CN114854424A - Soil organic matter pollution repairing agent and preparation method thereof - Google Patents
Soil organic matter pollution repairing agent and preparation method thereof Download PDFInfo
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Abstract
The application relates to the field of soil remediation agents, and particularly discloses a soil organic matter pollution remediation agent and a preparation method thereof. A soil organic matter pollution repairing agent comprises an active component containing nano zero-valent iron and an organic polymer coated on the outer side of the active component; the active ingredient containing the nano zero-valent iron is prepared by the following method: (1) adding ferric salt or ferrous salt solution into yeast subjected to freeze drying treatment, stirring, centrifuging, and washing to obtain the yeast with Fe adsorbed 2+ Or Fe 3+ The yeast of (1); (2) under the condition of introducing nitrogen, Fe is adsorbed 2+ Or Fe 3+ The yeast is dropped into sodium borohydride or potassium borohydride, after stirring reaction, filtration is carried out, and the obtained solid is washed and freeze-dried, thus obtaining the active ingredient containing nano zero-valent iron. The soil repairing agent field has a good repairing effect, the repairing effect is stable, and effective degradation of chlorine-containing organic matters can be realized.
Description
Technical Field
The application relates to the field of soil remediation agents, in particular to a soil organic matter pollution remediation agent and a preparation method thereof.
Background
The chlorine-containing organic matter has wide industrial application and can be used for synthesizing intermediate products of dye and pesticide, etc. In recent years, chlorine-containing organic matters become one of the common pollutants in sediment sediments due to the discharge of wastewater, accidental leakage and the like. The performance of the chlorine-containing organic matter is stable, and the chlorine-containing organic matter has the characteristics of high toxicity, easy accumulation and the like.
At present, the degradation technology of chlorine-containing organic matters mainly comprises photocatalytic degradation, electrochemical degradation, microbial degradation and the like. The method for repairing soil and groundwater pollution by utilizing zero-valent iron is a new method proposed in recent years, and due to the wide sources of the zero-valent iron and the low repair cost, the zero-valent iron gradually receives the attention of researchers in the field.
In view of the above-mentioned related technologies, the inventors found that although zero-valent iron can repair soil and effectively reduce the repair cost, the repair effect still needs to be further improved.
Disclosure of Invention
In order to improve the repairing effect of the soil repairing agent, the application provides a soil organic matter pollution repairing agent and a preparation method thereof.
In a first aspect, the application provides a soil organic matter pollution remediation agent, which adopts the following technical scheme:
a soil organic matter pollution repairing agent comprises an active component containing nano zero-valent iron and an organic polymer coated on the outer side of the active component;
the active ingredient containing the nano zero-valent iron is prepared by the following method:
(1) adding ferric salt or ferrous salt solution into yeast subjected to freeze drying treatment, stirring, centrifuging, and washing to obtain the yeast with Fe adsorbed 2+ Or Fe 3+ The yeast of (1);
(2) under the condition of introducing nitrogen, Fe is adsorbed 2+ Or Fe 3+ The yeast is dropped into sodium borohydride or potassium borohydride, after stirring reaction, filtration is carried out, and the obtained solid is washed and freeze-dried, thus obtaining the active ingredient containing nano zero-valent iron.
Because the nanometer zero-valent iron can reunite, so its stability and activity can receive certain restriction, this application adopts the saccharomycete as the carrier, with nanometer zero-valent iron load to the saccharomycete on, can improve nanometer zero-valent iron's dispersibility on the one hand to improve the activity of active ingredient, on the other hand, can also improve nanometer zero-valent iron's stability, thereby improve active ingredient's stability and life.
In addition, the yeast is used as a biological matrix, the raw material source is wide, the yeast is an environment-friendly material, secondary pollution to the environment is avoided, the preparation method of the active ingredient containing the nano zero-valent iron is simple to operate, the process parameters are easy to realize, and the preparation method is suitable for large-scale batch production or small-scale fine production.
In addition, the organic polymer is coated outside the active component, so that the self-aggregation phenomenon of the active component can be further reduced, and the dispersibility and stability of the active component are improved, thereby ensuring the repairing effect and the stability of the repairing effect of the soil organic matter pollution repairing agent.
Preferably, in the step (1), the yeast freeze-drying treatment comprises the following specific steps: centrifuging yeast, suspending in any solution of hydrochloric acid, sodium hydroxide, ethanol, potassium chloride and sodium chloride, modifying, centrifuging, washing, and lyophilizing.
Preferably, the hydrochloric acid refers to a hydrochloric acid solution with the mass percentage concentration of 0.5-10%; the sodium hydroxide refers to a sodium hydroxide solution with the mass percentage concentration of 0.5-10%; the ethanol refers to an ethanol solution with the mass percentage concentration of 0.5-20%; the potassium chloride refers to a potassium chloride solution with the mass percentage concentration of 0.5-20%; the sodium chloride refers to a sodium chloride solution with the mass percentage concentration of 0.5-20%.
By adopting the technical scheme, the chemical solvent is adopted to chemically modify the saccharomycetes, so that the stability and the reactivity of the saccharomycetes can be effectively improved, the loading effect on the nano zero-valent iron is further improved, and the stability and the repairing effect of active ingredients are improved.
Preferably, the temperature of the modification treatment is 40-50 ℃, and the time is 12-48 h.
The modification effect of the saccharomycetes is further improved by controlling the temperature and the time, so that the repairing effect of the repairing agent is improved.
Preferably, in the step (1), the concentration of the ferric salt or ferrous salt solution is 0.05-2 mol/L.
Preferably, the weight ratio of the ferric salt or ferrous salt solution to the yeast is (0.05-0.5): 1.
Within the proportion range, ferric salt or ferrous salt and yeast can be fully mixed, so that the nano zero-valent iron and the yeast carrier have a proper proportion, and the repairing effect of the repairing agent is improved.
Preferably, the nitrogen flow rate is 0.4-0.6 mL/min.
Preferably, in the step (2), Fe is adsorbed 2+ Or Fe 3+ The dropping rate of the yeast is 0.2-1 mL/min.
By controlled adsorption of Fe 2+ Or Fe 3+ The dropping rate of yeast is to make Fe 2+ Or Fe 3+ The content of the zero-valent iron in the active ingredients is ensured by fully reducing the zero-valent iron, so that the repairing effect of the soil organic matter pollution repairing agent is ensured.
Preferably, in step (2), Fe 2+ Or Fe 3+ With boron hydrogenThe molar ratio of sodium hydroxide to potassium borohydride is 1 (2-6).
By controlling Fe 2+ Or Fe 3+ The molar ratio of the Fe to the sodium borohydride or the potassium borohydride is Fe on the yeast carrier 2+ Or Fe 3+ Fully reducing, and ensuring the content of zero-valent iron in the active ingredients, thereby ensuring the repairing effect of the soil organic matter pollution repairing agent.
Preferably, the organic polymer comprises one or more of chitosan, hydroxymethyl cellulose, cyclodextrin, polyacrylic acid, polyvinylpyrrolidone, polystyrene sulfate.
The organic polymer adopted by the application is a biodegradable high molecular polymer, is an environment-friendly material, and is simple and easy to obtain.
In a second aspect, the application provides a preparation method of a soil organic matter pollution remediation agent, which adopts the following technical scheme:
a preparation method of a soil organic matter pollution repairing agent comprises the following steps: and (3) dipping the active component containing the nano zero-valent iron into an organic polymer solution with the mass concentration of 0.1-3%, reacting in an inert atmosphere, filtering, and drying to obtain the nano zero-valent iron-containing nano-composite material.
The preparation method is simple to operate, the process is easy to realize, and the soil organic matter pollution remediation agent with a good remediation effect can be stably prepared in a large scale.
In summary, the present application has the following beneficial effects:
1. according to the application, the biological matrix saccharomycetes is used as the carrier of the zero-valent iron, so that the agglomeration phenomenon of the nano zero-valent iron is improved, the dispersity and the stability of the nano zero-valent iron are improved, the repairing effect of the soil organic matter pollution repairing agent is improved, and the repairing effect is stable;
2. the organic polymer is coated on the outer side of the active ingredient, so that the dispersibility and stability of the active ingredient are further improved, and the repairing effect and the stability of the repairing effect of the soil organic matter pollution repairing agent are ensured;
3. the saccharomycetes are chemically modified, so that the stability and the reactivity of the saccharomycetes are effectively improved, and the stability and the repairing effect of active ingredients are further improved.
Detailed Description
The present application will be described in further detail with reference to examples.
The starting materials used in the examples of the present application are all commercially available.
Examples of preparation of active ingredients
Preparation example 1
An active ingredient, prepared by the steps comprising:
(1) mixing Fe 3+ Adding 0.05mol/L ferric salt solution into yeast subjected to conventional freeze drying treatment, wherein the weight ratio of the ferric salt solution to the yeast is 0.05:1, stirring, centrifuging, and washing to obtain yeast containing adsorbed Fe 3+ The yeast of (1);
(2) under the condition of introducing nitrogen, Fe is adsorbed 3+ The microzyme is dropped into sodium borohydride solution with the molar concentration of 1mol/L at the speed of 0.2mL/min to lead Fe 3+ The molar ratio of the active component to sodium borohydride is 1:2, the active component containing the nano zero-valent iron is obtained by stirring, reacting for 2 hours, filtering, washing the obtained solid and freeze-drying.
In other preparation examples, a ferrous salt solution may be used instead of the ferric salt solution in preparation example 1, and potassium borohydride may be used instead of sodium borohydride in preparation example 1. When the obtained active ingredients are applied to the preparation of the soil organic matter pollution remediation agent, the remediation effect and the stability of the remediation effect are not obviously different from those of the preparation example 1. Therefore, the above options should not be construed as limiting the technical solutions and the specific embodiments of the present application.
Preparation example 2
An active ingredient, which is different from preparation example 1 in that: in the step (1), Fe is contained in the iron salt solution 3+ The concentration of (2) is 1 mol/L. Other conditions were the same as above.
Preparation example 3
An active ingredient, which is different from preparation example 1 in that: in the step (1), Fe is contained in the iron salt solution 3+ The concentration of (2) is 2 mol/L. Other conditions were the same as above.
In addition, in other preparation examples, Fe in iron salt solution 3+ The concentration of (b) can be arbitrarily selected within the range of 0.02-5 mol/L, and the present application is only illustrated by the above three groups of preparation examples, and should not be taken as a limitation on the technical scheme and the specific embodiment of the present application.
Preparation example 4
An active ingredient, which is different from preparation example 2 in that: in the step (1), the weight ratio of the ferric salt solution to the yeast is 0.3: 1. Other conditions were the same as above.
Preparation example 5
An active ingredient, which is different from preparation example 2 in that: in the step (1), the weight ratio of the ferric salt solution to the yeast is 0.5: 1. Other conditions were the same as above.
In addition, in other preparation examples, the weight ratio of the ferric salt solution to the yeast can be (0.01-1): 1, such as 0.01:1, 0.1:1 or 0.8:1, and the obtained active ingredient has good activity and stability when being applied to preparation of the soil organic matter pollution remediation agent. Therefore, the weight ratio of the ferric salt solution to the yeast should not be construed as limiting the technical solution and embodiments of the present application.
Preparation example 6
An active ingredient, which is different from preparation example 4 in that: in the step (2), Fe is adsorbed 3+ The dropping rate of the yeast (2) was 0.6 mL/min. Other conditions were the same as above.
Preparation example 7
An active ingredient, which is different from preparation example 4 in that: in the step (2), Fe is adsorbed 3+ The dropping rate of the yeast (2) was 1 mL/min. Other conditions were the same as above.
In addition, in other preparation examples, Fe was adsorbed 3+ The dropping speed of the saccharomycetes can be selected within 0.1-2 mL/min, and the obtained active ingredients still have good activity and stability when being applied to the preparation of the soil organic matter pollution remediation agent. Therefore, the weight ratio of the ferric salt solution to the yeast should not be construed as limiting the technical solution and embodiments of the present application.
Preparation example 8
An active ingredient, which is different from preparation example 6 in that: in the step (2), Fe 3+ The molar ratio to sodium borohydride was 1: 4. Other conditions were the same as above.
Preparation example 9
An active ingredient, which is different from preparation example 6 in that: in the step (2), Fe 3+ The molar ratio to sodium borohydride was 1: 6. Other conditions were the same as above.
In addition, in other preparation examples, Fe 3+ The molar ratio of the active ingredient to the sodium borohydride can be selected within the range of 1 (1-10), and the obtained active ingredient still has good activity and stability when being applied to preparation of a soil organic matter pollution remediation agent. Therefore, the weight ratio of the ferric salt solution to the yeast should not be construed as limiting the technical solution and the specific embodiments of the present application.
Preparation example 10
An active ingredient, which is different from preparation example 8 in that: in the step (1), the yeast freeze drying treatment comprises the following specific steps: centrifuging yeast, resuspending in 5% hydrochloric acid solution for modification at 40 deg.C for 48 hr, centrifuging after modification, washing, and freeze drying. Other conditions were the same as above.
In addition, in other preparation examples, the organic solution may also be a hydrochloric acid solution with a mass percentage concentration of 0.5-10%, a sodium hydroxide solution with a mass percentage concentration of 0.5-10%, an ethanol solution with a mass percentage concentration of 0.5-20%, a potassium chloride solution with a mass percentage concentration of 0.5-20%, a sodium chloride solution with a mass percentage concentration of 0.5-20%, and the like, and therefore, the selection of the organic solution should not be taken as a limitation to the technical scheme of the present application.
Preparation example 11
An active ingredient, which is different from preparation example 10 in that: the temperature of the modification treatment was 45 ℃ and the time was 30 hours. Other conditions were the same as above.
Preparation example 12
An active ingredient, which is different from preparation example 10 in that: the temperature of the modification treatment is 50 ℃ and the time is 12 h. Other conditions were the same as above.
Performance test-detection of 1, 3-dichlorobenzene pollution remediation Effect
The soil organic matter pollution repairing agents prepared in the following examples and comparative examples were subjected to repairability detection.
The main physicochemical properties of the test substrate sludge are shown in the following table:
wherein, the water content of the bottom mud is measured by a drying method; the content of organic matters is measured by adopting a K2Cr2O7 volumetric method; measuring the total nitrogen content by adopting a Kjeldahl method; the quick-acting nitrogen is subjected to lateral undetermined determination by an alkaline hydrolysis diffusion method; the total phosphorus content is measured by adopting a molybdenum-antimony colorimetric-resistance method; the content of fast-acting phosphorus is determined by the Olsen method.
The test samples comprise a blank group (1, 3-dichlorobenzene polluted bottom mud), an experimental group (the repairing agent obtained in the embodiment repairs the 1, 3-dichlorobenzene polluted bottom mud) and a control group (the repairing agent obtained in the comparative example repairs the 1, 3-dichlorobenzene polluted bottom mud). The preparation method of the blank group comprises the following steps: firstly preparing an acetone solution with the content of 1, 3-dichlorobenzene of 10g/L, then adding 10g of the test substrate sludge into 90mL of distilled water, adding the acetone solution of 1, 3-dichlorobenzene, and fully oscillating to ensure that the content of 1, 3-dichlorobenzene in the substrate sludge reaches 500 mg/kg; the preparation method of the experimental group comprises the following steps: preparing 1, 3-dichlorobenzene polluted bottom mud according to a blank group method, then adding 0.2g of the repairing agent obtained in the example, repeating 3 times for each treatment, plugging a rubber plug coated with a polytetrafluoroethylene membrane, and culturing in a dark place under a constant temperature shaking table at 25 ℃ and 120 r/min; the control group was prepared in the same manner as the experimental group except that the repairing agent obtained in example was replaced with the repairing agent obtained in comparative example.
The amount of chloride ions generated by dechlorination of 1, 3-dichlorobenzene was measured by silver nitrate titration, and the removal rate (7d) was calculated therefrom, and the calculation results in each group were averaged.
Examples
Example 1
A soil organic matter pollution repairing agent consists of an active component containing nano zero-valent iron and an organic polymer coated on the outer side of the active component.
The preparation method of the soil organic matter pollution repairing agent comprises the following steps: the active ingredient containing the nano zero-valent iron prepared in the preparation example 1 is soaked into a chitosan solution with the mass concentration of 2%, and is filtered and dried after reacting for 2 hours in a nitrogen atmosphere.
In addition, in other embodiments, the mass concentration of the chitosan solution may be optionally 0.1-3%, and one or more organic polymer solutions of hydroxymethyl cellulose, cyclodextrin, polyacrylic acid, polyvinylpyrrolidone, and polystyrene sulfate may be used instead of the chitosan solution. Therefore, the selection and mass concentration of the organic polymer are not intended to limit the technical solutions and embodiments of the present application.
Examples 2 to 3
A soil organic matter pollution repairing agent consists of an active component containing nano zero-valent iron and an organic polymer coated on the outer side of the active component. The difference from example 1 is that the active ingredients obtained in preparation examples 2 and 3 were used, respectively. Namely, examples 1 to 3 are different in that Fe in the iron salt solution is used for preparing the active ingredient 3+ Are different.
The soil organic matter pollution remediation agent obtained in example 1 to example 3 was subjected to 1, 3-dichlorobenzene pollution remediation effect detection, and the calculation results are shown in the following table:
as can be seen from the data in the table, the repairing agents obtained in the examples 1-3 have good repairing effects on 1, 3-dichlorobenzene pollution, and the removal rate of 1, 3-dichlorobenzene after 7 days of treatment can reach more than 82%.
Examples 4 to 5
A soil organic matter pollution repairing agent consists of an active component containing nano zero-valent iron and an organic polymer coated on the outer side of the active component. The difference from example 2 is that the active ingredients obtained in preparation example 4 and preparation example 5 were used, respectively. Namely, examples 2, 4 and 5 are different in the weight ratio of the iron salt solution to the yeast when preparing the active ingredient.
The soil organic matter pollution remediation agent obtained in example 4-5 was subjected to 1, 3-dichlorobenzene pollution remediation effect detection, and the calculation results are shown in the following table:
as can be seen from the data in the table, the repairing agents obtained in the examples 4-5 have good repairing effects on the 1, 3-dichlorobenzene pollution, and the removal rate of the 1, 3-dichlorobenzene after 7 days of treatment can reach over 84%. Further analysis revealed that the removal of 1, 3-dichlorobenzene increased with increasing weight of iron salt solution within a certain range, but in contrast, the removal of 1, 3-dichlorobenzene in example 5 was only 0.3% higher than that in example 4, thus showing that the improvement is no longer significant when the weight ratio of iron salt solution to yeast is higher than 0.3: 1.
Examples 6 to 7
A soil organic matter pollution repairing agent consists of an active component containing nano zero-valent iron and an organic polymer coated on the outer side of the active component. The difference from example 4 is that the active ingredients obtained in preparation examples 6 and 7 were used, respectively. That is, examples 4, 6 and 7 are different in that Fe is adsorbed when preparing the active ingredient 3+ The dropping rate of the yeast is different.
The soil organic matter pollution remediation agent obtained in examples 6 to 7 was subjected to 1, 3-dichlorobenzene pollution remediation effect detection, and the calculation results were included in the following table:
as can be seen from the data in the table, the repairing agents obtained in examples 6-7 have good repairing effects on 1, 3-dichlorobenzene pollution, and the removal rates of 1, 3-dichlorobenzene after 7d treatment can respectively reach 84.8% and 84.2%. As can be seen from the data in comparative examples 4, 6 and 7, when the dropping rate is 0.6mL/min, the obtained soil organic matter pollution remediation agent has a better remediation effect.
Examples 8 to 9
A soil organic matter pollution repairing agent consists of an active component containing nano zero-valent iron and an organic polymer coated on the outer side of the active component. The difference from example 6 is that the active ingredients obtained in preparation examples 8 and 9 were used, respectively. Namely, the difference among examples 6, 8 and 9 is that Fe is used for preparing the active ingredient 3+ In a different molar ratio to sodium borohydride.
The soil organic matter pollution remediation agent obtained in examples 8 to 9 was subjected to 1, 3-dichlorobenzene pollution remediation effect detection, and the calculation results were included in the following table:
as can be seen from the data in the table, the repairing agents obtained in the examples 8-9 have good repairing effects on the 1, 3-dichlorobenzene pollution, and the removal rates of the 1, 3-dichlorobenzene after 7 days of treatment can respectively reach 85.2% and 84.9%. It can be seen that, in the above-described 3 sets of embodiments, embodiment 8 is the preferred embodiment.
Examples 10 to 12
A soil organic matter pollution repairing agent consists of an active component containing nano zero-valent iron and an organic polymer coated on the outer side of the active component. The difference from example 8 is that the active ingredients obtained in preparation examples 10, 11 and 12 were used, respectively.
Examples 10-12 in all three groups of examples, the yeast carrier was modified by chemical treatment, and the difference between examples 10, 11, 12 is that the conditions of the modification treatment were not passed.
The soil organic matter pollution remediation agent obtained in examples 10 to 12 was subjected to 1, 3-dichlorobenzene pollution remediation effect detection, and the calculation results were included in the following table:
from the data in the table, it can be seen that, when the active ingredient in the repairing agent is prepared, the repairing effect of the finally obtained repairing agent can be obviously improved by modifying the yeast carrier, in examples 10 to 12, the removal rate of 1, 3-dichlorobenzene after detection can reach more than 86% by modifying the yeast carrier through chemical treatment, and is obviously higher than 85.2% in example 8.
Comparative example
Comparative example 1
A repairing agent is reduced iron powder.
Comparative example 2
A repairing agent, which is the active ingredient prepared in preparation example 1.
And (3) detecting the repairing effect of the 1, 3-dichlorobenzene pollution by using the repairing agent obtained in the comparative example 1-2, and calculating the result according to the following table:
as can be seen from the data in the above table, the repairing effect of the repairing agent in comparative example 2 of comparative example 1 is significantly reduced compared to that of example 1, wherein the removal rate of 1, 3-dichlorobenzene in comparative example 1 is only 62.3%, and the removal rate of 1, 3-dichlorobenzene in comparative example 2 is only 74.6%. Therefore, the organic pollutant repairing agent has the advantages that the organic matter is used for wrapping the active ingredient, and the active ingredient is formed by yeast loaded with the nano zero-valent iron, so that the repairing effect of the repairing agent on organic pollutants is greatly improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The soil organic matter pollution repairing agent is characterized by comprising an active ingredient containing nano zero-valent iron and an organic polymer coated on the outer side of the active ingredient;
the active ingredient containing the nano zero-valent iron is prepared by the following method:
(1) adding ferric salt or ferrous salt solution into yeast subjected to freeze drying treatment, stirring, centrifuging and washing to obtain the yeast adsorbed with Fe 2+ Or Fe 3+ The yeast of (1);
(2) under the condition of introducing nitrogen, Fe is adsorbed 2+ Or Fe 3+ The yeast is dropped into sodium borohydride or potassium borohydride, after stirring reaction, filtration is carried out, and the obtained solid is washed and freeze-dried, thus obtaining the active ingredient containing nano zero-valent iron.
2. The soil organic matter pollution remediation agent of claim 1, wherein in step (1), the yeast freeze-drying treatment comprises the following steps: centrifuging yeast, suspending in any solution of hydrochloric acid, sodium hydroxide, ethanol, potassium chloride and sodium chloride, modifying, centrifuging, washing, and lyophilizing.
3. The soil organic matter pollution remediation agent of claim 2, wherein the temperature of the modification treatment is 40-50 ℃ and the time is 12-48 hours.
4. The soil organic matter pollution remediation agent of claim 1, wherein in step (1), the concentration of the ferric salt or ferrous salt solution is 0.05-2 mol/L.
5. The soil organic matter pollution remediation agent of claim 4, wherein the weight ratio of the ferric salt or ferrous salt solution to the yeast is (0.05-0.5): 1.
6. The organic matter contamination remediating agent as recited in claim 1, wherein the agent is selected from the group consisting ofCharacterized in that in the step (2), Fe is adsorbed 2+ Or Fe 3+ The dropping rate of the yeast is 0.2-1 mL/min.
7. The organic matter contamination remediating agent as recited in claim 1, wherein in step (2), Fe 2+ Or Fe 3+ The molar ratio of the sodium borohydride to the potassium borohydride is 1 (2-6).
8. The soil organic matter pollution remediation agent of claim 1, wherein the organic polymer comprises one or more of chitosan, hydroxymethyl cellulose, cyclodextrin, polyacrylic acid, polyvinylpyrrolidone, polystyrene sulfate.
9. The method for preparing the soil organic matter pollution remediation agent of any one of claims 1 to 8, comprising the steps of: and (3) dipping the active component containing the nano zero-valent iron into an organic polymer solution with the mass concentration of 0.1-3%, reacting in an inert atmosphere, filtering, and drying to obtain the nano zero-valent iron-containing nano-composite material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105081305A (en) * | 2014-05-04 | 2015-11-25 | 中国人民解放军63971部队 | Porous nanometer zero-valent iron and porous nanometer zero-valent iron composite material |
| CN105080027A (en) * | 2014-05-09 | 2015-11-25 | 中国人民解放军63971部队 | Disinfecting material taking nano zero-valent iron as main disinfecting component and preparation method thereof |
| CN108714413A (en) * | 2018-06-08 | 2018-10-30 | 湖南农业大学 | One Yeasts carry nano zero valence iron and application thereof |
| CN111234842A (en) * | 2020-03-29 | 2020-06-05 | 江西普瑞丰生态科技有限公司 | Soil heavy metal composite repairing agent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105081305A (en) * | 2014-05-04 | 2015-11-25 | 中国人民解放军63971部队 | Porous nanometer zero-valent iron and porous nanometer zero-valent iron composite material |
| CN105080027A (en) * | 2014-05-09 | 2015-11-25 | 中国人民解放军63971部队 | Disinfecting material taking nano zero-valent iron as main disinfecting component and preparation method thereof |
| CN108714413A (en) * | 2018-06-08 | 2018-10-30 | 湖南农业大学 | One Yeasts carry nano zero valence iron and application thereof |
| CN111234842A (en) * | 2020-03-29 | 2020-06-05 | 江西普瑞丰生态科技有限公司 | Soil heavy metal composite repairing agent |
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