CN112390337B - Preparation method of modified montmorillonite, product and application thereof - Google Patents
Preparation method of modified montmorillonite, product and application thereof Download PDFInfo
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- CN112390337B CN112390337B CN202011189050.0A CN202011189050A CN112390337B CN 112390337 B CN112390337 B CN 112390337B CN 202011189050 A CN202011189050 A CN 202011189050A CN 112390337 B CN112390337 B CN 112390337B
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Abstract
The invention discloses a preparation method of modified montmorillonite, a product and application thereof, belonging to the technical field of water body algae removal, wherein the montmorillonite is pretreated and activated by acid to obtain the modified montmorillonite, and the modified montmorillonite is used as a raw material and is respectively subjected to iron treatment, acid modification and high iron treatment to obtain a water body algae remover and an algae exocytosis remover; the water algaecide prepared by the invention can make algae rapidly settle; the prepared algae exocytosis remover can effectively oxidize and remove algae exocytosis, can secondarily destroy the integrity of algae cells, and solves the problems that the traditional flocculation adsorption method causes the secondary explosion of the algae cells without inactivation and water body pollution caused by untreated algae exocytosis; when the water algaecide and the algae exocytosis remover prepared by the invention are used for removing algae, the material consumption is less, the time required by treatment is short, the treatment effect is good, and the water algaecide and the algae exocytosis remover are particularly suitable for emergency treatment during lake and reservoir algae outbreak.
Description
Technical Field
The invention belongs to the technical field of water body algae removal, and particularly relates to a preparation method of modified montmorillonite, a product and application thereof.
Background
The phenomenon that the ecological balance is damaged due to the mass propagation of algae caused by the deterioration of water resource environment is called algae outbreak, and the death of fishes and shrimps caused by the algae outbreak causes water body pollution and causes serious influence on the production and the life of human beings. Meanwhile, the algal toxin released when algae die can cause damage to nerves, muscles and livers of human bodies, and even death is caused seriously. Therefore, how to rapidly settle the algae and remove extracellular substances secreted when the algae die becomes an emerging hot research.
Although there are many methods for managing algal blooms, each method has its own advantages and disadvantages. Therefore, it is highly desirable to find a long-lasting, economical and safe method of preventing and controlling algae outbreaks. The common method for removing algae is manual salvage, which is characterized by quick response but easy to cause secondary outbreak. The growth of the blue algae cells and the like is controlled by other organisms, for example, by utilizing the competition and allelopathy of other phytoplankton, the biological method has slow effect, less stable effect, great influence by environmental conditions and difficult popularization. The clay algae removal is one of emergency algae removal methods which are concerned in recent years, and clay minerals are sufficient in source, natural and non-toxic, convenient to use and low in cost. At present, the biggest limiting factor of clay algae removal is large clay usage amount, and the clay usage amount can be reduced by improving the flocculation effect of clay through modification.
The traditional organic modification means of the clay mineral, such as quaternary ammonium salt, CTAB and the like, can greatly reduce the adding amount of the clay mineral, but is not suitable for lakes and reservoirs due to the toxicity of the clay mineral. Therefore, the development of the modified clay which is low in dosage and nontoxic and is used for removing algae in the water body is of great significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of modified montmorillonite, a product and application thereof.
One of the technical schemes of the invention is a preparation method of modified montmorillonite, which comprises the following steps: after the montmorillonite is pretreated, acid solution is added for activation, and the modified montmorillonite is obtained.
Further, the pretreatment method comprises the steps of preserving the temperature of montmorillonite for 3-5 hours at the temperature of 100-110 ℃; the acid solution is sulfuric acid, and the concentration of the acid solution is 18-22 wt%; the mass ratio of the acid solution to the pretreated montmorillonite is 1: 1-1.5, and the activation time is 2-4 h.
Furthermore, the pretreatment method comprises the steps of preserving the temperature of the montmorillonite for 4 hours at 105 ℃; the acid solution is sulfuric acid with the concentration of 20 wt%; the mass ratio of the acid solution to the pretreated montmorillonite is 1: 1, and the activation time is 3 h.
The activity of the activated montmorillonite acid solution is enhanced, and interlayer cations are separated out to increase the specific surface area of the montmorillonite and enhance the adsorbability.
The second technical scheme of the invention is that the modified montmorillonite is prepared according to the preparation method.
According to the third technical scheme, the preparation method of the water algaecide comprises the following steps: adding an iron ion solution into the modified montmorillonite to obtain iron-modified montmorillonite; and then adding an acid solution, stirring, centrifuging, drying, cooling and grinding to obtain the water algaecide.
Further, the iron ion solution is an iron chloride solution, the concentration is 0.5-1 mol/L, the mass ratio of the montmorillonite to the iron ion solution is 1: 2-4, and the method further comprises the step of stirring for 1.5-2.5 hours after the iron ion solution is added; the acid solution is sulfuric acid, and the concentration of the acid solution is 0.5-1.5 mol/L; the mass ratio of the montmorillonite to the acid solution is 1: 2-4.
Furthermore, the iron ion solution is an iron chloride solution, the concentration is 0.5mol/L, the mass ratio of the montmorillonite to the iron ion solution is 1: 3, and the step of stirring for 2 hours is included after the iron ion solution is added; the acid solution is sulfuric acid, and the concentration is 1 mol/L; the mass ratio of the montmorillonite to the acid solution is 1: 3.
Because the isoelectric point of algae is very low, the surface of the algae in the water body is negatively charged, and the surface of montmorillonite is also negatively charged by introducing Fe3+The modification mode can raise the isoelectric point of the surface of the montmorillonite, and the montmorillonite plays a role in electrically neutralizing algae in the water body, so that the montmorillonite is destabilized to achieve the effect of flocculating settling.
The sulfuric acid is added to modify the montmorillonite, so that on one hand, the ferric chloride solution can be prevented from being hydrolyzed in water to generate ferric hydroxide precipitate, and the effect of preventing the precipitate from wrapping the montmorillonite to block an interlayer channel is achieved; on the other hand, the acidic solution is capable of dissolving water-insoluble calcium salts in the montmorillonite.
Further, the stirring time is 6-10 h; the centrifugal rotating speed is 4000-6000 rpm, and the centrifugal time is 5-10 min; the drying is to dry for 10-14 h at 50-70 ℃, then heat to 100-110 ℃, and continue to dry for 2-3 h; and sieving the ground powder by a sieve of 100-200 meshes.
Further, the stirring time is 8 hours; the drying is to dry for 12 hours at 60 ℃, then to heat to 105 ℃, and to continue to dry for 2 hours; and sieving the ground powder through a 100-mesh sieve.
In the fourth technical scheme of the invention, the water algaecide prepared by the preparation method is provided.
The fifth technical scheme of the invention is that the preparation method of the algae extracellular secretion remover comprises the following steps:
(1) adding an iron ion solution into the modified montmorillonite, stirring, centrifuging, drying and grinding to obtain iron-modified montmorillonite;
(2) adding the ferrified montmorillonite obtained in the step (1) into a saturated potassium hypochlorite solution to obtain high-ferrified montmorillonite, and aging, centrifuging, drying and grinding to obtain the algal exocytosis remover.
The ferrated montmorillonite is added into a saturated potassium hypochlorite solution to generate potassium ferrate in situ to obtain the ferrated montmorillonite, extracellular secretion can be effectively removed by utilizing the strong oxidizing property of the ferrate, and the stability of the high-iron ions can be enhanced by combining the montmorillonite with the high-iron ions, so that the failure caused by extremely poor stability of the high-iron ions and extremely easy reduction is avoided.
Further, the iron ion solution in the step (1) is an iron chloride solution, and the concentration is 1-2 mol/L; the mass ratio of the montmorillonite to the iron ion solution is 1: 2-4.
Further, the aging temperature was 4 ℃.
Further, the drying in the step (2) is vacuum freeze drying.
Sixthly, the invention relates to an extracellular secretion remover for algae prepared by the preparation method.
Seventhly, the invention relates to a method for removing algae in water, which uses the algaecide and/or the exocytosis remover to remove algae in water.
Compared with the prior art, the invention has the following beneficial effects:
(1) the water algaecide prepared by the invention can adsorb, settle and destroy algae cells, so that the algae quickly settle; the algae extracellular secretion remover prepared by the invention can effectively oxidize and remove extracellular secretions generated when algae die, can secondarily destroy the integrity of algae cells, and overcomes the problems that the algae cells are not inactivated and secondarily burst due to the traditional flocculation adsorption method and water body pollution is caused due to untreated algae extracellular secretions.
(2) The preparation method is simple, and the raw material montmorillonite is low in cost and has a good application prospect.
(3) The montmorillonite is modified by adopting a non-toxic material, so that the montmorillonite is safe to animals and plants growing in a water body, has small influence, cannot cause oxygen deficiency of the water body, and a final product after the material is settled is non-toxic and has no secondary pollution.
(4) When the water algaecide and the algae exocytosis remover prepared by the invention are used for removing algae, the material consumption is less, the time required by treatment is short, the treatment effect is good, and the water algaecide and the algae exocytosis remover are particularly suitable for emergency treatment during lake and reservoir algae outbreak.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a diagram of a reaction apparatus used in an effect verification example of the present invention, in which 1 is a mixed algae liquid barrel, 2 is a suspension barrel for removing algae in a water body, 3 is a magnetic stirrer, 4 and 5 are peristaltic pumps, 6 is a flow guide groove, a drain outlet is provided, 7 is a built inclined plane, and 8 is a drain outlet in a b-zone.
Fig. 2 is a graph showing the results of measuring the contents of chlorophyll a and chlorophyll b in effect test example 1.
Fig. 3 is a graph showing the results of measuring the total phosphorus content in effect test example 1.
FIG. 4 is a three-dimensional fluorescence spectrum of the supernatant of region a in Effect verification example 1.
FIG. 5 is a three-dimensional fluorescence spectrum of the supernatant of region b in effect test example 1.
FIG. 6 is a three-dimensional fluorescence spectrum of the supernatant of region b in effect test example 10.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
The preparation of the water algaecide comprises the following steps:
(1) keeping the temperature of the sodium-based montmorillonite in a drying oven at 105 ℃ for 4h to obtain pretreated montmorillonite;
(2) adding a sulfuric acid solution with the mass fraction of 20% into the pretreated montmorillonite obtained in the step (1) according to the mass ratio of 1: 1, uniformly stirring, and standing and activating for 3 hours to obtain modified montmorillonite;
(3) adding a ferric chloride solution with the concentration of 0.5mol/L into the modified montmorillonite obtained in the step (2), and stirring for 2 hours to obtain iron-modified montmorillonite, wherein the mass ratio of the ferric chloride solution to the sodium-based montmorillonite is 3: 1;
(4) adding 1mol/L sulfuric acid into the iron-modified montmorillonite obtained in the step (3), wherein the mass ratio of the sulfuric acid to the sodium-based montmorillonite is 3: 1, stirring for 8 hours, centrifuging at the rotating speed of 4000rpm for 10 minutes, then placing in a drying oven, drying for 12 hours at the temperature of 60 ℃, heating to 105 ℃, and continuing to dry for 2 hours; and grinding and sieving the water body through a 100-mesh sieve after cooling to obtain the water body algaecide, and storing the water body algaecide in a drying box.
Example 2
Preparing the water algaecide:
(1) preserving the heat of the sodium-based montmorillonite in a 100 ℃ oven for 5 hours to obtain pretreated montmorillonite;
(2) adding a sulfuric acid solution with the mass fraction of 18% into the pretreated montmorillonite obtained in the step (1) according to the mass ratio of 1.5: 1, uniformly stirring, and standing and activating for 2 hours to obtain modified montmorillonite;
(3) adding an iron chloride solution with the concentration of 0.8mol/L into the modified montmorillonite obtained in the step (2), and stirring for 1.5 hours to obtain iron-modified montmorillonite, wherein the mass ratio of the iron chloride solution to the sodium-based montmorillonite is 2: 1;
(4) adding sulfuric acid with the concentration of 0.5mol/L into the iron-modified montmorillonite obtained in the step (3), wherein the mass ratio of the sulfuric acid to the sodium-based montmorillonite is 4: 1, stirring for 6 hours, centrifuging for 5 minutes at the rotating speed of 5000rpm, then placing in a drying oven, drying for 14 hours at the temperature of 50 ℃, heating to 110 ℃, and continuing to dry for 2 hours; and grinding and sieving the water body through a 200-mesh sieve after cooling to obtain the water body algaecide, and storing the water body algaecide in a drying box.
Example 3
The preparation of the water algaecide comprises the following steps:
(1) the sodium-based montmorillonite is heated in a drying oven at 110 ℃ for 3 hours to obtain pretreated montmorillonite;
(2) adding a sulfuric acid solution with the mass fraction of 22% into the pretreated montmorillonite obtained in the step (1) according to the mass ratio of 1.2: 1, uniformly stirring, and standing and activating for 4 hours to obtain modified montmorillonite;
(3) adding ferric chloride solution with the concentration of 1.0mol/L into the modified montmorillonite obtained in the step (2), and stirring for 2.5 hours to obtain iron-modified montmorillonite, wherein the mass ratio of the ferric chloride solution to the sodium-based montmorillonite is 4: 1;
(4) adding 1.5mol/L sulfuric acid into the iron-modified montmorillonite obtained in the step (3), wherein the mass ratio of the sulfuric acid to the sodium-based montmorillonite is 2: 1, stirring for 10 hours, centrifuging at the rotating speed of 6000rpm for 8 minutes, then placing in a drying oven, drying for 10 hours at 70 ℃, heating to 100 ℃, and continuing to dry for 3 hours; and grinding and sieving the water body through a 100-mesh sieve after cooling to obtain the water body algaecide, and storing the water body algaecide in a drying box.
Example 4
The preparation of the algae extracellular secretion remover comprises the following steps:
(1) keeping the temperature of the sodium-based montmorillonite in a drying oven at 105 ℃ for 4h to obtain pretreated montmorillonite;
(2) adding a sulfuric acid solution with the mass fraction of 20% into the pretreated montmorillonite obtained in the step (1) according to the mass ratio of 1: 1, uniformly stirring, and standing and activating for 3 hours to obtain modified montmorillonite;
(3) adding an iron chloride solution with the concentration of 1.0mol/L into the modified montmorillonite obtained in the step (2), stirring for 2h, wherein the mass ratio of the iron chloride solution to the sodium-based montmorillonite is 3: 1, centrifuging for 10min at the rotating speed of 5000rpm, drying in vacuum at 70 ℃ for 24h, and grinding and sieving with a 100-mesh sieve to obtain the iron-modified montmorillonite;
(4) dissolving calcium hypochlorite, anhydrous potassium carbonate and potassium hydroxide in deionized water to prepare a saturated potassium hypochlorite solution, adding the ferrated montmorillonite obtained in the step (3) into the potassium hypochlorite solution to generate potassium ferrate in situ to obtain the ferrated montmorillonite, wherein the mass ratio of the potassium hypochlorite solution to the sodium-based montmorillonite is 8: 1, and aging the sodium-based montmorillonite in a refrigerator at 4 ℃ for 3 days;
(5) and (4) centrifuging the aged high-iron montmorillonite obtained in the step (4) at the rotating speed of 5000rpm for 10min, carrying out vacuum freeze drying for 24h, and then grinding and sieving with a 100-mesh sieve to obtain the algal exocytosis remover.
Example 5
Preparation of an extracellular secretion remover of algae:
(1) preserving the heat of the sodium-based montmorillonite in a 100 ℃ oven for 5 hours to obtain pretreated montmorillonite;
(2) adding a sulfuric acid solution with the mass fraction of 18% into the pretreated montmorillonite obtained in the step (1) according to the mass ratio of 1.5: 1, uniformly stirring, and standing and activating for 2 hours to obtain modified montmorillonite;
(3) adding an iron chloride solution with the concentration of 2.0mol/L into the modified montmorillonite obtained in the step (2), stirring for 1.5h, wherein the mass ratio of the iron chloride solution to the sodium-based montmorillonite is 2: 1, centrifuging for 5min at the rotating speed of 6000rpm, carrying out vacuum drying at 60 ℃ for 36h, and then grinding and sieving with a 100-mesh sieve to obtain the iron-modified montmorillonite;
(4) dissolving calcium hypochlorite, anhydrous potassium carbonate and potassium hydroxide in deionized water to prepare a saturated potassium hypochlorite solution, adding the ferrated montmorillonite obtained in the step (3) into the potassium hypochlorite solution to generate potassium ferrate in situ to obtain the ferrated montmorillonite, wherein the mass ratio of the potassium hypochlorite solution to the sodium-based montmorillonite is 10: 1, and aging the sodium-based montmorillonite in a refrigerator at 4 ℃ for 7 days;
(5) and (4) centrifuging the aged high-iron montmorillonite obtained in the step (4) at the rotating speed of 6000rpm for 5min, carrying out vacuum freeze drying for 24h, and then grinding and sieving by using a 200-mesh sieve to obtain the algal exocytosis remover.
Example 6
The preparation of the algae extracellular secretion remover comprises the following steps:
(1) the sodium-based montmorillonite is heated in a drying oven at 110 ℃ for 3 hours to obtain pretreated montmorillonite;
(2) adding a sulfuric acid solution with the mass fraction of 22% into the pretreated montmorillonite obtained in the step (1) according to the mass ratio of 1.2: 1, uniformly stirring, and standing and activating for 4 hours to obtain modified montmorillonite;
(3) adding an iron chloride solution with the concentration of 1.5mol/L into the modified montmorillonite obtained in the step (2), stirring for 2.5h, wherein the mass ratio of the iron chloride solution to the sodium-based montmorillonite is 4: 1, centrifuging for 8min at the rotating speed of 4000rpm, carrying out vacuum drying at 80 ℃ for 20h, and then grinding and sieving by a 100-mesh sieve to obtain the iron-modified montmorillonite;
(4) dissolving calcium hypochlorite, anhydrous potassium carbonate and potassium hydroxide in deionized water to prepare a saturated potassium hypochlorite solution, adding the ferrated montmorillonite obtained in the step (3) into the potassium hypochlorite solution to generate potassium ferrate in situ to obtain the ferrated montmorillonite, wherein the mass ratio of the potassium hypochlorite solution to the sodium-based montmorillonite is 5: 1, and aging the sodium-based montmorillonite in a refrigerator at 4 ℃ for 5 days;
(5) and (4) centrifuging the aged high-iron montmorillonite obtained in the step (4) for 8min at the rotating speed of 4000rpm, carrying out vacuum freeze drying for 24h, and then grinding and sieving by using a 100-mesh sieve to obtain the extracellular secretion remover for algae.
Comparative example 1
The preparation of the water algaecide comprises the following steps:
(1) keeping the temperature of the sodium-based montmorillonite in a drying oven at 105 ℃ for 4h to obtain pretreated montmorillonite;
(2) adding an iron chloride solution with the concentration of 0.5mol/L into the pretreated montmorillonite obtained in the step (1), and stirring for 2 hours to obtain iron-modified montmorillonite, wherein the mass ratio of the iron chloride solution to the sodium-based montmorillonite is 3: 1;
(3) adding 1mol/L sulfuric acid into the modified montmorillonite obtained in the step (2), wherein the mass ratio of the sulfuric acid to the sodium montmorillonite is 3: 1, stirring for 8 hours, centrifuging at the rotating speed of 4000rpm for 10 minutes, then placing in a drying oven, drying for 12 hours at the temperature of 60 ℃, heating to 105 ℃, and continuing to dry for 2 hours; and grinding and sieving the water body through a 100-mesh sieve after cooling to obtain the water body algaecide, and storing the water body algaecide in a drying box.
Comparative example 2
The difference from example 1 is that ferric chloride in step (3) is replaced with aluminum chloride.
Comparative example 3
The difference from example 1 is that the sulfuric acid in step (4) is replaced with nitric acid.
Comparative example 4
The preparation of the algae extracellular secretion remover comprises the following steps:
(1) keeping the temperature of the sodium-based montmorillonite in a drying oven at 105 ℃ for 4h to obtain pretreated montmorillonite;
(2) adding a sulfuric acid solution with the mass fraction of 20% into the pretreated montmorillonite obtained in the step (1) according to the mass ratio of 1: 1, uniformly stirring, and standing and activating for 3 hours to obtain modified montmorillonite;
(3) adding 1mol/L potassium ferrate solution into the modified montmorillonite obtained in the step (2) to obtain the ferrated montmorillonite, wherein the mass ratio of the potassium ferrate solution to the sodium-based montmorillonite is 8: 1, and aging the montmorillonite in a refrigerator at 4 ℃ for 3 days;
(4) and (4) centrifuging the aged high-iron montmorillonite obtained in the step (3) at the rotating speed of 5000rpm for 10min, freeze-drying for 24h, and grinding and sieving with a 100-mesh sieve to obtain the algal exocytosis remover.
The water body algae removal simulation test is carried out on the water body algae removal agents prepared in the examples 1-3 and the comparative examples 1-3 and the algae exocytosis removal agents prepared in the examples 4-6 and the comparative example 4, the intermittent flow mode is adopted, the device is shown as the attached figure 1, and the device is assembled by self-made common glass: the total volume of the area a of the device is 48L, the effective volume is 35L, an inclined plane is constructed in the area a, a groove is formed, overflow holes are formed in intermediate partition plates of the area a and the area b, the total volume of the area b is 16L, the effective volume is 12L, 1 is a mixed algae liquid barrel, 2 is a suspension liquid barrel of a water body algaecide, 3 is a magnetic stirrer, 4 and 5 are peristaltic pumps of different flowmeters, 6 is a flow guide groove, a drain outlet is arranged, 7 is an inclined plane and 8 is a drain outlet in the area b.
Effect test example 1
A reaction device is set up according to the attached figure 1, firstly, mixed algae liquid and suspension of the water algaecide (hereinafter referred to as material A) prepared in the embodiment 1 are directly added to a water level line of a region a, wherein the adding amount of the material A is 80 mg/L; then, 2.8g of the material A was added to 28mL of pure water to prepare a suspension of 0.1g/mL, and the suspension was uniformly mixed and sprayed to the region a. Standing for 3h, obviously clearing the supernatant liquid, starting the peristaltic pump, feeding the algae liquid by the peristaltic pump 4, feeding the algae liquid by the driver by BT-100L, and using a pump head YZ15, wherein the hose is a 2 x 4mm silicone tube, the rotating speed is 120rpm, the flow rate of the algae liquid is 2.6ml/s, the peristaltic pump 5 is a feeding pump for the suspension of the material A, the driver by BT-100L, and the pump head DG are provided, and the hose is a 13# silicone tube, the rotating speed is 3rpm, and the flow rate of the suspension of the material A is 0.2 ml/min. When the clear liquid in the area a enters the area b through the overflow port and reaches the water level line in the area b, the work of the peristaltic pump 4 and the peristaltic pump 5 is stopped. At this time, 0.12g of the extracellular secretion removing agent (hereinafter referred to as "material B") obtained in example 4 was directly added to zone B, and after standing for 60min, water was discharged from zone B, and the peristaltic pump was started again to reciprocate.
Taking the original algae liquid, the supernatant liquid treated in the area a and the supernatant liquid treated in the area b, testing the contents of chlorophyll a, chlorophyll b and total phosphorus in the original algae liquid and the supernatant liquid treated in the area a, and calculating the removal rates of the chlorophyll a, the chlorophyll b and the total phosphorus in the area a as shown in the figures 2-3, wherein the results are shown in the table 1; and the supernatant processed by the area a and the supernatant processed by the area b are subjected to fluorescence analysis, and the content of the extracellular secretion of the algae is detected, and the results are shown in figures 4-5. As can be seen from table 1, fig. 2 and fig. 3, chlorophyll a, chlorophyll b and total phosphorus are all in a significant decrease trend after being treated in zone a, the removal rates of chlorophyll a and chlorophyll b are 82.5% and 82.2%, and the removal rate of total phosphorus is 94.5%. Indicating that 3 hours of settling will settle most of the algae to the bottom of the apparatus.
As shown in FIGS. 4-5, the three-dimensional fluorescence maps showed that extracellular secretion was substantially cleared after treatment of the supernatant from zone a with material B.
Effect test example 2
A reaction device is set up according to the attached drawing 1, firstly, mixed algae liquid and suspension of the water body algaecide (hereinafter referred to as material A) prepared in the embodiment 1 are directly added to a water level line of a zone a, wherein the adding amount of the material A is 150mg/L, then, 5.25g of the material A is added into 105mL of pure water to prepare 0.05g/mL of suspension, and the suspension is uniformly mixed and then uniformly sprayed and added to the zone a. Standing for 5h, obviously clearing the supernatant liquid, starting the peristaltic pump 4 as an algae liquid feeding pump, adopting BT-100L as a driver, adopting YZ15 as a pump head, adopting 2 x 4mm silicone tubes as a hose, rotating at the speed of 120rpm, enabling the algae liquid to enter at the flow rate of 2.6ml/s, adopting BT-100L as a driver, adopting DG as a pump head, adopting 13# silicone tubes as a hose, rotating at the speed of 6.5rpm, and enabling the material A suspension to enter at the flow rate of 0.36 ml/min. When the clear liquid in the area a enters the area b through the overflow port and reaches the water level line in the area b, the work of the peristaltic pump 4 and the peristaltic pump 5 is stopped. At this time, 0.24g of the extracellular secretion removing agent (hereinafter referred to as "material B") obtained in example 4 was directly added to zone B, and after 15min, water was drained from zone B, and the peristaltic pump was started again to reciprocate.
Taking three point positions of the original algae liquid, the supernatant processed by the area a and the supernatant processed by the area b, testing the contents of chlorophyll a, chlorophyll b and total phosphorus in the original algae liquid and the supernatant processed by the area a, calculating the removal rate of the chlorophyll a, the chlorophyll b and the total phosphorus in the area a, wherein the results are shown in table 1, performing fluorescence analysis on the supernatant processed by the area a and the supernatant processed by the area b, and detecting the content of extracellular secretion of algae, wherein the results show that the content of the extracellular secretion in the supernatant in the area a is basically the same as the content of the extracellular secretion in the supernatant in the area a in the effect verification example 1, and the supernatant in the area b basically has no extracellular secretion.
Effect verification examples 3 to 7
The water algaecides prepared in example 1 of the effect verification example 1 were replaced with the water algaecides prepared in examples 2 to 3 and comparative examples 1 to 3, respectively, and as effect verification examples 3 to 7, the contents of chlorophyll a, chlorophyll b, and total phosphorus in the original algal solution and the supernatant of the region a were measured, and the removal rates thereof were calculated, and the results are shown in table 1.
Examples 8 to 9 for Effect verification
The extracellular secretion removing agents of algae prepared in example 4 of the effect verification example 1 were replaced with the extracellular secretion removing agents of algae prepared in examples 5 to 6, respectively, and as the effect verification examples 8 to 9, the supernatants of the b-zone were found to be substantially free of extracellular secretion by fluorescence analysis.
Effect test example 10
The extracellular secretion removing agent prepared in example 4 in the effect verification example 1 was replaced with the extracellular secretion removing agent prepared in comparative example 4, and as the effect verification example 10, the supernatant in the b region was analyzed by fluorescence, and it was found that a large amount of extracellular secretion remained in the supernatant in the b region, and the effect of removing extracellular secretion was not obvious as compared with the effect of removing extracellular secretion in the supernatant in the a region. The results of the detection are shown in FIG. 6.
TABLE 1
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (8)
1. The preparation method of the water algaecide is characterized by comprising the following steps: after the montmorillonite is pretreated, acid solution is added for activation, and modified montmorillonite is obtained; adding an iron ion solution into the modified montmorillonite to obtain iron-modified montmorillonite; and then adding a sulfuric acid solution, stirring, centrifuging, drying, cooling and grinding to obtain the water algaecide.
2. The preparation method of claim 1, wherein the pretreatment comprises the steps of preserving the montmorillonite at 100-110 ℃ for 3-5 h; the acid solution is sulfuric acid, and the concentration of the acid solution is 18-22 wt%; the mass ratio of the acid solution to the pretreated montmorillonite is 1: 1-1.5, and the activation time is 2-4 h.
3. The preparation method of claim 1, wherein the iron ion solution is an iron chloride solution with a concentration of 0.5-1 mol/L, the mass ratio of the montmorillonite to the iron ion solution is 1: 2-4, and the method further comprises the step of stirring for 1.5-2.5 hours after the iron ion solution is added; the concentration of the sulfuric acid solution is 0.5-1.5 mol/L; the mass ratio of the montmorillonite to the sulfuric acid solution is 1: 2-4.
4. The water body algaecide prepared by the preparation method according to any one of claims 1 to 3.
5. A preparation method of an extracellular secretion remover for algae is characterized by comprising the following steps:
(1) pretreating montmorillonite, adding an acid solution for activation to obtain modified montmorillonite, adding an iron ion solution into the modified montmorillonite, stirring, centrifuging, drying and grinding to obtain iron-modified montmorillonite;
(2) adding the ferrified montmorillonite obtained in the step (1) into a saturated potassium hypochlorite solution to obtain high-ferrified montmorillonite, and aging, centrifuging, drying and grinding to obtain the algal exocytosis remover.
6. The preparation method according to claim 5, wherein the iron ion solution in the step (1) is an iron chloride solution with a concentration of 1-2 mol/L; the mass ratio of the montmorillonite to the iron ion solution is 1: 2-4.
7. An extracellular secretion remover for algae prepared by the method according to any one of claims 5 to 6.
8. A method for removing algae from a water body, which comprises using the algaecide for a water body according to claim 4 and/or the extracellular secretion remover for algae according to claim 7.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232484A (en) * | 1991-08-13 | 1993-08-03 | The Connecticut Agricultural Experiment Station | Degradation of pesticides by ferric reagents and peroxide in the presence of light |
| CN1962474A (en) * | 2006-11-22 | 2007-05-16 | 哈尔滨工业大学 | Method for removing pollutant from water |
| CN102923835A (en) * | 2012-11-09 | 2013-02-13 | 中国科学技术大学 | Nano zero-valent iron with montmorillonite serving as carrier, and preparation method and application thereof |
| CN103241793A (en) * | 2013-05-17 | 2013-08-14 | 杭州一清环保工程有限公司 | Multifunctional water treatment agent used for treating refractory wastewater |
| CN103880030A (en) * | 2012-12-21 | 2014-06-25 | 青岛中仁药业有限公司 | A preparation method of montmorillonite inhibiting heterosigma akashiwo |
| CN104258816A (en) * | 2014-10-24 | 2015-01-07 | 安徽工业大学 | Preparation method of magnetic stripping type montmorillonite nanocomposite material for wastewater treatment |
| CN105253919A (en) * | 2015-10-14 | 2016-01-20 | 上海大学 | Preparation method for slow-release type ferrate solid oxidizing agent and application of preparation method |
| CN106423045A (en) * | 2016-11-23 | 2017-02-22 | 兰州理工大学 | Preparation method of modified montmorillonite adsorbent for treating zinc-bearing wastewater |
| CN107473345A (en) * | 2017-07-31 | 2017-12-15 | 常州诺澜复合材料有限公司 | A kind of preparation method of composite algicide |
| CN107935098A (en) * | 2017-12-25 | 2018-04-20 | 芜湖皖江知识产权运营中心有限公司 | A kind of method for handling organic wastewater |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6863825B2 (en) * | 2003-01-29 | 2005-03-08 | Union Oil Company Of California | Process for removing arsenic from aqueous streams |
| IN2015CH04611A (en) * | 2015-09-01 | 2015-09-18 | Manjanna Jayappa | |
| CN108558019B (en) * | 2018-01-04 | 2021-12-03 | 中冶华天工程技术有限公司 | Preparation method of microorganism reinforced flocculation algaecide |
| CN108339526B (en) * | 2018-02-26 | 2020-07-31 | 西南科技大学 | Modified sodium alginate adsorption material for adsorbing tetracycline antibiotics and preparation method thereof |
| CN109772271B (en) * | 2019-03-14 | 2021-04-02 | 中国科学院生态环境研究中心 | Ferro-manganese modified algae adsorbent and preparation method thereof |
-
2020
- 2020-10-30 CN CN202011189050.0A patent/CN112390337B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232484A (en) * | 1991-08-13 | 1993-08-03 | The Connecticut Agricultural Experiment Station | Degradation of pesticides by ferric reagents and peroxide in the presence of light |
| CN1962474A (en) * | 2006-11-22 | 2007-05-16 | 哈尔滨工业大学 | Method for removing pollutant from water |
| CN102923835A (en) * | 2012-11-09 | 2013-02-13 | 中国科学技术大学 | Nano zero-valent iron with montmorillonite serving as carrier, and preparation method and application thereof |
| CN103880030A (en) * | 2012-12-21 | 2014-06-25 | 青岛中仁药业有限公司 | A preparation method of montmorillonite inhibiting heterosigma akashiwo |
| CN103241793A (en) * | 2013-05-17 | 2013-08-14 | 杭州一清环保工程有限公司 | Multifunctional water treatment agent used for treating refractory wastewater |
| CN104258816A (en) * | 2014-10-24 | 2015-01-07 | 安徽工业大学 | Preparation method of magnetic stripping type montmorillonite nanocomposite material for wastewater treatment |
| CN105253919A (en) * | 2015-10-14 | 2016-01-20 | 上海大学 | Preparation method for slow-release type ferrate solid oxidizing agent and application of preparation method |
| CN106423045A (en) * | 2016-11-23 | 2017-02-22 | 兰州理工大学 | Preparation method of modified montmorillonite adsorbent for treating zinc-bearing wastewater |
| CN107473345A (en) * | 2017-07-31 | 2017-12-15 | 常州诺澜复合材料有限公司 | A kind of preparation method of composite algicide |
| CN107935098A (en) * | 2017-12-25 | 2018-04-20 | 芜湖皖江知识产权运营中心有限公司 | A kind of method for handling organic wastewater |
Non-Patent Citations (6)
| Title |
|---|
| "Efficient removal of bisphenol A by superoxide radical and singlet oxygen generated from peroxymonosulfate activated with Fe-0-montmorillonite";Yang, Shanshan et al.;《CHEMICAL ENGINEERING JOURNAL 》;20181015;第350卷;第484-495页 * |
| "Surface Catalyzed Oxidative Oligomerization of 17 beta-Estradiol by Fe3+-Saturated Montmorillonite";Qin, Chao et al.;《ENVIRONMENTAL SCIENCE & TECHNOLOGY 》;20150120;第49卷(第2期);第956-964页 * |
| "蒙脱土的改性方法及应用现状";向莹等;《北京印刷学院学报》;20070831(第4期);第30-31页第2节 * |
| "高铁酸钾预氧化并复合高岭土与PAC絮凝去除水中的颤藻";赵春禄等;《环境工程学报》;20120505;第6卷(第5期);第1604-1608页 * |
| 向莹等."蒙脱土的改性方法及应用现状".《北京印刷学院学报》.2007,(第4期), * |
| 周艳等." 有机蒙脱土对单宁酸的吸附性能".《化工进展》.2014,第33卷(第7期), * |
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Inventor after: Liu Jie Inventor after: Yang Yuankun Inventor after: Wen Xinyu Inventor after: Feng Xiaoqian Inventor after: Chen Shu Inventor after: Wang Bin Inventor before: Yang Yuankun Inventor before: Liu Jie Inventor before: Wen Xinyu Inventor before: Feng Xiaoqian Inventor before: Chen Shu Inventor before: Wang Bin |