOH of 1:1.6, stirring for 10min to fully mix and react, and adding 10g of glycoprotein microbial flocculant. Stirring the mixture at room temperature at the rotating speed of 80 r/mm for 1.8h, fully and uniformly mixing, putting the mixture into a constant temperature box to react for 3 hours at the temperature of 85 ℃, adding water into the mixture after the reaction is completed until the mixture is completely dissolved, and then adding absolute ethyl alcohol for extraction, wherein the volume ratio of the absolute ethyl alcohol extraction is 1:4. Separating out precipitate, centrifuging, discarding supernatant, and drying the precipitate to obtain the mixture of the cationized glycoprotein microbial flocculant.
Purifying the cationized glycoprotein microbial flocculant:
and (3) completely dissolving the mixture obtained in the step in 10mL of deionized water, adding 40mL of absolute ethyl alcohol to separate out a precipitate, filtering, repeatedly washing the precipitate for three times, discarding supernatant, retaining the precipitate, centrifuging at 10000r/min at 4 ℃ for 1min, and drying to obtain the purified cationized glycoprotein microbial flocculant.
Step three, magnetization of the cationized glycoprotein microbial flocculant:
1.5g of the cationized glycoprotein microbial flocculant was dissolved in 100mL of 0.1mol/L FeCl 3 After stirring the solution at room temperature for 20min, 1.35g of magnetic powder Fe was added under vigorous stirring 3 O 4 Stir for 2h until completely dispersed. Adding absolute ethanol again to precipitate solid, and washing off excessive FeCl with absolute ethanol 3 The supernatant was discarded. Drying and grinding to obtain a black-brown solid, namely a cationized glycoprotein flocculant-Fe compound, and immersing the black-brown solid in 100mL glutaraldehyde absolute ethanol solution (glutaraldehyde mass concentration is 3%) for 2h at room temperature for crosslinking reaction. For every 10g of cationized glycoprotein flocculant-Fe complexGlutaraldehyde is used in an amount of 0.02mol. Finally, the chemical crosslinking product is subjected to magnetic separation, ultra-pure water washing and drying to obtain the magnetic cationized bioflocculant.
Example 4
Step one, cationizing modification of glycoprotein microbial flocculant:
0.02mol of epoxypropyl trimethyl ammonium chloride and NaOH solution with the concentration of 1mol/L are mixed according to the mol ratio of the epoxypropyl trimethyl ammonium chloride to the NaOH of 1:1.4, stirring for 10min to fully mix and react, and adding 10g of glycoprotein microbial flocculant. Stirring the mixture at room temperature at the rotating speed of 80 r/mm for 1.5h, fully and uniformly mixing, putting the mixture into a constant temperature box to react for 4 hours at the temperature of 82 ℃, adding water into the mixture after the reaction is completed until the mixture is completely dissolved, and then adding absolute ethyl alcohol for extraction, wherein the volume ratio of the absolute ethyl alcohol extraction is 1:5. Separating out precipitate, centrifuging, discarding supernatant, and drying the precipitate to obtain the mixture of the cationized glycoprotein microbial flocculant.
Purifying the cationized glycoprotein microbial flocculant:
and (3) completely dissolving the mixture obtained in the step in 10mL of deionized water, adding 50mL of absolute ethyl alcohol to separate out a precipitate, filtering, repeatedly washing the precipitate for three times, discarding supernatant, retaining the precipitate, centrifuging at 10000r/min at 4 ℃ for 1min, and drying to obtain the purified cationized glycoprotein microbial flocculant.
Step three, magnetization of the cationized glycoprotein microbial flocculant:
1.5g of the cationized glycoprotein microbial flocculant was dissolved in 100mL of 0.1mol/L FeCl 3 After stirring the solution at room temperature for 0.5h, 1g of magnetic powder Fe was added under vigorous stirring 3 O 4 Stir for 2h until completely dispersed. Adding absolute ethanol again to precipitate solid, and washing off excessive FeCl with absolute ethanol 3 The supernatant was discarded. Drying and grinding to obtain black brown solid, namely the cationic glycoprotein flocculant-Fe compound, immersing the black brown solid in 100mL of glyoxal absolute ethanol solution (the mass concentration of butanedial is 3 percent)) And (4) for 4 hours, and carrying out a crosslinking reaction. The amount of succinaldehyde corresponding to each 10g of the cationized glycoprotein flocculant-Fe complex was 0.03mol. Finally, the chemical crosslinking product is subjected to magnetic separation, ultra-pure water washing and drying to obtain the magnetic cationized bioflocculant.
Claims (5)
1. The preparation method of the magnetic cationized bioflocculant is characterized by comprising the following steps:
1) Adding a cationized bioflocculant to FeCl 3 In the solution, uniformly stirring, and reacting the nano magnetic powder to obtain a glycoprotein flocculant-Fe compound; wherein, the cationized bioflocculant is prepared by the following steps:
uniformly mixing the epoxypropyl trimethyl ammonium chloride with the NaOH solution, adding the glycoprotein microbial flocculant, uniformly mixing, and reacting at 80-90 ℃ for 2-4 hours to obtain the cationized glycoprotein microbial flocculant; the mass ratio of the cationized bioflocculant to the magnetic powder is 1:0.6 to 0.9; the nanometer magnetic powder is nanometer Fe 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The reaction time is 1-2 h, and the reaction time in the step 2) is 2-4 h;
2) Adding glycoprotein flocculant-Fe complex into absolute ethanol solution containing a cross-linking agent, and performing cross-linking reaction to obtain a magnetic cationic biological flocculant; the cross-linking agent is glutaraldehyde or succinaldehyde.
2. The method for preparing a magnetic cationized bioflocculant according to claim 1, wherein each 15g of the cationized glycoprotein flocculant corresponds to FeCl 3 The dosage of (2) is 0.01-0.02 mol; feCl 3 The concentration of the solution is 0.1-0.2mol/L.
3. The method for preparing the magnetic cationized bioflocculant according to claim 1, wherein the molar ratio of the epoxypropyl trimethyl ammonium chloride to the NaOH is 1 (1-1.6).
4. The method for preparing a magnetic cationized bioflocculant according to claim 1, wherein the concentration of NaOH solution is 1mol/L; the dosage of the epoxypropyl trimethyl ammonium chloride corresponding to each 10g glycoprotein microbial flocculant is 0.01-0.03 mol.
5. The method for preparing a magnetic cationized bioflocculant according to claim 1, wherein the amount of the crosslinking agent corresponding to 10g of the cationized glycoprotein flocculant-Fe complex is 0.01 to 0.03mol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210631290.4A CN114873699B (en) | 2022-06-06 | 2022-06-06 | Magnetic cationized biological flocculant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210631290.4A CN114873699B (en) | 2022-06-06 | 2022-06-06 | Magnetic cationized biological flocculant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114873699A CN114873699A (en) | 2022-08-09 |
| CN114873699B true CN114873699B (en) | 2023-08-18 |
Family
ID=82678841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210631290.4A Active CN114873699B (en) | 2022-06-06 | 2022-06-06 | Magnetic cationized biological flocculant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114873699B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229966A (en) * | 2014-08-30 | 2014-12-24 | 齐鲁工业大学 | Magnetic collagen starch modified cationic flocculant and preparation method thereof |
| CN105130014A (en) * | 2015-09-14 | 2015-12-09 | 西安建筑科技大学 | Preparation method and application of cation-modified glycoprotein type microorganism flocculating agent |
| CN105367715A (en) * | 2015-12-16 | 2016-03-02 | 杭州电子科技大学 | Preparing method for amphiphilic positive ion and chitosan based magnetic flocculating agent |
| CN109019879A (en) * | 2018-10-26 | 2018-12-18 | 江苏哈宜环保研究院有限公司 | A kind of preparation method and application of magnetic bio flocculant |
-
2022
- 2022-06-06 CN CN202210631290.4A patent/CN114873699B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229966A (en) * | 2014-08-30 | 2014-12-24 | 齐鲁工业大学 | Magnetic collagen starch modified cationic flocculant and preparation method thereof |
| CN105130014A (en) * | 2015-09-14 | 2015-12-09 | 西安建筑科技大学 | Preparation method and application of cation-modified glycoprotein type microorganism flocculating agent |
| CN105367715A (en) * | 2015-12-16 | 2016-03-02 | 杭州电子科技大学 | Preparing method for amphiphilic positive ion and chitosan based magnetic flocculating agent |
| CN109019879A (en) * | 2018-10-26 | 2018-12-18 | 江苏哈宜环保研究院有限公司 | A kind of preparation method and application of magnetic bio flocculant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114873699A (en) | 2022-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109734145B (en) | Composite flocculant for treating printing and dyeing wastewater | |
| CN111592069B (en) | Modified diatomite-nano calcium hydroxide composite sewage treatment agent | |
| CN113200658A (en) | Method for cooperatively treating antibiotic production wastewater | |
| CN108514870B (en) | Hydrotalcite-poly (m-phenylenediamine) composite material and preparation method and application thereof | |
| CN112978879A (en) | Double-compound magnetic modified flocculant for separating suspended particles in high-turbidity water and preparation and application thereof | |
| CN114735795B (en) | Sodium alginate-diatomite composite magnetic flocculant and preparation method thereof | |
| Sun et al. | Effective sludge dewatering technique using the combination of Fenton's reagent and CPAM | |
| Lin et al. | One-step removal of harmful algal blooms by dual-functional flocculant based on self-branched chitosan integrated with flotation function | |
| Du et al. | Insight into the purification of algael water by a novel flocculant with enhanced branched nanochitosan structure | |
| CN114873699B (en) | Magnetic cationized biological flocculant and preparation method thereof | |
| CN111559805B (en) | Defluorination agent for pretreatment of reverse osmosis inlet water and preparation method thereof | |
| CN114751597B (en) | Water treatment process based on composite magnetic flocculant | |
| Luo et al. | Effect of calcium ions on dewaterability of enzymatic-enhanced anaerobic digestion sludge | |
| CN114956278B (en) | Modified plant tannin environment-friendly magnetic flocculant and method for treating high algae water in steps | |
| CN112516970B (en) | Cellulose nanocrystal loaded chitosan adsorbent and application thereof in recycling of rare earth elements in sewage | |
| Liang et al. | Preparation of cationic aggregates derived from sewage sludge for efficient capture of organic matter | |
| Fuc et al. | Flocculation property of composite flocculants PAC/CPAM for polluted landscape water pretreatment | |
| CN114590866A (en) | Environment-friendly heavy metal sewage treatment agent and application thereof | |
| CN110040831B (en) | Preparation method of sodium alginate-polymethacryloxyethyl trimethyl ammonium chloride organic flocculant | |
| CN112479328A (en) | Preparation method of magnetic polyaluminum ferric silicate flocculant | |
| Li et al. | A collaborative coagulation strategy for algae-laden and dye-containing water treatment | |
| CN112062100A (en) | Nano calcium peroxide, preparation method and application | |
| Yang et al. | Preparation and performance of CTS-AM-ETA as a modified chitosan flocculant | |
| CN110451729A (en) | A kind of processing method of high concentration organism P wastewater | |
| CN111036209A (en) | Preparation method and application of magnetic kaolin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |