CN110668545A - Water treatment agent based on nano system and preparation method thereof - Google Patents
Water treatment agent based on nano system and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 239000005642 Oleic acid Substances 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
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- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 6
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- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 5
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000012851 eutrophication Methods 0.000 description 3
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a water treatment agent based on a nano system and a preparation method thereof, belonging to the technical field of reclaimed water treatment. The invention converts the prepared Polyoxometallate (POM) nano wafer into a single-wall POM nanotube by winding, stretching and rearranging, combines the nanotube with modified chitosan to form a composite material, and finally assembles the prepared nano zero-valent iron into the POM nanotube to prepare the composite medicament. The medicament prepared by the invention realizes the adsorption and reduction of nitrate by utilizing the modified nano zero-valent iron, breaks through the limitation of conventional zero-valent iron for removing nitrate on conditions such as pH and the like, and overcomes the phenomena of passivation, agglomeration and the like generated in the removing process, thereby obtaining more efficient removing efficiency.
Description
Technical Field
The invention relates to a water treatment agent based on a nano system and a preparation method thereof, belonging to the technical field of reclaimed water treatment.
Background
At present, the water eutrophication phenomenon is common, and research results show that nitrogen pollution has obvious influence on water eutrophication, and nitrate nitrogen is one of the important reasons for water eutrophication. The harm caused by nitrogen pollution in the water body is very much, for example, the excessive nitrate nitrogen increases nutrient substances in the water body, promotes the autotrophic microorganisms to grow vigorously, causes water quality deterioration and destroys the ecological environment; human and aquatic animal health is threatened; increased cost of water treatment, etc. Therefore, further improvements in denitrification theory and process are needed to invent more efficient denitrification techniques.
At present, the removal of nitrate nitrogen in water mainly comprises three types, namely a physical method, a chemical method and a biological method. The physical methods mainly include reverse osmosis, ion exchange, electrodialysis, and the like. The physical method has relatively high operation cost, is difficult to remove nitrate with high concentration, and can cause the problems of secondary pollution and the like. The biological denitrification technology mainly refers to that nitrate accumulated in a water body is transferred or converted through the growth metabolism of microorganisms on the basis of the microorganisms. The biological method for removing nitrate nitrogen is already applied and is mature, but has a plurality of defects, such as complex process, high operation management requirement, slow denitrification speed, large reactor or structure volume, high construction investment cost and the like. The principle of the chemical method is to reduce and remove nitrate by using the oxidation-reduction reaction of chemical substances. Chemical denitrification has been widely used due to the advantages of easy operation of treatment equipment, easy realization of automatic monitoring and control, and multiple pollutant treatment types. Specific methods include metal reduction methods, catalytic denitrification, and the like.
The reducing agents which are widely researched and applied in the denitrification by the metal reduction method comprise metallic iron, metallic aluminum, metallic zinc and the like. Among them, zero-valent iron has the advantages of wide sources, fast reaction speed, low price, etc., so that the method for removing nitrate by taking zero-valent iron as reduction denitrification has been widely concerned. Although zero-valent iron has various advantages compared with other reducing agents, the application of zero-valent iron technology is limited by itself, such as the zero-valent iron is easy to generate passivation phenomenon in the reaction process, and the reaction conditions such as the need of adjusting pH are harsh.
Chinese patent 'a method for efficiently removing nitrate in underground water by Fe-graphene particles' (application number: 201510604939.3; published: 2016, 1/6/2016) is that an Fe-graphene particle material is prepared by using graphene oxide powder and iron powder, and the prepared material is used as a reducing agent to reduce and remove nitrate. In the process, the electrons obtained by the nitrate are reduced into nitrogen, nitrite or ammonia, thereby achieving the purpose of removing the nitrate. However, the prepared reducing agent cannot well overcome the passivation phenomenon, the problem of iron loss exists, the removed nitrate is not completely converted into nitrogen, most of the nitrate is converted into nitrite, ammonia exists in water, and the nitrite and the ammonia need to be removed in subsequent links. Chinese patent 'a method for removing nitrate in water by using a zero-valent iron/oxidant/zeolite synergistic system' (application number: 201310312657.7; published: 2015, 02, 11), the nitrate is removed by using common iron powder, common oxidant and natural zeolite, in the system, the oxidant oxidizes and peels off a passivation layer formed on the surface of the zero-valent iron, so that internal zero-valent iron electrons can be continuously transmitted to the outside, thereby the zero-valent iron can keep high reduction activity to reduce the nitrate into ammonia nitrogen, and the removal is realized by using adsorption of the zeolite on the ammonia nitrogen. However, this method simply adds the effects of some common substances, and has a limited effect. And in addition, the oxidation-reduction effect is generated with the zero-valent iron in the process of stripping the passivation layer on the surface of the zero-valent iron by the oxidant, the zero-valent iron and the oxidant in the system are consumed, and the use effect of the medicament is reduced.
Therefore, how to utilize the zero-valent iron, the reduction effect of the zero-valent iron is exerted to the maximum, the use condition of the zero-valent iron for removing nitrate nitrogen is improved, the problems of passivation and the like are avoided, and the complete removal of nitrate by the zero-valent iron can be realized more stably and more efficiently, which is the key point that the development of the technology for removing nitrate by the zero-valent iron needs to break through.
Disclosure of Invention
The purpose is as follows: in order to overcome the defects in the prior art, the invention provides a water treatment medicament based on a nano system and a preparation method thereof.
The technical scheme is as follows: in order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a water treatment medicament based on a nano system comprises the following steps:
step (1): weighing sodium tungstate dihydrate and disodium hydrogen phosphate, dissolving in deionized water, adding absolute ethyl alcohol, adding oleic acid and oleylamine, stirring and mixing uniformly to obtain a mixture, and then placing the mixture in a reaction kettle for anaerobic heating reaction to obtain a reaction mixture;
weighing modified chitosan, adding the modified chitosan into the reaction mixture, and stirring for a set time to obtain a mixture A, namely a POM nano wafer mixture;
step (2): weighing ferrous sulfate, dispersing the ferrous sulfate in absolute ethyl alcohol, and mechanically stirring uniformly to obtain a mixture B;
weighing potassium borohydride, dissolving the potassium borohydride into de-oxygenated deionized water to obtain a potassium borohydride solution, and dropwise adding or adding the potassium borohydride solution into the mixture B for a plurality of times within a set time of maintaining a set temperature for ultrasonic treatment reaction to obtain a mixed solution C, namely a nanoscale zero-valent iron mixed solution;
and (3): and mixing the mixture A and the mixed solution C, adding hydrochloric acid to adjust the pH value to 1-3, performing ultrasonic treatment, and placing the mixture in a reaction kettle for anaerobic heating reaction to obtain the water treatment agent based on the nano system.
In some embodiments, in the step (1), the mass ratio of the sodium tungstate to the disodium hydrogen phosphate to the deionized water is 2:1 (10-20);
in the step (1), the mass ratio of the added deionized water to the absolute ethyl alcohol to the added oleic acid to the added oleylamine is 20: (4-8): (2-3): (0.5 to 1); the stirring speed is 200-300 r/min, and the stirring time is 10 min.
In some embodiments, in the step (1), the temperature of the anaerobic heating reaction is 150 to 180 ℃, and the reaction time is 0.5 to 1 hour.
In some embodiments, in the step (1), the modified chitosan is trimethyl ammonium chloride modified chitosan,
the adding amount of the modified chitosan is 0.1-0.2 time of the mass of the disodium hydrogen phosphate, the stirring speed is 200-300 rpm, and the stirring reaction is carried out for 3-5 hours.
In some embodiments, in step (1), the ratio of sodium tungstate dihydrate added: disodium hydrogen phosphate: deionized water: anhydrous ethanol: oleic acid: oleylamine: the mass ratio of the modified chitosan is 2:1 (10-20): (4-8): (2-3): (0.5-1): (0.1-0.2).
In some embodiments, in the step (2), the mass-to-volume ratio of the ferrous sulfate to the absolute ethyl alcohol is (3-5) g/100 ml; the mechanical stirring speed was 500-800 rpm.
In some embodiments, in the step (2), the volume of the deoxygenated deionized water is the same as that of the absolute ethyl alcohol, and the deoxygenation treatment method is to perform deoxygenation treatment on the deionized water by using nitrogen aeration.
In some embodiments, in step (2), the potassium borohydride solution is added to mixture B in three times at the time points of 0, 10, and 20min of the sonication reaction.
In some embodiments, in the step (2), the temperature of the ultrasonic treatment reaction is 20-25 ℃, the ultrasonic condition is 400-500W, and the treatment time is 30 min.
In some embodiments, in step (2), the ratio of added ferrous sulfate: the mass ratio of the potassium borohydride is 1: 0.6.
In some embodiments, in step (3), the mixing ratio of mixture a to mixture C based on the mass of the added disodium hydrogen phosphate in mixture a and the mass of the added ferrous sulfate in mixture C is disodium hydrogen phosphate: and (3) 1 (0.3-0.9) of ferrous sulfate. (Here also the delete bar)
In some embodiments, in the step (3), the concentration of the added hydrochloric acid is 24% by mass and the density is 1.12g/cm3。
In some embodiments, in the step (3), the ultrasonic condition is 200-.
In some embodiments, in the step (3), the heating temperature for the anaerobic heating reaction is 120 ℃ and the reaction time is 0.5-1 h.
On the other hand, the invention also provides a water treatment medicament based on the nano system, which is prepared by the preparation method of the water treatment medicament based on the nano system.
Iron is the second highest metal content in the earth's crust due to its electrode potential E0(Fe2+the/Fe) is-0.41V, so that the catalyst has stronger reducing capability and can realize the reduction removal of a plurality of pollutants. Research shows that zero-valent iron has strong reducing property in the aspect of removing pollutants and can reduce a plurality of pollutants, but the performance of the zero-valent iron is gradually reduced when the zero-valent iron is operated for a long time. This is because the zero-valent iron surface generates a corrosion layer (hydroxide or oxide) during long-term operation, so that the activity of the zero-valent iron is decreased.
Due to the rapid development of the nano technology, the great attention to the nano material is promoted, and the nano zero-valent iron technology is the improvement and development of the zero-valent iron technology, and is one of the most widely researched engineering materials in environmental management and toxic waste treatment. The nanoscale zero-valent iron size is in the transition region of conventional fine iron powder and microscopic atomic clusters, and thus exhibits many unique properties, the most significant of which is its surface effect. Compared with the conventional iron powder, the specific surface area of the nano zero-valent iron is increased by tens of times to tens of thousands of times, so that the number of active sites on the surface is greatly increased, and the degradation efficiency of pollutants is remarkably improved. However, the nano zero-valent iron particles have the defects of easy agglomeration, easy oxidation, difficult storage, low stability and the like, and the application and popularization of the nano zero-valent iron technology are limited, so that the nano zero-valent iron is usually modified to a certain extent in pollutant remediation. There are several such modification methods: loading other metals to form the bimetallic nanoparticles, such as Pd, Au, Cu or Ni and the like on the surface of the nano zero-valent iron to improve the reducibility; the modification of the surface nano zero-valent iron, namely the nano zero-valent iron is coated in the activated carbon and the mesoporous carbon, so that the defect that the nano zero-valent iron is easy to oxidize can be effectively overcome; dispersing and modifying, namely dispersing or stabilizing and modifying the nano zero-valent iron by using a dispersing agent or a stabilizing agent, such as agar, cellulose or starch, so that the nano zero-valent iron exists more uniformly and stably in an aqueous solution, aggregation among particles is reduced, and the reaction activity is enhanced. The application utilizes the modified nano POM to realize the assembly modification of the nano zero-valent iron, so that the nano zero-valent iron can stably exist in a solution, is not easy to agglomerate, and realizes the effect of improving the activity.
Polyoxometallate (POM) as a metal oxygen cluster anion is a compound with a very wide application range, has unique structural characteristics, and can undergo a reversible redox process on the premise of not changing the self structure. The POM has very high catalytic activity in the oxidation-reduction reaction of organic matters, can be recycled, has long service life and certain oxidation resistance, can be used for various homogeneous and heterogeneous catalytic systems, and can be used as a medium to accelerate electron transfer so as to catalyze the oxidation-reduction reaction. POM is a basic building unit for the construction of new functional materials such as catalysts due to its novel, diversified, tunable, and modifiable structure. With the progress of research, it has become possible to completely control the size, morphology, composition and surface modification of nanoparticles during synthesis, and thus the research of nanocomposites has been rapidly developed, in which the composite materials based on POM and noble metal nanoparticles have attracted attention. POMs on the nanometer scale have unique nanomolecular structures and a wide range of physical and chemical properties. The nano composite material based on the nano-level POM and the metal has multiple functions through the synergistic effect among the components, and the multiple functions are not possessed by single components, so that the POM has the characteristics of adjustable and controllable diverse structures, rich compositions, high charge density and reversible oxidation-reduction property of the POM, good biocompatibility, high reduction property, catalytic activity and the like of the metal nano material. These properties enable the use of composite materials based on POM and metal nano-materials in a variety of fields such as catalysis, biology, etc. Modifying the nano-scale POM by utilizing nano zero-valent iron to obtain a modified composite intermediate material, and then converting the nano-material of the intermediate into the POM single-walled nanotube assembled with the nano zero-valent iron through winding, stretching and rearrangement. The zero-valent iron in the composite material has stronger reducibility to nitrate, and the POM is used as a medium to accelerate electron transfer, can catalyze the reduction effect of the zero-valent iron to the nitrate, and improve the reduction performance of the zero-valent iron. In addition, the POM single-walled nanotube realizes the protection effect on the nano zero-valent iron, so that the nano zero-valent iron with high activity is not easy to be oxidized to generate passivation phenomenon, thereby causing the problem of activity reduction. In the using process of the medicament, due to the special structure of the material and the action of the POM, the agglomeration problem of the nano particles is relieved, the action effect of the medicament is ensured, and the removal capability is further enhanced.
Chitosan, one of the most abundant natural biomaterials in the world, has an adsorption effect on various pollutants. The amino group of chitosan is protonated in dilute acid solution, so that molecular chain has great amount of positive charge, and the chitosan becomes a typical cationic adsorbent, has double functions of electric neutralization and adsorption flocculation, and can be used for adsorbing anions. Meanwhile, the chitosan molecular structure has a plurality of active groups such as amino, hydroxyl and the like, so that a plurality of chemical modifications can be carried out to improve the adsorption performance. According to the invention, trimethyl ammonium chloride modified chitosan is selected as an intermediate, the modification is beneficial to enhancing the dissolving property of chitosan, and the adsorption capacity for adsorbing nitrate anions can be further improved; through the combination of the modified chitosan and the nano composite material, the adsorption and aggregation of the nitrate are realized, so that the nitrate can be rapidly aggregated near the effective components of the nitrate in the wastewater by the medicament, and the nitrate is rapidly reduced by the zero-valent iron, thereby realizing the rapid removal effect of the nitrate.
Has the advantages that: the invention provides a water treatment medicament based on a nano system and a preparation method thereof.A prepared Polyoxometallate (POM) nano wafer is wound, stretched and rearranged to be converted into a single-wall POM nanotube, the nanotube and modified chitosan are combined to form a composite material, and finally, the prepared nano zero-valent iron is assembled into the POM nanotube to prepare the composite medicament. The medicament prepared by the invention realizes the adsorption and reduction of nitrate by utilizing the modified nano zero-valent iron, breaks through the limitation of conventional zero-valent iron for removing nitrate on conditions such as pH and the like, and overcomes the phenomena of passivation, agglomeration and the like generated in the removing process, thereby obtaining more efficient removing efficiency.
Has the following advantages:
(1) the nitrate can be removed efficiently under acidic condition and neutral condition;
(2) POM is used as a medium to accelerate electron transfer, can catalyze the reduction of zero-valent iron on nitrate, improve the reduction performance of the zero-valent iron, and has continuous reduction activity because the protection of the POM single-walled nanotube ensures that the zero-valent iron does not have passivation phenomenon;
(3) the structure of the medicament is special, the stability is good, agglomeration and other phenomena can not occur even based on a nano system, and the medicament stably exists;
(4) the reagent is simple to use and low in dosage, a new reactor and the like are not required to be constructed, the upgrading reconstruction can be realized on the original basis, the nitrate removal process is greatly simplified, and the investment cost is reduced.
Drawings
FIG. 1 is a graph showing the effect of the pharmaceutical product prepared in the example on the treatment of nitrate in sewage.
Detailed Description
The present invention will be further described with reference to the following examples.
The trimethyl ammonium chloride modified chitosan adopted in the invention is purchased from Wuhan La Na white pharmaceutical chemical company Limited, other reagents are commercially available analytical pure reagents, and water adopts deionized water.
Example 1
A preparation method of a water treatment medicament based on a nano system comprises the following steps:
20g of sodium tungstate dihydrate and 10g of disodium hydrogen phosphate are weighed out and dissolved in 100ml of deionized water, 50ml of absolute ethanol is added, 12ml of oleic acid and 3ml of oleylamine are simultaneously added to the mixture, and the mixture is stirred at 200rpm for 10 min. Then the mixture is placed in a reaction kettle and is heated in the absence of oxygen at 150 ℃ for reaction for 1 h. Weigh 1.0g of trimethyl ammonium chloride modified chitosan is added into the mixed solution, and the mixture is stirred and reacted for 3 hours at the intensity of 200rpm to obtain a mixture A. 3.00g of ferrous sulfate was weighed and dispersed in 100ml of absolute ethanol, and mechanically stirred for 5min at a stirring intensity of 500rpm, to obtain a mixture B. And (2) aerating 100ml of deionized water by using nitrogen to perform deoxidation treatment, weighing 1.80g of potassium borohydride, dissolving the potassium borohydride into the deionized water, evenly adding the solution into the mixed solution containing ferrous sulfate for three times, and simultaneously maintaining the temperature at 20 ℃ for ultrasonic treatment for 30min, wherein the adding time points of the solution are 0min, 10min and 20min of ultrasonic reaction, and the ultrasonic intensity is 400W, so as to obtain a mixed solution C. Mixing A and C, and adding 24 wt% of the mixture with a density of 1.12g/cm3And (3) carrying out ultrasonic treatment on 1.75ml of hydrochloric acid for 5min, wherein the ultrasonic intensity is 200W, then putting the mixture into the reaction kettle, carrying out anaerobic heating reaction for 0.5h at the heating temperature of 120 ℃, taking out the mixture, and cooling the mixture to room temperature to obtain the water treatment agent based on the nano system.
Example 2
A preparation method of a water treatment medicament based on a nano system comprises the following steps:
20g of sodium tungstate dihydrate and 10g of disodium hydrogen phosphate are weighed out and dissolved in 150ml of deionized water, and 75ml of absolute ethanol is added, while 18ml of oleic acid and 4.5ml of oleylamine are added to the mixture, and stirred at 250rpm for 10 min. Then the mixture is placed in a reaction kettle and is heated in the absence of oxygen at the temperature of 170 ℃ for reaction for 0.5 h. 2.25g of trimethyl ammonium chloride modified chitosan is weighed into the mixed solution, and stirred and reacted for 3 hours at the intensity of 200rpm to obtain a mixture A. 4.70g of ferrous sulfate was weighed and dispersed in 150ml of absolute ethanol, and mechanically stirred for 5min at a stirring intensity of 600rpm, to obtain a mixture B. And (2) carrying out deoxidation treatment by using nitrogen to aerate 150ml of deionized water, weighing 2.82g of potassium borohydride, dissolving the potassium borohydride into the deionized water, evenly adding the solution into the mixed solution containing ferrous sulfate for three times, and simultaneously maintaining the temperature at 20 ℃ for ultrasonic treatment for 30min, wherein the adding time points of the solution are 0min, 10min and 20min of ultrasonic reaction, and the ultrasonic intensity is 450W, so as to obtain mixed solution C. Mixing A and C, and adding 24 wt% of the mixture with a density of 1.12g/cm32.5ml of hydrochloric acid, carrying out ultrasonic treatment for 5min, placing the mixture into the reaction kettle, carrying out anaerobic heating reaction for 1h, and heating to a temperatureThe temperature is 120 ℃, and the mixture is taken out and cooled to room temperature to obtain the water treatment agent based on the nano system.
Example 3
A preparation method of a water treatment medicament based on a nano system comprises the following steps:
20g of sodium tungstate dihydrate and 10g of disodium hydrogen phosphate are weighed out and dissolved in 200ml of deionized water, 100ml of absolute ethanol is added, and 24ml of oleic acid and 6ml of oleylamine are simultaneously added to the mixture and stirred at 300rpm for 10 min. Then the mixture is placed in a reaction kettle and is heated in the absence of oxygen at 180 ℃ for reaction for 0.5 h. 4.0g of trimethyl ammonium chloride modified chitosan is weighed into the mixed solution, and stirred and reacted for 3 hours at the intensity of 200rpm to obtain a mixture A. 9.00g of ferrous sulfate was weighed and dispersed in 200ml of absolute ethanol, and mechanically stirred for 5min at a stirring intensity of 800rpm, to obtain a mixture B. And (2) carrying out deoxidation treatment by using nitrogen to aerate 200ml of deionized water, weighing 5.40g of potassium borohydride, dissolving the potassium borohydride into the deionized water, evenly adding the solution into the mixed solution containing ferrous sulfate for three times, and simultaneously maintaining the temperature at 25 ℃ for ultrasonic treatment for 30min, wherein the adding time points of the solution are 0min, 10min and 20min of ultrasonic reaction, and the ultrasonic intensity is 500W, so as to obtain mixed solution C. Mixing A and C, and adding 24 wt% of the mixture with a density of 1.12g/cm33.25ml of hydrochloric acid, performing ultrasonic treatment for 5min, placing the mixture into the reaction kettle, performing anaerobic heating reaction for 1h at the heating temperature of 120 ℃, taking out the mixture, and cooling the mixture to room temperature to obtain the water treatment agent based on the nano system.
Example 4 nitrate removal experiments
The experiment was carried out in a beaker, laboratory configured with simulated wastewater with a nitrate concentration of 35mg/L, and nitrate removal experiments were carried out at pH 4 and 7, respectively. The experimental parameter settings are shown in table 1, and the experimental results are shown in fig. 1.
Table 1 experimental parameter settings
As can be seen from FIG. 1, the nitrate in the wastewater is removed quickly after the preparation of the example chemicals, which fully illustrates the rapid adsorption-reduction process of the chemicals for nitrate. The removal rate of nitrate of the medicament of the embodiment under the conditions of pH 4 and pH 7 is obviously higher than that of common nano-iron under the same conditions. Although the removal rate of nitrate of the example medicament is slightly reduced at the pH of 7, the standard of the first class A can be completely met for the effluent concentration, and the standard can not be met by common nano-iron. It is also demonstrated that the agent of the present invention has a good effect of removing nitrate under neutral conditions.
Note that: in this embodiment, the finished product of the above embodiment is not concentrated, and if in actual use, the finished product can be appropriately concentrated, so as to reduce the volume of the added medicament.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. A preparation method of a water treatment medicament based on a nano system is characterized by comprising the following steps:
step (1): weighing sodium tungstate dihydrate and disodium hydrogen phosphate, dissolving in deionized water, adding absolute ethyl alcohol, adding oleic acid and oleylamine, stirring and mixing uniformly to obtain a mixture, and then placing the mixture in a reaction kettle for anaerobic heating reaction to obtain a reaction mixture;
weighing modified chitosan, adding the modified chitosan into the reaction mixture, and stirring for a set time to obtain a mixture A, namely a POM nano wafer mixture;
step (2): weighing ferrous sulfate, dispersing the ferrous sulfate in absolute ethyl alcohol, and mechanically stirring uniformly to obtain a mixture B;
weighing potassium borohydride, dissolving the potassium borohydride into de-oxygenated deionized water to obtain a potassium borohydride solution, and dropwise adding or adding the potassium borohydride solution into the mixture B for a plurality of times within a set time of maintaining a set temperature for ultrasonic treatment reaction to obtain a mixed solution C, namely a nanoscale zero-valent iron mixed solution;
and (3): and mixing the mixture A and the mixed solution C, adding hydrochloric acid to adjust the pH value to 1-3, performing ultrasonic treatment, and placing the mixture in a reaction kettle for anaerobic heating reaction to obtain the water treatment agent based on the nano system.
2. The preparation method of the nano-system based water treatment agent according to claim 1, wherein in the step (1), the mass ratio of the sodium tungstate to the disodium hydrogen phosphate to the deionized water is 2:1 (10 ~ 20);
in the step (1), the mass ratio of the added deionized water to the absolute ethyl alcohol to the added oleic acid to the added oleylamine is 20 (4 ~ 8): (2 ~ 3): 0.5 ~ 1, the stirring speed is 200 ~ 300r/min, and the stirring time is 10 min.
3. The method for preparing water treatment agent based on nano system according to claim 1, wherein in the step (1), the temperature of the anaerobic heating reaction is 150 ~ 180 ℃ and the reaction time is 0.5 ~ 1 h.
4. The method for preparing water treatment agent based on nano system according to claim 1, wherein in the step (1), the modified chitosan is trimethyl ammonium chloride modified chitosan,
the adding amount of the modified chitosan is 0.1 ~ 0.2.2 times of the mass of the disodium hydrogen phosphate, the stirring speed is 200 ~ 300rpm, and the stirring reaction is carried out for 3 ~ 5 hours.
5. The method for preparing water treatment agent based on nano system as claimed in claim 1, wherein in the step (2), the mass volume ratio of ferrous sulfate to absolute ethyl alcohol is (3 ~ 5) g/100ml, and the mechanical stirring speed is 500-800 rpm;
and/or in the step (2), the volume of the de-ionized water subjected to deoxidation treatment is the same as that of the absolute ethyl alcohol, and the deoxidation treatment method is to perform deoxidation treatment on the de-ionized water by using nitrogen aeration;
and/or in the step (2), adding the potassium borohydride solution into the mixture B for three times, wherein the adding time points are 0, 10 and 20min of the ultrasonic treatment reaction;
and/or in the step (2), the temperature of the ultrasonic treatment reaction is 20-25 ℃, the ultrasonic condition is 400-500W, and the treatment time is 30 min.
6. The method for preparing water treatment agent based on nano system according to claim 1, wherein in the step (2), the ratio of the added ferrous sulfate: the mass ratio of the potassium borohydride is 1: 0.6.
7. The method for preparing a nano-system based water treatment agent according to claim 1, wherein in the step (3), the mixing ratio of the mixture A to the mixture C is disodium hydrogen phosphate to ferrous sulfate =1 (0.3 ~ 0.9.9) based on the mass of the added disodium hydrogen phosphate and the mass of the added ferrous sulfate in the mixture C.
8. The method for preparing water treatment agent based on nano system according to claim 1, wherein in the step (3), the concentration of the added hydrochloric acid is 24% by mass and the density is 1.12g/cm3；
And/or in the step (3), the ultrasonic condition is 200-300W, and the treatment time is 5-10 min.
9. The method for preparing water treatment agent based on nano system according to claim 1, wherein in the step (3), the heating temperature of the anaerobic heating reaction is 120 ℃, and the reaction time is 0.5-1 h.
10. A water treatment chemical based on a nano system, which is prepared by the preparation method of the water treatment chemical based on the nano system according to any one of claims 1 to 9.
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