CN114014418A - Preparation method of magnetic flocculant and application of magnetic flocculant in removing microcystis aeruginosa - Google Patents

Preparation method of magnetic flocculant and application of magnetic flocculant in removing microcystis aeruginosa Download PDF

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CN114014418A
CN114014418A CN202111426991.6A CN202111426991A CN114014418A CN 114014418 A CN114014418 A CN 114014418A CN 202111426991 A CN202111426991 A CN 202111426991A CN 114014418 A CN114014418 A CN 114014418A
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magnetic
flocculant
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microcystis aeruginosa
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CN114014418B (en
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付宇
张潆元
秦丹铃
路瑶
张依
孙海达
代姣
梁琦
邓颖
史倩
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GUIZHOU ACADEMY OF TESTING AND ANALYSIS
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/48Treatment of water, waste water, or sewage with magnetic or electric fields
    • C02F1/488Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation

Abstract

The invention relates to a preparation method of a magnetic flocculant and application of the magnetic flocculant in removing microcystis aeruginosa, wherein the environmental temperature is set, and Fe is regulated and controlled2+/Fe3+The preparation method comprises the steps of mixing the solution, magnetically stirring and homogenizing, and the like, and the magnetic flocculant is used for flocculating and magnetically separating the microcystis aeruginosa. The magnetic flocculant is easy to prepare, high in flocculation efficiency, capable of being recycled and capable of efficiently removing microcystis aeruginosa in water within 5 minutes.

Description

Preparation method of magnetic flocculant and application of magnetic flocculant in removing microcystis aeruginosa
Technical Field
The invention relates to the field of environmental protection, and particularly relates to a magnetic flocculant and application thereof in removing microcystis aeruginosa.
Background
The cyanobacterial bloom is one of the global major water environment problems. The mass propagation of the harmful blue algae can quickly consume the dissolved oxygen in the water body, and the ecological environment of the water body is seriously influenced. Meanwhile, blue algae such as Microcystis aeruginosa and the like can also generate algal toxins with strong carcinogenic effect, and the algal toxins can cause serious threat to human health through aquatic products, drinking water and other ways.
At present, the common methods for treating the cyanobacterial bloom comprise mechanical fishing, biological control, flocculation and the like. Although the mechanical fishing has better treatment effect, the engineering quantity is large and the operation cost is high. The biological control has the advantages of lasting effect, small environmental toxic and side effects and the like, but has the defects of slow effect and the like. In contrast, the flocculation method has a popularization prospect due to the characteristics of quick effect, high removal efficiency and the like. The traditional flocculation method usually adopts a chemical reagent method to flocculate the blue algae, so as to achieve the effect of removing the blue algae by sedimentation, and the removal rate of the blue algae can reach more than 90 percent. But it still takes several hours for the flocs to settle and separate, and part of the flocculant (such as aluminum chloride, ferric chloride, etc.) will inevitably remain in the water body, thus causing secondary pollution. In addition, conventional chemical flocculants are usually disposable reagents and are difficult to recycle.
In recent years, magnetic flocculants have attracted extensive attention because of their characteristics of high floc separation speed, low separation cost, high flocculation efficiency, simple operation and the like. Jiang et al developed a Fe3O4Polymeric ferromagnetic chloride flocculant (Jiang el al., The effect of magnetic nanoparticles removal by a composite flocculant. Cold Surface A,2010,369:260-Microcystis aeruginosa. In a slightly acidic solution (pH 4.0-7.0), Fe3O4The nanoparticles are positively charged and the microcystis aeruginosa is negatively charged, and the nanoparticles and the microcystis aeruginosa are electrostatically attracted to form flocs, so that the microcystis aeruginosa is removed. But when the pH value of the solution is larger than Fe3O4At isoelectric point (about pH 6.8) of the nanoparticles, Fe3O4The surface of the nano particles is negatively charged, and the isoelectric point of the microcystis aeruginosa is far lower than that of Fe3O4And (3) nanoparticles. Thus, in a more basic solution, Fe3O4The nano particles and microcystis aeruginosa generate electrostatic repulsion to lead Fe3O4The flocculation efficiency of the nanoparticles decreases. In view of the above problem, Yang et al developed a magnetic flocculant modified with polyethyleneimine (Yang et al, Interpretation of the discrimination in pharmaceutical efficacy of differential types of microorganisms using Polyethylene (PEI) -coated magnetic nanoparticles, alumina Res,2018,29: 257), wherein the modified magnetic flocculant has a removal rate of Microcystis aeruginosa of about 90%, and a removal rate of Microcystis aeruginosa of 63.5% after 3 times of recycling. Yin et al report a chitosan-modified Fe3O4A nano composite flocculant (Yin et al, Biocompatible magnetic flocculation for flocculation of microbial cells: Isotherms, mechanics and water recycling. Sep purification. 2021,279:119679) can flocculate 95.49% of Chlorella vulgaris within 10min, but the pH of the solution needs to be maintained at 3.0-4.0 to exert a better flocculation effect.
Although the flocculation performance of the magnetic flocculant can be improved by utilizing the modification of the high molecular polymer, the synthesis steps are complicated, and the required reagents are various and long in time consumption. Furthermore, there is still a need to carefully consider the potential environmental and health risks of high molecular polymers. Therefore, the development of the high-efficiency magnetic flocculant which is environment-friendly, simple in synthesis steps, quick in response and recyclable has very important significance for controlling the water bloom caused by blue algae such as microcystis aeruginosa and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a magnetic flocculant.
The invention also aims to provide an application of the magnetic flocculant in removing microcystis aeruginosa.
The preparation method of the magnetic flocculant comprises the following specific steps:
1) setting the environmental temperature to be 20-30 ℃;
2) preparing Fe with a concentration of 1.0mol/L with 1.0-2.0N hydrochloric acid or sulfuric acid solution2+A solution;
3) preparing Fe with a concentration of 1.0mol/L with 1.0-2.0N hydrochloric acid or sulfuric acid solution3+A solution;
4) preparing NaOH solution with the concentration of 1.0mol/L as precipitation solution;
5) respectively putting 1mL of the solution obtained in the step 2) and 2mL of the solution obtained in the step 3) into a 50mL beaker, and uniformly mixing to obtain Fe2+/Fe3+Mixing the solution;
6) adopting 1.0mol/L NaOH solution as a precipitation solution, taking 25mL of the precipitation solution, and dripping Fe into the precipitation solution by using a speed-adjustable titration device2+/Fe3+Mixing the solution;
7) adding a magnetic stirrer with the diameter of 6 multiplied by 20mm in the coprecipitation process for homogenizing;
8) after the dropwise addition of the NaOH solution is finished, forming a black or brown black magnetic fluid in the beaker, washing the obtained magnetic fluid by using deionized water with the volume of 20-80 times that of the obtained magnetic fluid, adhering a neodymium iron boron magnet to the wall of the beaker to perform solid-liquid separation, and removing supernatant after 5-10 min of separation; or cleaning with an ultrasonic cleaner or a vortex oscillator, separating with a magnet, removing supernatant, adding deionized water for cleaning, and repeating the steps for 3-10 times to obtain the magnetic flocculant.
Preferably, the ambient temperature in step 1) is set to 25 ℃.
Preferably, the Fe with the concentration of 1.0mol/L is prepared in the step 2)2+The solution is specifically as follows: weighing 9.94g FeCl2·4H2Adding 1.0-2.0N hydrochloric acid or sulfuric acid into a 25mL beaker, stirring and dissolving, transferring to a 50mL volumetric flask, and carrying out constant volume by using 1.0-2.0N hydrochloric acid or sulfuric acid to obtain 1.0mol/L Fe2+And (3) solution.
Preferably, the Fe with the concentration of 1.0mol/L is prepared in the step 3)3+The solution is specifically as follows: weighing 8.11g FeCl3Adding 1.0-2.0N hydrochloric acid or sulfuric acid into a 25mL beaker, stirring and dissolving, transferring to a 50mL volumetric flask, and fixing the volume by using 1.0-2.0N hydrochloric acid or sulfuric acid to obtain 1.0mol/L Fe3+And (3) solution.
Preferably, the dropping rate of the step 6) is set to be 10-60 drops/min.
Preferably, the magnetic stirrer is used for homogenizing in the coprecipitation process in the step 7), the early-stage rotation speed is 120-130 rpm, and the early stage is defined as that black precipitates are dripped into Fe along with 1.0mol/L NaOH solution2+/Fe3+A period of rapid dissolution after mixing the solution.
Preferably, the magnetic stirrer is used for homogenizing in the coprecipitation process of the step 7), the rotation speed at the later stage is 180-240 rpm, and the term 'later stage' in the invention is defined as that black precipitate is dripped into Fe along with 1.0mol/L NaOH solution2+/Fe3+Period after mixing the solution without dissolution.
The invention provides an application of a magnetic flocculant in removing microcystis aeruginosa.
Preferably, the concentration of the microcystis aeruginosa is 1.21g/L, pH-7.0 by the dry weight of the algal cells, and the adding amount of the magnetic flocculating agent is 0.40 g/L-1.00 g/L.
Preferably, the concentration of the microcystis aeruginosa is 1.21g/L, pH-5.0 by the dry weight of the algal cells, and the adding amount of the magnetic flocculating agent is 0.50 g/L.
Preferably, the concentration of the microcystis aeruginosa is 1.21g/L, pH-9.0 by the dry weight of the algal cells, and the adding amount of the magnetic flocculating agent is 0.50 g/L.
Advantageous effects
1. The invention proves Fe by experiments2+And Fe3+When the magnetic flocculant is dissolved in 1.0mol/L HCl, the prepared magnetic flocculant has higher Zeta potential, namely higher isoelectric point, and is beneficial to flocculating the electronegative microcystis aeruginosa.
2. Under the condition that the pH value is 7.0, 0.40, 0.50, 0.60, 0.80 and 1.00g/L of magnetic flocculating agent is respectively added, and the removal rate of microcystis aeruginosa in 5min is respectively 78.2%, 85.5%, 95.6%, 98.5% and 99.0%, which shows that the magnetic flocculating agent has better removal effect on microcystis aeruginosa.
3. Under the condition that the pH value is 5.0 and 9.0, and the adding amount of the flocculating agent is 0.50g/L, the removal rate of the magnetic flocculating agent to the microcystis aeruginosa can reach 99.6 percent and 91.2 percent respectively, which shows that the magnetic flocculating agent can obtain better flocculation effect in a wider pH range.
4. After the flocculation and the magnetic separation are finished, n-hexane is used for ultrasonically extracting the magnetic flocculant-microcystis aeruginosa magnetic floc, and then 1mol/L NaOH solution is used for cleaning the magnetic flocculant, so that the recovery and the utilization of the magnetic flocculant can be realized; under the conditions that the pH value is 7.0 and the primary adding amount of the magnetic flocculant is 0.50g/L, the magnetic flocculant realizes 5 times of cyclic utilization, the average removal rate of microcystis aeruginosa reaches 87.8 percent, and the magnetic flocculant has good reusability and is beneficial to reducing the treatment cost of the microcystis aeruginosa.
5. Compared with the high polymer modified magnetic flocculant, the preparation method provided by the invention is simple to operate, does not need nitrogen protection, requires few chemical reagents in the synthesis process, is green and environment-friendly, has short time, and can synthesize the target magnetic flocculant in one step.
6. The magnetic flocculant is a goethite/magnetite composite material, both of which are common iron minerals in the environment, and is environment-friendly.
7. The flocculation time is short, the floc separation is fast, the flocculant can be used in a wider pH range, and the flocculant can be used for emergency treatment.
Drawings
FIG. 1 is an X-ray diffraction pattern of the magnetic flocculant of the present invention.
FIG. 2 is a graph showing the magnetization curve of the magnetic flocculant of the present invention.
FIG. 3 is a scanning electron micrograph of the magnetic flocculant of the present invention.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1 preparation of magnetic flocculant
1) Setting the ambient temperature to be 25 ℃;
2) preparing Fe with the concentration of 1.0mol/L2+Solution: 9.94g FeCl was weighed2·4H2Adding 20mL of 1.0N hydrochloric acid or sulfuric acid into a 25mL beaker, stirring and dissolving, transferring to a 50mL volumetric flask, and fixing the volume by using 1.0N hydrochloric acid or sulfuric acid to obtain 1.0mol/L Fe2+A solution;
3) preparing Fe with the concentration of 1.0mol/L3+Solution: 8.11g FeCl was weighed3Adding 20mL of 1.0N hydrochloric acid or sulfuric acid into a 25mL beaker, stirring and dissolving, transferring into a 50mL volumetric flask, and adding 1.0N hydrochloric acid or sulfuric acid to a constant volume to obtain 1.0mol/L Fe3+A solution;
4) preparing NaOH solution with the concentration of 1.0mol/L as precipitation solution;
5) respectively putting 1mL of the solution obtained in the step 2) and 2mL of the solution obtained in the step 3) into a 50mL beaker, and uniformly mixing to obtain Fe2+/Fe3+Mixing the solution;
6) adopting 1.0mol/L NaOH solution as a precipitation solution, taking 25mL of the precipitation solution, and dripping Fe into the precipitation solution by using a speed-adjustable titration device2+/Fe3+Mixing the solution, wherein the early-stage dropping rate is set to be 10-15 drops/min, and the later-stage dropping rate is set to be 30-60 drops/min;
7) adding a 6 multiplied by 20mm magnetic stirrer for homogenizing in the coprecipitation process, wherein the rotation speed is 120-130 rpm in the early stage, and 180-240 rpm in the later stage;
8) after the dropwise addition of the NaOH solution is finished, forming a black or brown black magnetic fluid in the beaker, washing the obtained magnetic fluid by using deionized water with the volume of 20 times that of the obtained magnetic fluid, performing solid-liquid separation by using a neodymium iron boron magnet with the size of 40 multiplied by 20 multiplied by 10mm, and removing a supernatant after the separation is performed for 5-10 min; or cleaning with ultrasonic cleaner or vortex oscillator, separating with magnet, removing supernatant, adding deionized water, cleaning, and repeating the steps for 5 times to obtain magnetic flocculant.
Example 2 preparation of magnetic flocculant
1) Setting the ambient temperature to be 25 ℃;
2) preparing Fe with the concentration of 1.0mol/L2+Solution: 9.94g FeCl was weighed2·4H2Adding 20mL of 1.5N hydrochloric acid or sulfuric acid into a 25mL beaker, stirring and dissolving, transferring to a 50mL volumetric flask, and fixing the volume by using 1.5N hydrochloric acid or sulfuric acid to obtain 1.0mol/L Fe2+A solution;
3) preparing Fe with the concentration of 1.0mol/L3+Solution: 8.11g FeCl was weighed3Adding 20mL of 1.5N hydrochloric acid or sulfuric acid into a 25mL beaker, stirring and dissolving, transferring into a 50mL volumetric flask, and adding 1.5N hydrochloric acid or sulfuric acid to a constant volume to obtain 1.0mol/L Fe3+A solution;
4) preparing NaOH solution with the concentration of 1.0mol/L as precipitation solution;
5) respectively putting 1mL of the solution obtained in the step 2) and 2mL of the solution obtained in the step 3) into a 50mL beaker, and uniformly mixing to obtain Fe2+/Fe3+Mixing the solution;
6) adopting 1.0mol/L NaOH solution as a precipitation solution, taking 25mL of the precipitation solution, and dripping Fe into the precipitation solution by using a speed-adjustable titration device2+/Fe3+Mixing the solution, wherein the early-stage dropping rate is set to be 10-15 drops/min, and the later-stage dropping rate is set to be 30-60 drops/min;
7) adding a 6 multiplied by 20mm magnetic stirrer for homogenizing in the coprecipitation process, wherein the rotation speed is 120-130 rpm in the early stage, and 180-240 rpm in the later stage;
8) after the dropwise addition of the NaOH solution is finished, forming a black or brown black magnetic fluid in the beaker, washing the obtained magnetic fluid by using deionized water with the volume of 20 times that of the obtained magnetic fluid, performing solid-liquid separation by using a neodymium iron boron magnet with the size of 40 multiplied by 20 multiplied by 10mm, and removing a supernatant after the separation is performed for 5-10 min; or cleaning with ultrasonic cleaner or vortex oscillator, separating with magnet, removing supernatant, adding deionized water, cleaning, and repeating the steps for 5 times to obtain magnetic flocculant.
Example 3 preparation of magnetic flocculant
1) Setting the ambient temperature to be 25 ℃;
2) preparing Fe with the concentration of 1.0mol/L2+Solution: 9.94g FeCl was weighed2·4H2In a 25mL beaker, O,adding 20mL of 2.0N hydrochloric acid or sulfuric acid, stirring for dissolving, transferring to a 50mL volumetric flask, and adding 2.0N hydrochloric acid or sulfuric acid to constant volume to obtain 1.0mol/L Fe2+A solution;
3) preparing Fe with the concentration of 1.0mol/L3+Solution: 8.11g FeCl was weighed3Adding 20mL of 2.0N hydrochloric acid or sulfuric acid into a 25mL beaker, stirring and dissolving, transferring into a 50mL volumetric flask, and adding 2.0N hydrochloric acid or sulfuric acid to a constant volume to obtain 1.0mol/L Fe3+A solution;
4) preparing NaOH solution with the concentration of 1.0mol/L as precipitation solution;
5) respectively putting 1mL of the solution obtained in the step 2) and 2mL of the solution obtained in the step 3) into a 50mL beaker, and uniformly mixing to obtain Fe2+/Fe3+Mixing the solution;
6) adopting 1.0mol/L NaOH solution as a precipitation solution, taking 25mL of the precipitation solution, and dripping Fe into the precipitation solution by using a speed-adjustable titration device2+/Fe3+Mixing the solution, wherein the early-stage dropping rate is set to be 10-15 drops/min, and the later-stage dropping rate is set to be 30-60 drops/min;
7) adding a 6 multiplied by 20mm magnetic stirrer for homogenizing in the coprecipitation process, wherein the rotation speed is 120-130 rpm in the early stage, and 180-240 rpm in the later stage;
8) after the dropwise addition of the NaOH solution is finished, forming a black or brown black magnetic fluid in the beaker, washing the obtained magnetic fluid by using deionized water with the volume of 20 times that of the obtained magnetic fluid, performing solid-liquid separation by using a neodymium iron boron magnet with the size of 40 multiplied by 20 multiplied by 10mm, and removing a supernatant after the separation is performed for 5-10 min; or cleaning with ultrasonic cleaner or vortex oscillator, separating with magnet, removing supernatant, adding deionized water, cleaning, and repeating the steps for 5 times to obtain magnetic flocculant.
To prove the scientificity and rationality of the invention, the inventors conducted the following experimental studies:
experimental example 1: screening test for preparation method of magnetic flocculant
First, experimental facilities
In the experiment, microcystis aeruginosa is cultured in a light incubator (GZX-150 BSH-III, CIMO), the mineral components of the magnetic flocculant are determined by an X-ray diffractometer (XRD DLMAX-2550, Rigaku), the morphology of the magnetic flocculant is observed by a scanning electron microscope (SEM, JSM-6700F), and the saturation magnetization of the magnetic flocculant, the nanometer particle size and a Zeta potential analyzer (Zetasizer 3000HS, Malvern Instruments) are used for measuring the Zeta (Zeta) potential of the magnetic flocculant by using a vibration sample magnetometer (Lake Shore-7407).
Second, experimental materials and sources
FeCl2·4H2O (analytically pure > 98.0%) FeCl3(Sigma-Aldrich, reagent pure, 97.0% or more), hydrochloric acid (national drug group, chemical pure, 36.0-38.0%), sodium hydroxide (national drug group, analytical pure, 96.0% or more)
Third, Experimental methods
Screening test for hydrochloric acid concentration
Taking Fe2+And Fe3+The Zeta potentials (pH 7.0,25 ℃) of the magnetic flocculants obtained after dissolution in different concentrations of HCl are given in table 1.
TABLE 1 Fe2+And Fe3+Zeta (Zeta) potential of magnetic flocculant obtained after dissolving in HCl with different concentrations
Figure BDA0003378972400000071
The data in the above table show that Fe2+And Fe3+When the magnetic flocculant is dissolved in 1.0mol/L HCl, the prepared magnetic flocculant has higher zeta potential, namely higher isoelectric point, and is beneficial to flocculating the negatively charged microcystis aeruginosa. Further, as shown in fig. 1, the X-ray diffraction result indicates that the obtained magnetic flocculant is a goethite and magnetite binary composite material; as shown in fig. 2, the magnetic flocculant obtained on the surface of the hysteresis loop test has the saturation magnetization of 35.7emu/g, has stronger magnetism, and can realize rapid magnetic separation under the action of an external magnetic field; as shown in fig. 3, the resulting magnetic flocculant is composed of elongated rod-like goethite (shown by white solid oval circles) and spherical magnetite particles (shown by white dotted oval circles), both of nanometer scale, indicating that it has a considerable specific surface area. Wherein goethite has a size of about 20 × 100nm, and magnetismThe diameter of the iron ore is about 20nm, and the fine rod-shaped goethite can play a bridging role in the flocculation process to enhance the flocculation effect. As described above, it is preferable that the magnetic flocculant synthesized under the condition of hydrochloric acid concentration of 1.0mol/L is applied to Experimental example 2.
Experimental example 2: application of magnetic flocculant
The source of the algae species: microcystis aeruginosa is purchased from fresh water algae seed bank of Chinese academy of sciences, and the serial number of the algae is FACHB-315.
The culture conditions are as follows: inoculating into 500mL conical flask, culturing with BG11 culture medium with light quantum flux density of 40 μmol · m-2·s-1The light-dark ratio is 12h to 12h, the shaking is carried out once in the morning and at the evening, and the culture temperature is 25 ℃. After 22 days of culture under the above conditions, the cell concentration of Microcystis aeruginosa in the culture medium was 1.21g/L (algal cell dry weight).
And (3) adding a proper amount of flocculant into a proper amount of microcystis aeruginosa culture solution, uniformly mixing, and separating flocs for 5min by using a neodymium iron boron magnet to test the flocculation performance of the flocculant prepared in the invention on microcystis aeruginosa. The removal rate of microcystis aeruginosa is determined by measuring the optical density OD at 680nm of the algae liquid680The calculation is carried out according to the following formula:
removal rate (%) of Microcystis aeruginosa (OD)0-ODt)/OD0×100%
In the formula, OD0The optical density value, OD, of the microcystis aeruginosa liquid before the magnetic flocculant is addedtOptical density of supernatant after flocculation and separation of flocs with magnet.
In the experiment, hydrochloric acid or sodium hydroxide solution is used for adjusting the pH value of the solution.
Under the condition that the pH value is 7.0, 0.40, 0.50, 0.60, 0.80 and 1.00g/L of flocculating agents are respectively added, the removal rate of microcystis aeruginosa is 78.2 percent, 85.5 percent, 95.6 percent, 98.5 percent and 99.0 percent, and the flocculating agents have better removal effect on the microcystis aeruginosa.
Under the conditions that the pH value is 5.0 and 9.0 and the adding amount of the flocculating agent is 0.50g/L, the removal rate of the flocculating agent to the microcystis aeruginosa can reach 99.6 percent and 91.2 percent respectively, which shows that the flocculating agent can obtain better flocculation effect in a wider pH range.
After the magnetic flocculant is applied, n-hexane is used for ultrasonically extracting the magnetic flocculant-microcystis aeruginosa magnetic flocs, and then 1mol/L NaOH solution is used for cleaning the magnetic flocculant, so that the magnetic flocculant can be recycled. Under the conditions that the pH value is 7.0 and the primary adding amount of the magnetic flocculant is 0.50g/L, the magnetic flocculant realizes 5 times of cyclic utilization, and the average removal rate of microcystis aeruginosa reaches 87.8 percent, which shows that the magnetic flocculant has good reusability.
While the invention has been described in detail in the foregoing by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that certain changes and modifications may be made therein based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. The preparation method of the magnetic flocculant is characterized by comprising the following specific steps:
1) setting the environmental temperature to be 20-30 ℃;
2) preparing Fe with a concentration of 1.0mol/L with 1.0-2.0N hydrochloric acid or sulfuric acid solution2+A solution;
3) preparing Fe with a concentration of 1.0mol/L with 1.0-2.0N hydrochloric acid or sulfuric acid solution3+A solution;
4) preparing NaOH solution with the concentration of 1.0mol/L as precipitation solution;
5) respectively putting 1mL of the solution obtained in the step 2) and 2mL of the solution obtained in the step 3) into a 50mL beaker, and uniformly mixing to obtain Fe2+/Fe3+Mixing the solution;
6) adopting 1.0mol/L NaOH solution as a precipitation solution, taking 25mL of the precipitation solution, and dripping Fe into the precipitation solution by using a speed-adjustable titration device2 +/Fe3+Mixing the solution;
7) homogenizing by a magnetic stirrer in the coprecipitation process;
8) after the dropwise addition of the NaOH solution is finished, forming a black or brown black magnetic fluid in the beaker, washing the obtained magnetic fluid by using deionized water with the volume of 20-80 times that of the obtained magnetic fluid, performing solid-liquid separation by using a neodymium iron boron magnet, and removing a supernatant after 5-10 min of separation; or cleaning with an ultrasonic cleaner or a vortex oscillator, separating with a magnet, removing supernatant, adding deionized water for cleaning, and repeating the steps for 3-10 times to obtain the magnetic flocculant.
2. The method according to claim 1, wherein the ambient temperature is set to 25 ℃ in step 1).
3. The method according to claim 1, wherein step 2) is performed to prepare Fe with a concentration of 1.0mol/L2+The solution is specifically as follows: 9.94g FeCl was weighed2·4H2Adding 1.0-2.0N hydrochloric acid or sulfuric acid into a 25mL beaker, stirring and dissolving, transferring to a 50mL volumetric flask, and carrying out constant volume by using 1.0-2.0N hydrochloric acid or sulfuric acid to obtain 1.0mol/L Fe2+And (3) solution.
4. The method according to claim 1, wherein step 3) is performed to prepare Fe with a concentration of 1.0mol/L3+The solution is specifically as follows: 8.11g FeCl was weighed3Adding 1.0-2.0N hydrochloric acid or sulfuric acid into a 25mL beaker, stirring and dissolving, transferring to a 50mL volumetric flask, and fixing the volume by using 1.0-2.0N hydrochloric acid or sulfuric acid to obtain 1.0mol/L Fe3+And (3) solution.
5. The production method according to claim 1, wherein the dropping rate in the step 6) is set to 10 to 60 drops/min.
6. The preparation method according to claim 1, wherein magnetic stirrer is used for homogenizing in the coprecipitation process in the step 7), and the rotation speed is 80-300 rpm.
7. The preparation method according to claim 6, wherein the homogenization is carried out by a magnetic stirrer in the coprecipitation process in the step 7), and the rotating speed is 120-240 rpm.
8. Use of the magnetic flocculant prepared by the preparation method according to any one of claims 1 to 7 in removing microcystis aeruginosa.
9. The use of claim 8, wherein the concentration of microcystis aeruginosa is 1.21g/L, pH-5.0-9.0 by dry weight of algal cells, and the dosage of the magnetic flocculant is 0.40 g/L-1.00 g/L.
10. The use of claim 9, wherein the concentration of microcystis aeruginosa is 1.21g/L, pH-7.0 by dry cell weight, and the addition amount of the magnetic flocculating agent is 0.50 g/L.
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