CN118084156A - Red tide eliminating agent and preparation method thereof - Google Patents
Red tide eliminating agent and preparation method thereof Download PDFInfo
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- CN118084156A CN118084156A CN202410184638.9A CN202410184638A CN118084156A CN 118084156 A CN118084156 A CN 118084156A CN 202410184638 A CN202410184638 A CN 202410184638A CN 118084156 A CN118084156 A CN 118084156A
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000203 mixture Substances 0.000 claims description 3
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- 239000002734 clay mineral Substances 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- YDCPQRQGABOSRY-UHFFFAOYSA-N iron;urea Chemical compound [Fe].NC(N)=O YDCPQRQGABOSRY-UHFFFAOYSA-N 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 239000005422 algal bloom Substances 0.000 abstract description 5
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- 239000005995 Aluminium silicate Substances 0.000 description 16
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 15
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
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- 241000223600 Alternaria Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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Abstract
The invention belongs to the field of harmful algal bloom prevention and treatment, and in particular relates to a red tide eliminating agent and a preparation method thereof. The preparation method of red tide eliminating agent includes dispersing fine clay particle in urea solution, adding iron ion solution while stirring to react, and drying to obtain red tide eliminating agent. The urea iron-containing modified clay prepared by the invention not only can effectively eliminate red tide microalgae, but also has good effect of removing pollution factors such as active phosphate and the like in water, and is a preparation method of the red tide treatment agent with application prospect.
Description
Technical Field
The invention belongs to the field of harmful algal bloom prevention and treatment, and in particular relates to a red tide eliminating agent and a preparation method thereof.
Background
Red tide is an ecological abnormal phenomenon that micro plankton in the ocean rapidly proliferates and gathers to cause water body to change color, often damages the structure and the function of an ecological system, influences the development of ocean economy, and even endangers human health. How to safely and effectively prevent and treat red tides is a difficult problem which puzzles the current international ocean environment science. Although various red tide control methods are proposed by red tide control specialists at home and abroad, most of the methods are still limited to laboratory researches, and the methods can be truly applied to a few in-situ. The modified clay method is the only red tide emergency treatment method applied on a large scale on site at present, and is widely focused and researched by domestic and foreign specialists.
The development of safe and efficient algae removal modified clay materials is one of the hot spots of attention for red tide treatment technology development. It has been found that changing the surface properties of natural clay is an effective way to promote flocculation of clay to eliminate red tide organisms, and based on the method guidance, modified clay materials with various series and different functions including inorganic modification, organic-inorganic composite modification, biological modification and the like have been formed so far. The successful research and development of the modified clay provides choices for red tide treatment with different characteristics, and lays a foundation for the construction of a modified clay technical system.
Along with the aggravation of climate change and coastal human activities, red tide disasters in the global coastal sea area are continuously aggravated, and the characteristics of large outbreak scale, changeable disaster causing species, extended affected areas, increased hazard modes, aggravated damage results and the like are presented. In the face of red tide 'magic height' the performance of modified clay materials is urgently required to be further improved, and particularly new materials with special effect treatment effects are developed for newly-appearing red tide organisms, so that support is provided for improving red tide treatment efficiency and enhancing the water environment restoration function polluted by the red tide. Therefore, the development of the novel material is not only the driving force for the technical development of the modified clay, but also the urgent application requirement for coping with red tide disasters and improving the scientific and efficient treatment capability.
The rapid development of nanotechnology provides an effective means for the development of novel environment-friendly functional materials. Nanotechnology refers to technology that purposefully "controls", "manipulates" and "processes" substances and processes at very small scales (nanoscale range). The nano material has high specific surface area, high activity, more sufficient contact with reactants, more efficient reaction, great attention paid to good performances such as greatly reducing the material addition amount, reducing the economic cost and the like, and is widely applied to the field of environmental modification and repair materials. The nanometer material is directly applied to the algal bloom treatment in research, and provides new theory and technical support for controlling harmful algal bloom at home and abroad. Related researches show that the nano material can effectively inhibit or kill algae cells through the actions of photocatalysis, flocculation sedimentation, physical adsorption, stimulus induction, regulation and control of nutritive salts and the like. In addition, researches show that the nano material can effectively change the material property and promote the sterilization effect after the nano material is subjected to surface modification. For example, nano silver is loaded on illite, so that the nano silver has strong capability of capturing and killing bacteria and viruses; the COF-SCU1 is used as a carrier, and the COF-AgNPs prepared by fixing AgNPs on the surface of the COF SCU1 by adopting an in-situ synthesis method have excellent antibacterial performance and can inhibit bacterial growth by destroying the cell membrane of bacteria. However, microalgae and bacteria are two different organisms, and no research on synergistic algae removal by compounding nano materials with clay has been reported so far.
Disclosure of Invention
The invention aims to provide a red tide eliminating agent and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the technical scheme that:
A process for preparing red tide eliminating agent includes such steps as dispersing fine-grained clay in urea solution, stirring, adding Fe ion solution, reacting, and drying.
The mass ratio of the urea to the clay to the iron ions is 1 (0.1-16) to 0.1-3.5.
Further, dispersing the fine-grained clay in a urea solution, adding an iron ion solution at a rate of 1-300 mL/min under stirring, reacting at 30-70 ℃ for 1-3 h, and drying to obtain the red tide scavenger (urea iron-synthesizing modified clay).
The clay powder is one or a mixture of clay minerals, and the particle size of the powder after crushing is less than 40 mu m.
The urea solution is a diluted solution of 5-50 g/L formed by dissolving urea in an ethanol solvent; the ferric ion solution is prepared by dissolving soluble ferric salt in an ethanol solvent.
The soluble ferric salt is ferric chloride or ferric nitrate.
The red tide eliminating agent prepared by the method has particle attachments on the surfaces of clay particles, curled slice sections, blurred interlayer gaps and rough interfaces.
The application of the red tide eliminating agent in treating red tide organisms and/or soluble phosphate pollution factors in water environment.
The invention has the advantages that:
The invention uses nontoxic harmless, cheap and easily available functional nano materials for modifying the surface of clay particles, takes active sites on the surface of the clay particles as the center, and grafts and anchors urea-iron complex base groups, thereby obtaining urea-iron complex modified clay, which not only can effectively eliminate red tide microalgae, but also has good removal effect on pollution factors such as active phosphate and the like in water body, and is a preparation method of red tide treating agent with application prospect.
Drawings
FIG. 1 is an electron microscope image of the urea iron-alloy modified clay prepared according to the embodiment of the invention.
Fig. 2 is a graph showing comparison of algae removal rates of red tide eliminating agents (red tide organisms are red tide isokinetic algae) obtained by different synthesis modes provided by the embodiment of the invention, wherein significance of the graph is analyzed based on the principle of Woller-Duncan a,b.
Fig. 3 is a graph showing the comparison result of algae removal efficiency (red tide organisms are red tide isocurvularia) of red tide eliminating agents obtained by urea and ferric ions with different mass ratios, wherein significance of the graph is analyzed based on the principle of Woller-Duncan a , b.
Fig. 4 is a graph of comparison results of algae removal efficiency of red tide eliminating agents (red tide organisms are red tide isoglena) obtained by urea iron and kaolin with different mass ratios, wherein significance of the graph is analyzed based on the principle of Wolr-Duncan a,b.
Fig. 5 is a standard operating curve for phosphate concentration determination provided in an example of the present invention.
FIG. 6 shows the phosphate removal rate (red tide organism is Alternaria akabane) of red tide eliminating agent prepared under different conditions according to the embodiment of the invention, wherein the significance of the figure is analyzed based on the principle of Woller-Duncan a,b.
FIG. 7 shows the phosphate removal rate of the red tide eliminating agent provided by the embodiment of the invention (red tide organisms are red tide isocurvularia) at different dosing doses, wherein the significance of the red tide eliminating agent is analyzed based on the principle of Woller-Duncan a,b.
Detailed Description
The following examples are given to illustrate the preparation of modified clay materials having high efficiency in eliminating harmful algal bloom organisms, but are not meant to limit the invention.
Example 1
Influence of different synthesis methods on algae removal rate of obtained red tide eliminator
Surface synthesis: according to 1: dissolving Urea in absolute ethyl alcohol according to the mass ratio of 21, completely dissolving the Urea under the stirring condition, and preparing Urea solution for later use, wherein the Urea solution is marked as Urea; 2.8g of ferric nitrate nonahydrate was dissolved in 50mL of absolute ethanol with stirring to completely dissolve the ferric nitrate, and marked as Fe solution. According to the mass ratio of kaolin to urea of 1.1:1, taking 70mL of Urea solution, controlling the temperature to be 50 ℃, adding 2.8g of Kaolin, uniformly mixing, then adding 50mL of Fe solution (the mass ratio of Urea iron-in-Urea to Kaolin is 1.5:1) at the speed of 50mL/min, controlling the temperature, continuously reacting for 2 hours, eluting and crushing after completion, and obtaining Urea iron-in-Urea modified clay, namely NFC-on-Kaolin (see figure 1).
The method for prefabricating and mixing comprises the following steps: according to 1: dissolving Urea in absolute ethyl alcohol according to the mass ratio of 21, completely dissolving the Urea under the stirring condition, and preparing Urea solution for later use, wherein the Urea solution is marked as Urea; 2.8g of ferric nitrate nonahydrate was dissolved in 50mL of absolute ethanol with stirring to completely dissolve the ferric nitrate, and marked as Fe solution. The mass ratio of urea to ferric nitrate nonahydrate is 1:1.1, taking 70mL of Urea solution, controlling the temperature to be 50 ℃, adding 50mL of Fe solution at the speed of 50mL/min, controlling the temperature to continue reacting for 2 hours, eluting and crushing after completion, and preparing Urea and an iron material for standby, and marking as NFC. Then according to the mass ratio of kaolin to NFC of 1:1.5, mixing NFC material with Kaolin to obtain urea-iron modified clay, and marking the urea-iron modified clay as NFC-mix-Kaolin.
As can be seen from FIG. 1, after the urea iron-synthesizing material is introduced into the surface of the kaolin particles, obvious particle attachments appear on the surfaces of the particles, and the sections of the sheets are curled, gaps between the layers are blurred and interfaces become rough.
Algae removal experiment: red tide isoeuglena algae liquid (algae cell density is about 1-2×l0 6 cells/L) in an exponential growth phase is taken and added into a 25mL colorimetric tube according to a compound proportion, the kaolin raw soil, the obtained urea iron-containing modified clay and the modified clay MC I (the modified clay is prepared by mixing polyaluminium chloride and kaolin according to a mass ratio of 1:5) are respectively added into the colorimetric tube, so that the concentration of each treated kaolin in the algae liquid is 0.1g/L, the mixture is shaken uniformly and then is kept stand for 3 hours, and compared with the concentration of algae cells in a control group without the modified clay composite material, the algae removal rate is calculated (the result is shown in figure 2).
Algae removal rate= [1- (experimental group in vivo fluorescence value/control group in vivo fluorescence value) ]x100%.
The results show that under the experimental concentration, the two synthesis modes can obviously improve the algae removal effect (P is smaller than 0.05) of the kaolin, and the algae cell removal rate of the urea iron-synthesizing modified clay prepared by the two synthesis methods after 3 hours is higher than 80%. Compared with the algae removal rate of the two synthetic modes under the same experimental conditions, the removal rate of the urea iron-alloy modified clay group prepared by the surface synthesis method is obviously higher than that of the urea iron-alloy modified clay prepared by the pre-mixing method (P is less than 0.05). In contrast, the algae removal rate of the unmodified kaolin at the concentration of 0.1g/L is only 23%, and the algae removal capacity of the existing red tide isoeuglena algae liquid treated by using the modified clay MC I is lower, and the algae removal rate is less than 50%.
Example 2
The urea iron-synthesizing modified clay is prepared by referring to the surface synthesis method described in the example 1, and the ratio R U-Fe of urea to iron ions in the preparation process is regulated to be 1:3.4, 1:1.7, 1:1.1 and 1:0.8, so that the urea iron-synthesizing modified clay with different R U-Fe ratios is obtained.
Then, the obtained urea-iron-containing modified clay with different proportions is compared with the removal efficiency of the urea-iron-containing modified clay with different R U-Fe proportions on red tide isoglena according to the algae removal experimental method described in the example 1, and the result is shown in figure 3.
As can be seen from fig. 3, the 3h removal rate of the R U-Fe = 1:1.1 urea iron-on-modified clay on red tide isotrichum was 92%, and the removal rate of urea iron-on-modified clay was significantly (P < 0.05) higher than the same amount of other R U-Fe ratios.
Example 3
The surface synthesis method described in example 1 was used to prepare urea iron-containing modified clay, and the ratio of urea iron-containing to kaolin, R N-K, was adjusted to be 10:1, 5:1, 1.5:1, 1:1.5, 1:5, 1:10 during the preparation process to obtain urea iron-containing modified clay with different R N-K ratios.
The obtained urea-iron-containing modified clay with different proportions is compared with the removal efficiency of the urea-iron-containing modified clay with different R N-K proportions on red tide isoglena according to the algae removal experimental method described in the example 1, and the result is shown in figure 4.
As can be seen from fig. 4, the 3h removal rate of the urea-iron-combining modified clay with the ratio of R N-K =1:1 is 92%, the removal rate of the urea-iron-combining modified clay with the ratio of R N-K being 1:1.5, 1:5 and 1:10 is significantly higher than that of the urea-iron-combining modified clay with the same amount of R N-K (P < 0.05), and the 3h removal rate of the urea-iron-combining modified clay with the ratio of R N-K being 10:1, 5:1 and 1.5:1 has a great influence on the pH of the water body.
Example 4
The urea-iron modified clay was prepared by the surface synthesis method described in example 1, and the ratio R U-Fe of urea to iron ions during the preparation was controlled to be 1:1.1, the ratio R N-K of urea to iron and kaolin is 1:1, obtaining the urea iron-containing modified clay NFCK under the optimal preparation condition.
Example 5 Effect of Urea-iron modified Clay on removal of active phosphate in Water
Research shows that phosphorus is one of the most important influencing factors for aggravating water eutrophication, and the water eutrophication can cause problems of unbalanced species distribution of an aquatic ecosystem, damaged ecological system substances and energy flow and the like, so that the ecological environment of the water is endangered.
Drawing a standard curve: 7 25mL volumetric flasks were taken and 0.625,1.25,2.5,5.3125,8.75, 10, 12.5mL of standard phosphate use solution were added, respectively, and water was added to 25mL. The sample was then transferred to a 25mL cuvette and 1mL ascorbic acid solution was added. After 30s, 2mL of molybdate solution was added and thoroughly mixed. The mixed solution was left at room temperature for 15min to develop color, and after the color development was completed, a blank sample (ultrapure water) was used as a reference, and the absorbance value of the corresponding water sample was measured at a wavelength of 700nm using an ultraviolet spectrophotometer, and a working curve was drawn with the corresponding phosphorus content (see fig. 5 for the result).
Dephosphorization experiment: firstly, according to the algae removal experiment method described in example 1, an algae removal experiment is performed by using kaolin, modified clay MC I and urea iron-containing modified clay NFCK prepared in the above example 4, so that the mass concentration of each treatment in the algae liquid is 0.2g/L, after 3 hours, the algae liquid is carefully and evenly shaken, and a filter membrane with the aperture of 0.45 μm is used for filtering, so as to obtain filtrate. Then, after the filtrate to be measured was respectively transferred to 25mL of the score line in a 25mL cuvette, 1mL of an ascorbic acid solution was added. After 30s, 2mL of molybdate solution was added and thoroughly mixed. The mixed solution is placed at room temperature for 15min for color development, a blank sample (ultrapure water) is used as a reference after color development, and an ultraviolet spectrophotometer is used for measuring the absorbance value of the corresponding water sample at the wavelength of 700 nm. The concentration of phosphorus in the water sample to be measured is calculated by the concentration-absorbance standard working curve, and compared with the concentration of phosphorus in the control group without the modified clay composite material, the phosphorus removal rate is calculated (the result is shown in fig. 6).
The results show that the urea iron-containing modified clay NFCK prepared in the example 4 has about 84% of the active phosphate in the water body at the experimental concentration, and has a significant (P < 0.05) height Yu Gaoling as-is soil and modified clay MC I, and the removal rate of the active phosphate in the water body is only 25% and 56%.
In addition, according to the above-mentioned dephosphorization experimental method, the efficiency of removing active phosphate from water body of the urea iron-containing modified clay NFCK prepared in the above-mentioned example 4 by different addition concentrations of 0.025g/L to 0.35g/L was compared, and the result is shown in fig. 7. Wherein, the removal rate of the urea iron-containing modified clay NFCK to the active phosphate gradually rises along with the increase of the adding concentration, and the removal rate of the active phosphate can reach 90 percent when the adding concentration is increased to 0.35 g/L; the removal rate of the active phosphate reaches about 84% when the algae removal rate is 90%, namely the consumption is 0.2 g/L.
Claims (8)
1. A preparation method of a red tide eliminating agent is characterized in that: dispersing fine clay in urea solution, adding iron ion solution under stirring to react, and drying to obtain red tide eliminating agent.
2. The method for preparing the red tide eliminating agent according to claim 1, characterized in that: the mass ratio of the urea to the clay to the iron ions is 1 (0.1-16) to 0.1-3.5.
3. The method for preparing the red tide eliminating agent according to claim 1 or 2, characterized in that: dispersing the fine clay particles in urea solution, adding iron ion solution at a rate of 1-300 mL/min under stirring, reacting at 30-70 ℃ for 1-3h, and drying to obtain the red tide eliminating agent.
4. A method for producing a red tide eliminating agent according to any one of claims 1 to 3, characterized in that: the clay powder is one or a mixture of clay minerals, and the particle size of the powder after crushing is less than 40 mu m.
5. A method for producing a red tide eliminating agent according to any one of claims 1 to 3, characterized in that: the urea solution is a diluted solution of 5-50 g/L formed by dissolving urea in an ethanol solvent; the ferric ion solution is prepared by dissolving soluble ferric salt in an ethanol solvent.
6. The method for producing a red tide eliminating agent according to claim 5, characterized in that: the soluble ferric salt is ferric chloride or ferric nitrate.
7. The red tide eliminating agent prepared by the method of claim 1, which is characterized in that: the red tide eliminating agent prepared by the method has particle attachments on the surfaces of clay particles, curled slice sections, blurred interlayer gaps and rough interfaces.
8. The use of the red tide eliminating agent as defined in claim 7, characterized in that: the red tide eliminating agent is applied to the treatment of red tide organisms and/or pollution factors such as soluble phosphate and the like in water body environment.
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| CN202410184638.9A CN118084156A (en) | 2024-02-19 | 2024-02-19 | Red tide eliminating agent and preparation method thereof |
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| CN202410184638.9A CN118084156A (en) | 2024-02-19 | 2024-02-19 | Red tide eliminating agent and preparation method thereof |
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