CN111250052B - Multi-group chelating magnetic hypha water purifying agent and preparation method and application thereof - Google Patents
Multi-group chelating magnetic hypha water purifying agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a multi-group chelating magnetic hypha water purifying agent and a preparation method and application thereof, wherein the preparation method comprises three steps of hypha graphene oxide composite precursor preparation, homogeneous grafting reduction and magnetic separation, oxidation drying and magnetization: culturing fungus hypha by using a culture medium, and inactivating, washing, crushing and dissolving the hypha to obtain a hypha suspension; adding an oxidant into the graphene oxide solution, and then carrying out ultrasonic treatment to obtain a graphene oxide activation solution; dropwise adding the graphene oxide activation solution into the hypha suspension to obtain a hypha graphene oxide composite precursor suspension; adding ferrous solution into the mixture, performing homogeneous grafting, adding a reducing agent, performing in-situ reduction and deposition, performing magnetic separation and recovery, and performing oxidation, drying and magnetization to obtain the multi-group chelate magnetic mycelium water purifying agent. The water purifying agent prepared by the method has strong heavy metal matching performance and adsorption-bridging coprecipitation effect, can be used for treating complex heavy metal wastewater, and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of heavy metal organic complex wastewater treatment, and particularly relates to a multi-group chelating magnetic hypha water purifying agent and a preparation method and application thereof.
Background
With the rapid development of economic society and the rapid growth of population, the global demand for high-quality water is increasing, and the treatment of wastewater by adopting an environment-friendly and efficient method is becoming a research focus. However, at present, industrial and agricultural wastewater, urban wastewater and various mining wastewater contain heavy metals such as copper, lead, arsenic, chromium, zinc and the like, and the concentration of the heavy metals exceeds a certain limit, so that the heavy metals can cause serious harm to human bodies, animals and plants. For example, arsenic has high toxicity and carcinogenic, mutagenic effects, enters human bodies or other organisms through food chains, ground water, and seriously harms human health and ecological environment; hexavalent chromium is also a heavy metal with high toxicity, and a large amount of chromium-containing wastewater is produced in the industries of electroplating, tanning, mining, steelmaking and the like, so that the chromium is seriously harmful to the life health of human bodies, and chromium is one of 129 key pollutants recognized by the United states EPA. With the economic development, a lot of generated heavy metal wastewater also contains high-content organic matters such as chelating agents, antibiotics and the like, the wastewater has complex components, high chromaticity, high biotoxicity, poor biodegradability and high chemical treatment cost, and the treatment of the heavy metal organic wastewater and residues is a recognized technical problem at home and abroad.
At present, in the traditional water treatment method, an adsorption method is widely applied to the purification treatment of heavy metal organic wastewater. Many natural adsorption materials such as activated carbon, plant wastes and the like have high specific surface area and high microporous structure, and are the most common and widely applied adsorbents in the current sewage treatment technology. Although widely used, the adsorption performance of the composite adsorbent is weak, and the composite adsorbent is not strong for certain specific heavy metal pollutants. In addition, inorganic mineral types such as clay and zeolite exist in the market, and although they are also applied, they have similar disadvantages to biochar. With the development of material science, people select a traditional adsorbent with strong adsorbability on heavy metals, and through modification of the traditional adsorbent, the adsorption of the adsorbent material on the heavy metals is obviously enhanced, for example, a patent with publication number of CN103143325A discloses a preparation method of a glutamic acid intercalated hydrotalcite heavy metal adsorbent, which can effectively adsorb a plurality of heavy metal pollutants such as Pb ions, Cu ions, Cr ions and the like in water pollution, but the adsorption quantity is still limited due to the structural problem of the adsorption material.
Therefore, the fungal hypha water purifying agent is based on the series characteristics that fungal hypha is rich in protein, polysaccharide and lipid, the molecular structure of the fungal hypha contains glycosidic bonds, hydrogen bonds and other bonding bonds, and also contains hydroxyl groups, carboxyl groups and other functional groups, the fungal hypha water purifying agent is cheap and easy to obtain, can be prepared in batch and the like, the two-dimensional long-chain-shaped multi-group chelating magnetic hypha water purifying agent is prepared by magnetization, chelating group functionalization and other technological means, has the characteristics of strong chelating adsorption capacity, fast magnetic driving separation and the like, overcomes the major defects of low adsorption capacity and slow sedimentation after treatment, and can greatly reduce engineering investment and water treatment operation cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a multi-group chelating magnetic hypha water purifying agent and a preparation method and application thereof, and aims to improve the chelating capacity of the water purifying agent on heavy metals and the flocculation sedimentation separation effect. Can effectively improve the effect of the water purifying agent on treating complex wastewater, increase the settling speed and reduce the investment of wastewater engineering construction.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a multi-group chelating magnetic hypha water purifying agent comprises the following steps:
s1 preparation of hypha oxidized graphene composite precursor
Culturing to obtain fungus hypha pellets, inactivating, washing and crushing the hypha pellets, and dissolving according to the mass concentration of mycelium of 100-200 g/L to obtain a hypha suspension;
slowly dropwise adding a graphene oxide activation solution into the obtained hypha suspension under the condition of constant-temperature stirring to obtain a spiny chain hypha graphene oxide composite precursor suspension;
s2 homogeneous grafting reduction and magnetic separation
Under the condition of constant-temperature stirring, adding an acidified ferrous ion aqueous solution into the obtained hypha oxidized graphene composite precursor suspension, slowly dropwise adding a dilute reducing agent aqueous solution after the homogeneous reaction is stable until the mixed solution has no phase change, and finally obtaining an intermediate product through magnetic field separation;
s3 oxidizing, drying and magnetizing
And (5) washing the intermediate product obtained in the step (S2) by using deionized water, and oxidizing and drying at constant temperature to obtain the multi-group chelating type magnetic hypha water purifying agent.
Preferably, the graphene oxide activation solution in the step S1 is a dispersion solution of ultrasonically dispersed sheet graphene oxide and hydrogen peroxide, wherein the mass concentration of the sheet graphene oxide is 2-10 mg/L, and the hydrogen peroxide accounts for 2-5% of the total volume of the solution.
Preferably, the dropping speed of the graphene oxide activation solution in the step S1 is 1-5 mL/min & L.
Preferably, the ratio of the surface area of the hyphae to the surface area of the graphene oxide in the hyphae suspension is 1: 1-5.
Preferably, in the step S2, the dropping speed of the dilute reducing agent aqueous solution is less than 5%/min; wherein, 5 percent is the ratio of the volume of the added solution to the volume of the system solution.
Preferably, the concentration of the acidified aqueous ferrous ion solution in step S2 is less than 200 g/L; the concentration of iron ions in the mixed solution is not more than 10 g/L.
Preferably, the reducing agent in step S2 is one or more of borohydride, ammonium salt and thiosulfate.
The invention provides a multi-group chelating magnetic hypha water purifying agent, which is prepared by the method.
The invention also provides an application idea of the multi-group chelating magnetic hypha water purifying agent in complex heavy metal wastewater treatment, which comprises the following steps:
(1) detecting the concentration of heavy metals in the complex heavy metal wastewater, and entering step S2 when the total concentration of the heavy metals is more than 2 g/L; when the total concentration of the heavy metals is less than 2g/L, the step S3 is carried out;
(2) adding alkali liquor into the wastewater, adding polyacrylamide or polyaluminium sulfate, adjusting the pH value to 9-12, stirring, filtering and separating to obtain a first supernatant, adding the polybase chelate magnetic hypha water purifying agent prepared by the method of any one of claims 1-7 into the obtained first supernatant, stirring, performing magnetic field separation to obtain residues and a second supernatant, and treating the second supernatant by an activated carbon packing layer to reach the standard and discharge;
(3) adding the multi-group chelating magnetic hypha water purifying agent prepared by the method of any one of claims 1 to 6 into heavy metal wastewater, stirring, performing magnetic field separation to obtain residues and a third supernatant, and treating the third supernatant by an activated carbon filler layer to reach the standard and discharging.
Preferably, the method for recycling the residues in the steps (2) and (3) is to perform acidification, desorption and washing treatment on the residues, and then obtain magnetic (direct utilization) and non-magnetic residues (reuse after magnetization treatment) through magnetic field separation.
The scheme of the invention has the following beneficial effects:
(1) the multi-group chelating ability is strong: the complex heavy metal wastewater can be treated due to the multi-group chelation effect. The traditional adsorbent can quickly adsorb heavy metal ions in a coordination ionic state, but trace heavy metals in a chelating state and a colloid state are difficult to remove, so that heavy metal residues are caused. The water purifying agent can realize the chelation removal of heavy metals through group competitive coordination, and has stronger processing capacity.
(2) The water treatment process has large adsorption capacity: the hypha is natural protein, the mild treatment process in the preparation method provided by the invention furthest ensures the groups on the surface of the hypha, and in addition, the grafted graphene oxide two-dimensional structure surface also contains the groups, so that the multiple groups greatly improve the number of adsorption sites on the surface of the hypha, and can adsorb more heavy metals to achieve larger adsorption capacity.
(3) The adsorption reaction process is quick: the multi-group chelating magnetic hypha water purifying agent provided by the invention has large specific surface area (the specific surface area refers to the area value of a unit weight material), the preparation method provided by the invention adopts two-dimensional graphene oxide nanosheets for activation, the specific surface area of the activated two-dimensional graphene oxide nanosheet suspension solution is more than 500 square meters per gram, the specific surface area of a conventional adsorbing material is less than 10 square meters per gram, the specific surface area of the hypha material can be greatly increased, more chemical reaction sites are provided by the large specific surface area, and the adsorption chemical reaction process is accelerated.
(4) The precipitation process is rapid: in the heavy metal wastewater treatment, heavy metals cannot be decomposed and can only be separated by precipitating to the wall or the bottom of a vessel, so the speed of the precipitation process directly influences the engineering investment (assuming 10000 m) 3 D waste water production, if the precipitation separation time is 1d, 10000m is required to be constructed 3 The sedimentation tank has huge investment), the multi-group chelating type magnetic hypha water purifying agent provided by the invention has extremely strong magnetism, and can be quickly separated to the wall or the bottom of the tank in the presence of a magnetic field. Therefore, the method has two remarkable characteristics of quick separation and large sediment bulk density.
(5) The coprecipitation effect is good: the heavy metal precipitation process mostly adopts a neutralization process and generates a large amount of small hydroxide particles, but the small hydroxide particles are difficult to precipitate. The preparation method provided by the invention is based on the modified design of the chain-shaped mycelium, provides a large number of macromolecular microcosmic flocculants such as adsorption, bridging and the like for small particles difficult to settle in the flocculation precipitation process, can effectively destroy the stable structure of the small colloidal particles, enables the volume of the suspended heavy metal hydroxide small particles to be increased and to be agglomerated around the chain-shaped mycelium material for coprecipitation, and enhances the flocculation agglomeration effect.
Drawings
FIG. 1 is a scanning electron microscope image of a multi-group chelating magnetic hypha water purifying agent;
FIG. 2 is a Fourier infrared spectrum of the multi-group chelating magnetic hypha water purifying agent;
FIG. 3 is a spectrum diagram of a multi-group chelating magnetic hypha water purifying agent;
FIG. 4 is a graph showing the comparison of the separation effect before and after the treatment with the multi-radical chelate-type magnetic hypha water purifying agent in example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
Example 1
S1 preparation of hypha oxidized graphene composite precursor
Culturing to obtain fungus mycelium pellets, inactivating, washing and crushing the mycelium pellets, and dissolving the mycelium pellets according to the mass concentration of 100g/L to obtain a mycelium suspension;
slowly dripping the ultrasonically dispersed flaky graphene oxide and hydrogen peroxide dispersion solution into the obtained hypha suspension at the speed of 1mL/min & L under the condition of constant-temperature stirring to obtain the spine chain hypha graphene oxide composite precursor suspension; the mass concentration of the flaky graphene oxide is 2mg/L, and hydrogen peroxide accounts for 2% of the total volume of the solution;
wherein 0.01mL/min & L is the adding amount of the flaky graphene oxide per minute in the mixed solution with unit volume, and the unit is as follows: volume of the mixed solution per minute (ml of the volume of the sheet graphene oxide suspension); the ratio of the surface area of the hyphae to the surface area of the graphene oxide in the hyphae suspension is 1:1.
S2 homogeneous grafting reduction and magnetic separation
Adding an acidified ferrous ion aqueous solution into the obtained hypha graphene oxide composite precursor suspension under the conditions of constant temperature of 60 ℃ and stirring at 120rpm, slowly dropwise adding a dilute reducing agent aqueous solution after the homogeneous reaction is stable until the mixed solution has no phase change, and finally obtaining an intermediate product through magnetic field separation; the purpose of adding the ferrous sulfate is to enable ferrous ions to be uniformly adsorbed on the surfaces of the graphene oxide and the hypha material, and the purpose of slowly dripping the dilute reducing agent aqueous solution is to enable the subsequent adsorption deposition process to be uniform, so that uniform zero-valent iron pellets are formed and attached to the surface of the material, and the powder material is uniformly distributed in magnetic property. The concentration of the acidified ferrous ion aqueous solution is 50g/L, so that the precipitation of iron due to high pH value or crystallization can be effectively prevented, and the reduction of the activity of iron ions is prevented; the concentration of iron ions in the mixed solution is not more than 10g/L, so that excessive iron is prevented from covering the surface of the hypha material to influence the adsorption effect;
the reducing agent is sodium borohydride, the sodium borohydride can reduce ferrous ions into zero-valent iron small spherical particles and attach the zero-valent iron small spherical particles to the surface of the material, and the dropping speed of the sodium borohydride is 1%/min; wherein, 5 percent is the volume ratio of the added solution to the system solution; the aim is to ensure that ferrous ions are slowly reduced and uniformly deposited on the surface of the hypha material.
S3 oxidizing, drying and magnetizing
And (5) washing the intermediate product obtained in the step (S2) by using deionized water, and oxidizing and drying at constant temperature to obtain the multi-group chelating type magnetic hypha water purifying agent.
The SEM spectrum of the obtained water purifying agent is shown in figure 1, the infrared spectrum is shown in figure 2, the energy spectrum is shown in figure 3, and the precipitation and separation effects are shown in figure 4.
The obtained water purifying agent is used for treating heavy metal wastewater with the nickel concentration of 186.2mg/L, and specifically comprises the following steps:
(1) detecting the heavy metal concentration of the heavy metal wastewater, and entering step S3 when the total concentration of the heavy metals is less than 2 g/L;
(3) adding the polybase chelate magnetic hypha water purifying agent prepared by the method into heavy metal wastewater, stirring for 60min at normal temperature, performing magnetic field separation on 10ml of suspension after stirring, separating for less than 1min to obtain residue and supernatant, and performing layering effect as shown in figure 4.
Example 2
S1 preparation of hypha oxidized graphene composite precursor
Culturing to obtain fungus hypha pellets, inactivating, washing and crushing the hypha pellets, and dissolving the hypha pellets according to the mass concentration of 200g/L of mycelium to obtain a hypha suspension;
slowly dripping ultrasonically dispersed flaky graphene oxide and hydrogen peroxide dispersion solution into the obtained hypha suspension at the speed of 5mL/min & L under the condition of constant-temperature stirring to obtain spine hypha graphene oxide composite precursor suspension; the mass concentration of the flaky graphene oxide is 10mg/L, and hydrogen peroxide accounts for 5% of the total volume of the solution; wherein 5mL/min & L is the adding amount of the flaky graphene oxide in the mixed solution in unit volume per minute, and the unit is as follows: volume of milliliter laminar graphene oxide suspension per minute liter of volume of mixed solution; the ratio of the surface area of the hyphae to the surface area of the graphene oxide in the hypha suspension is 1: 1.5.
S2 homogeneous grafting reduction and magnetic separation
Adding an acidified ferrous ion aqueous solution into the obtained hypha graphene oxide composite precursor suspension under the conditions of constant temperature of 60 ℃ and stirring at 120rpm, slowly dropwise adding a dilute reducing agent aqueous solution after the homogeneous reaction is stable until the mixed solution has no phase change, and finally obtaining an intermediate product through magnetic field separation; the purpose of adding the ferrous sulfate is to enable ferrous ions to be uniformly adsorbed on the surfaces of the graphene oxide and the hypha material, and the purpose of slowly dripping the dilute reducing agent aqueous solution is to enable the subsequent adsorption deposition process to be uniform, so that uniform zero-valent iron pellets are formed and attached to the surface of the material, and the powder material is uniformly distributed in magnetic property. The concentration of the acidified ferrous ion aqueous solution is 200g/L, so that the precipitation of iron due to high pH value or crystallization can be effectively prevented, and the reduction of the activity of iron ions is prevented; the concentration of iron ions in the mixed solution is not more than 10g/L, so that excessive iron is prevented from covering the surface of the hypha material to influence the adsorption effect;
the reducing agent is a mixed solution of sodium borohydride and ammonia water, the sodium borohydride is a reducing agent and can reduce ferrous ions into zero-valent iron pellet particles which are attached to the surface of the material, and the dilute ammonia water can induce the deposition reduction of the iron ions, so that the ferrous ions are favorably uniformly distributed on the surface of the hypha material. Wherein the dropping speed of the mixed solution of sodium borohydride and ammonia water is 5%/min; wherein, 5 percent is the volume ratio of the added solution to the system solution; the aim is to ensure that ferrous ions are slowly reduced and uniformly deposited on the surface of the hypha material.
S3 oxidizing, drying and magnetizing
And (5) washing the intermediate product obtained in the step (S2) by using deionized water, and oxidizing and drying at constant temperature to obtain the multi-group chelating type magnetic hypha water purifying agent.
The obtained water purifying agent is used for treating heavy metal wastewater with lead concentration of 2.3g/L, and specifically comprises the following steps:
(1) detecting the concentration of heavy metal in the heavy metal wastewater, and entering step S2 when the total concentration of the heavy metal is more than 2 g/L;
(2) adding alkali liquor into the wastewater, adding polyacrylamide or polyaluminium sulfate, adjusting the pH value to 9.5, stirring, filtering and separating to obtain a first supernatant, testing the lead ion concentration of the first supernatant to be 358.23mg/L, adding the polygenic chelate magnetic hypha water purifying agent prepared in the example 2 into the first supernatant, stirring and reacting for 120min at normal temperature, separating by a magnetic field to obtain a residue and a second supernatant, testing the lead ion concentration of the second supernatant to be 2.85mg/L, treating the second supernatant by an activated carbon filler layer, and discharging the second supernatant after the lead ions are not detected and reach the standard.
Example 3
S1 preparation of hypha oxidized graphene composite precursor
Culturing to obtain fungus mycelium pellets, inactivating, washing and crushing the mycelium pellets, and dissolving the mycelium pellets according to the mass concentration of 120g/L to obtain a mycelium suspension;
slowly dripping the dispersion solution of the sheet graphene oxide and hydrogen peroxide which are subjected to ultrasonic dispersion into the obtained hypha suspension at the speed of 2.5mL/min & L under the condition of constant-temperature stirring to obtain a spiny chain hypha graphene oxide composite precursor suspension; the mass concentration of the flaky graphene oxide is 6mg/L, and hydrogen peroxide accounts for 3% of the total volume of the solution; wherein 2.5mL/min & L is the adding amount of the flaky graphene oxide per minute in the mixed solution with unit volume, and the unit is as follows: volume of the mixed solution per minute (ml of the volume of the sheet graphene oxide suspension); the ratio of the surface area of the hyphae to the surface area of the graphene oxide in the hypha suspension is 1: 1.5.
S2 homogeneous grafting reduction and magnetic separation
Adding an acidified ferrous ion aqueous solution into the obtained spine hypha graphene oxide composite precursor suspension under the conditions of constant temperature of 60 ℃ and stirring at 120rpm, slowly dropwise adding a dilute reducing agent aqueous solution after the homogeneous reaction is stable until the mixed solution has no phase change, and finally obtaining an intermediate product through magnetic field separation; the purpose of adding the ferrous sulfate is to enable ferrous ions to be uniformly adsorbed on the surfaces of the graphene oxide and the hypha material, and the purpose of slowly dripping the dilute reducing agent aqueous solution is to enable the subsequent adsorption deposition process to be uniform, so that uniform zero-valent iron pellets are formed and attached to the surface of the material, and the powder material is uniformly distributed in magnetic property. The concentration of the acidified ferrous ion aqueous solution is 150g/L, so that the iron can be effectively prevented from precipitating due to high pH value or crystallization, and the activity of the iron ions is reduced; the concentration of iron ions in the mixed solution is not more than 10g/L, so that excessive iron is prevented from covering the surface of the hypha material to influence the adsorption effect;
the reducing agent is a mixed solution of sodium borohydride and ammonia water, the sodium borohydride is a reducing agent and can reduce ferrous ions into zero-valent iron pellet particles which are attached to the surface of the material, and the dilute ammonia water can induce the deposition reduction of the iron ions, so that the ferrous ions are favorably uniformly distributed on the surface of the hypha material. Wherein the dropping speed of the mixed solution of sodium borohydride and ammonia water is 2%/min; wherein, 2 percent is the volume ratio of the added solution to the system solution; the aim is to ensure that ferrous ions are slowly reduced and uniformly deposited on the surface of the hypha material.
S3 oxidizing, drying and magnetizing
And (5) washing the intermediate product obtained in the step (S2) by using deionized water, and oxidizing and drying at constant temperature to obtain the multi-group chelating type magnetic hypha water purifying agent.
The obtained water purifying agent is used for treating heavy metal wastewater with characteristic pollutant zinc ion concentration of 2.97g/L, and specifically comprises the following steps:
(1) detecting the concentration of heavy metal in the heavy metal wastewater, and entering step S2 when the total concentration of the heavy metal is more than 2 g/L;
(2) adding alkali liquor into the wastewater, adding polyaluminum sulfate, adjusting the pH value to 10, stirring, filtering and separating to obtain a first supernatant, testing the content of zinc ions in the first supernatant to be 468.74mg/L, adding the multi-group chelating type magnetic hypha water purifying agent prepared in the embodiment 3 into the first supernatant, stirring and reacting for 120min at normal temperature, separating by a magnetic field to obtain residues and a second supernatant, testing the content of the zinc ions in the second supernatant to be 7.25mg/L, treating the second supernatant by an activated carbon packing layer, and discharging the second supernatant which meets the standard without detecting the zinc ions.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. A preparation method of a multi-group chelating magnetic hypha water purifying agent is characterized by comprising the following steps:
s1 preparation of hypha oxidized graphene composite precursor
Culturing to obtain fungus hypha pellets, inactivating, washing and crushing the hypha pellets, and dissolving according to the mass concentration of hypha of 100-200 g/L to obtain a hypha suspension;
slowly dropwise adding a graphene oxide activation solution into the obtained hypha suspension under the condition of constant-temperature stirring to obtain a spine-chain hypha graphene oxide composite precursor suspension; the graphene oxide activation solution is a dispersion solution of ultrasonically dispersed flaky graphene oxide and hydrogen peroxide, wherein the mass concentration of the flaky graphene oxide is 2-10 mg/L, and the hydrogen peroxide accounts for 2-5% of the total volume of the solution;
s2 homogeneous grafting reduction and magnetic separation
Under the condition of constant-temperature stirring, adding an acidified ferrous ion aqueous solution into the obtained spine-like hypha graphene oxide composite precursor suspension, slowly dropwise adding a dilute reducing agent aqueous solution after the homogeneous reaction is stable until the mixed solution has no phase change, and finally obtaining an intermediate product through magnetic field separation;
s3 oxidizing, drying and magnetizing
And (5) washing the intermediate product obtained in the step S2 by using deionized water, and oxidizing and drying at constant temperature to obtain the multi-group chelate magnetic hypha water purifying agent.
2. The preparation method according to claim 1, wherein the dropping speed of the graphene oxide activation solution in the step S1 is 1-5 mL/min.
3. The method according to claim 1, wherein the ratio of the surface area of the mycelium to the surface area of the graphene oxide in the mycelium suspension is 1:1 to 5.
4. The method according to claim 1, wherein the dropping speed of the diluted reducing agent aqueous solution slowly dropped in step S2 is less than 5%/min; wherein, 5 percent is the ratio of the volume of the added solution to the volume of the system solution.
5. The method according to claim 1, wherein the concentration of the acidified aqueous solution of ferrous ions in step S2 is less than 200 g/L; the concentration of iron ions in the mixed solution is not more than 10 g/L.
6. The method of claim 1, wherein the reducing agent in step S2 is one or more selected from the group consisting of borohydride, ammonia salt and thiosulfate.
7. A multi-group chelating magnetic hypha water purifying agent, which is characterized in that the water purifying agent is prepared by the method of any one of claims 1 to 6.
8. The application of the multi-group chelating magnetic hypha water purifying agent prepared by the method of any one of claims 1 to 6 in the treatment of complex heavy metal wastewater is characterized by comprising the following steps:
(1) detecting the concentration of heavy metal in the complex heavy metal wastewater, and entering the step (2) when the total mass concentration of the heavy metal is more than 2 g/L; when the total mass concentration of the heavy metal is less than 2g/L, entering the step (3);
(2) adding alkali liquor into the wastewater, adding polyacrylamide or polyaluminium sulfate, adjusting the pH value to 9-12, stirring, filtering and separating to obtain a first supernatant, adding the polybase chelate magnetic hypha water purifying agent prepared by the method of any one of claims 1-6 into the first supernatant, stirring, performing magnetic field separation to obtain residue and a second supernatant, and treating the second supernatant with an activated carbon packing layer to reach the standard and discharge;
(3) adding the multi-group chelating magnetic hypha water purifying agent prepared by the method of any one of claims 1 to 6 into heavy metal wastewater, stirring, performing magnetic field separation to obtain residue and supernatant III, and treating the supernatant III by an activated carbon filler layer to reach the standard and discharge.
9. The use of claim 8, wherein the recycling method of the residues in steps (2) and (3) comprises subjecting the residues to acidic desorption and washing treatment, and separating the residues by magnetic field to obtain magnetic residues and non-magnetic residues; the residue with magnetism is directly used; and the residue without magnetism is magnetized and reused.
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