CN116768334B - Abnormal environment pollution treating agent and preparation method thereof - Google Patents
Abnormal environment pollution treating agent and preparation method thereof Download PDFInfo
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- CN116768334B CN116768334B CN202310731840.4A CN202310731840A CN116768334B CN 116768334 B CN116768334 B CN 116768334B CN 202310731840 A CN202310731840 A CN 202310731840A CN 116768334 B CN116768334 B CN 116768334B
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Classifications
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- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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Abstract
The invention provides a special-shaped environment pollution treating agent and a preparation method thereof, and belongs to the technical field of water treatment. And (3) performing magnetic modification on the halloysite nanotube after alkali treatment, adding the halloysite nanotube into a metal ion complexing plant polyphenol solution for composite modification after polydopamine modification on the surface, depositing silver on the surface, adding the silver, peracetic acid and hydrogen peroxide into a gelatin-acacia solution, homogenizing, adjusting the pH value of the solution, adding glutamine transaminase, performing magnet separation, washing and drying to obtain the special-shaped environment pollution treating agent. The special-shaped environment pollution treating agent prepared by the invention has excellent water treatment and disinfection effects, can well reduce COD and BOD, reduce metal ion pollution and the like, has almost no toxicity and easy decomposition of decomposition products, can be separated by magnets, can be repeatedly used, can be slowly released, prolongs the service period, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a special-shaped environment pollution treating agent and a preparation method thereof.
Background
Livestock drinking water sanitation has an important influence on livestock health. However, the problem of livestock drinking is not paid attention to, and a special disinfectant for livestock drinking does not exist in the market, but if livestock drink a germ-containing water body once, gastrointestinal diseases or parasitic diseases of livestock are often caused, and even dead animals are caused seriously.
The most common method of disinfection of drinking water in farms is chemical disinfection, i.e. disinfection using chemical disinfectants. The chemical disinfectant has several advantages, such as strong capability of killing pathogenic microorganisms in water, broad sterilization spectrum, convenient use, low cost, etc. More drinking water disinfectants are used as chlorine preparations in farms for years, and bleaching powder and sodium dichloroisocyanurate are mainly used, so that the disinfection effect is good, and the cost is low. However, the bleaching powder has poor stability, accelerates decomposition in sunlight, heat, humidity and the like, is unfavorable for transportation and storage, and has limited application. The sodium dichloroisocyanurate has stable property and strong sterilization capability, and is relatively suitable for sterilizing drinking water in large-scale farms. Recent years of research show that organic chlorine disinfectants easily react with organic substances in water to generate chlorinated byproducts such as trichloromethane and the like, and most of the byproducts are strong cancerogenic substances, have potential harm to animals or people, and future use of the organic chlorine disinfectants for drinking water disinfection is expected to be limited in the future.
When the conventional disinfectant is used, frequent dosing and monitoring are needed to maintain a good disinfection effect, the dosage is large, the medicine is easy to run off and waste, the disinfectant effect is greatly reduced, the labor and time are wasted, the method is uneconomical, pollution hidden danger can exist, the disinfectant possibly enters a human food chain to endanger human health, the general utilization rate of the conventional disinfectant is only 20% -30%, and the loss rate is as high as 50% -60% in the process of releasing the disinfectant to a target. The disinfectant in the slow release formulation fully plays the efficacy of the disinfectant, and can continuously and stably release the disinfectant according to the required dosage and specific time according to the occurrence rule, the hazard characteristics and the environmental conditions of harmful substances, so as to achieve the aim of controlling harmful microorganisms most economically, safely and effectively.
Chinese patent CN105360162B adopts sodium chloride coating to cover potassium bisulfate disinfectant, thus achieving the composite potassium bisulfate disinfectant which is not easy to absorb moisture and has stable components, and adopts a fluidized bed drying mode to prepare sodium chloride coating. But the coating and other additives have higher content and the potassium hydrogen persulfate content is lower.
The Chinese patent application CN108391673A discloses a preparation method of a nano silver/quaternary ammonium salt composite disinfectant, wherein quaternary ammonium salt in the prepared composite disinfectant exists in a cationic form in an aqueous solution, has strong affinity adsorption force on the surfaces of all bacteria and viruses and can destroy tissue cells of the bacteria and viruses, but the quaternary ammonium salt used by the composite disinfectant is small molecules, is easy to volatilize and cannot permanently maintain the sterilizing effect.
Also disclosed in chinese patent CN102387703B is a disinfectant composition comprising a biguanide compound, the biocidal composition comprising one or more biguanide polymers, one or more additional active agents selected from the group consisting of mono-quaternary ammonium salts, and one or more additional active agents selected from the group consisting of one or more isothiazolone compounds, which are currently being limited in use by europe and are at risk of allergy, for disinfecting fabrics in contact with the skin, are bacteriostatic preservatives, are not suitable for rapid disinfection, and have an undesirable killing effect on viruses.
Chinese patent CN106146835B discloses a preparation method and application of a high molecular quaternary ammonium salt antibacterial agent, which is characterized in that polyethylenimine is quaternized with short-chain halohydrocarbon (e.g. bromohexane and methyl iodide), but the short-chain quaternized polyethylenimine has poor inactivation effect on viruses (influenza virus, human coronavirus) containing lipophilic envelope.
Disclosure of Invention
The invention aims to provide a special-shaped environment pollution treating agent and a preparation method thereof, which have excellent water treatment and disinfection effects, can well reduce COD and BOD, reduce metal ion pollution and the like, have the advantages of almost no toxicity, easy decomposition of decomposition products, magnet separation, repeated use, slow release, prolonged service cycle and wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a special-shaped environment pollution treatment agent, which comprises the steps of carrying out alkali treatment on halloysite nanotubes, carrying out magnetic modification, carrying out polydopamine modification on the surfaces, adding metal ion complexing plant polyphenol solution to carry out compound modification, then depositing silver on the surfaces, adding the silver, peracetic acid and hydrogen peroxide into gelatin-acacia solution, homogenizing, regulating the pH value of the solution, adding glutamine transaminase, carrying out magnet separation, washing and drying to obtain the special-shaped environment pollution treatment agent.
As a further improvement of the invention, the method comprises the following steps:
s1, preprocessing halloysite nanotubes: immersing halloysite nanotubes in alkali liquor for treatment, filtering, washing and drying to obtain pretreated halloysite nanotubes;
s2, magnetic modification: dissolving ferric chloride and ferrous chloride in water, adding the pretreated halloysite nanotube prepared in the step S1 into water under the protection of inert gas, dropwise adding ammonia water, stirring for reaction, separating by a magnet, washing, and drying to obtain a magnetic halloysite nanotube;
s3, modifying polydopamine: adding the magnetic halloysite nanotube prepared in the step S2 into water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, separating a magnet, washing, and drying to prepare the polydopamine modified magnetic halloysite nanotube;
S4, complexing plant polyphenol with metal ions: dissolving metal salt in water, adding plant polyphenol, stirring and mixing to obtain metal ion complex plant polyphenol solution;
s5, composite modification: adding the polydopamine modified magnetic halloysite nanotube prepared in the step S3 into the metal ion complexing plant polyphenol solution prepared in the step S4, heating and stirring for reaction, separating by a magnet, washing and drying to prepare the modified magnetic halloysite nanotube;
s6, silver deposition: adding the modified magnetic halloysite nanotube prepared in the step S5 into an aqueous solution containing glucose, dropwise adding a silver ammino ion solution, heating and stirring for reaction, separating by a magnet, washing and drying to prepare a silver deposition modified magnetic halloysite nanotube;
s7, preparing a special-shaped environment pollution treating agent: dissolving gelatin and acacia in water to obtain gelatin-acacia solution, adding the silver deposition modified magnetic halloysite nanotube, peracetic acid and hydrogen peroxide solution prepared in the step S6 for homogenization, regulating the pH value of the solution to be a first pH value, stirring for reaction, regulating the pH value to be a second pH value, adding glutamine transaminase, stirring for reaction, separating by a magnet, washing and drying to obtain the special-shaped environment pollution treating agent.
As a further improvement of the invention, the solid-to-liquid ratio of the halloysite nanotubes to the alkali liquor in the step S1 is 1:5-10g/mL, and the alkali liquor is 7-12wt% of NaOH or KOH solution.
As a further improvement of the present invention, the inert gas in step S2 is at least one selected from nitrogen, argon, helium, neon; the molar ratio of the ferric chloride to the ferrous chloride is 2:1; the mass ratio of the ferric chloride to the pretreated halloysite nanotube to the ammonia water is 5-7:20-25:3-5; the concentration of the ammonia water is 22-25wt%.
As a further improvement of the present invention, the mass ratio of the magnetic halloysite nanotube, dopamine hydrochloride and catalyst in step S3 is 10:12-15:1-2; the catalyst contains 3-5wt% of CoCl 2 Tris-HCl solution at ph=5-6; the temperature of the heating and stirring reaction is 40-45 ℃ and the time is 2-3h.
As a further improvement of the present invention, the metal salt in step S4 is at least one selected from copper chloride, zinc chloride, copper sulfate, zinc sulfate, manganese chloride, manganese sulfate, calcium chloride, calcium sulfate, cobalt chloride, cobalt sulfate, ferric chloride, aluminum sulfate, lead chloride, and lead sulfate, preferably a mixture of copper chloride and zinc chloride, in a mass ratio of 3-5:7; the plant polyphenol is at least one selected from tea polyphenol, apple polyphenol and grape polyphenol, preferably is a mixture of tea polyphenol and apple polyphenol, and the mass ratio is 7-10:3; the mass ratio of the metal salt to the water to the plant polyphenol is 2-3:100:15-20.
As a further improvement of the invention, the mass ratio of the polydopamine modified magnetic halloysite nanotube to the metal ion complexing plant polyphenol solution in the step S5 is 12-15:100; the temperature of the heating and stirring reaction is 35-45 ℃ and the time is 30-50min.
As a further improvement of the present invention, the preparation method of the silver ammine ion solution in step S6 is as follows: dropwise adding 22-25wt% ammonia water into 1-2mol/L silver nitrate solution until the precipitate just disappears, so as to obtain silver ammino ion solution; the content of glucose in the aqueous solution containing glucose is 12-20wt%; the mass ratio of the modified magnetic halloysite nanotube to the aqueous solution containing glucose to the silver ammino ion solution is 10:30-50:20-25; the temperature of the heating and stirring reaction is 90-100 ℃ and the time is 20-30min.
As a further improvement of the present invention, the concentration of gelatin in the gelatin-acacia solution in step S7 is 12-20wt% and the concentration of acacia is 15-17wt%; the mass ratio of the gelatin-Arabic gum solution to the silver deposition modified magnetic halloysite nanotube to the peroxyacetic acid to the hydrogen peroxide to the glutamine transaminase is 100:12-15:4-7:7-10:3-5; the homogenizing condition is 12000-15000r/min for 5-10min; the first pH value is 4.1-4.3, and the second pH value is 6.1-6.3.
The invention further protects the special-shaped environment pollution treating agent prepared by the preparation method.
The invention has the following beneficial effects:
halloysite nanotubes are a natural aluminosilicate [ Al ] 2 Si 2 O 5 (OH) 4 ·nH 2 O]The nano tube is generally in a hollow nano tube structure, the outer wall of the nano tube is a Si-O-Si group, a large number of Al-OH groups are contained in the tube cavity, and Si-OH and Al-OH groups exist at the edge of the nano tube, so that the nano tube has the characteristics of wide distribution, abundant reserves, good biocompatibility, acid and alkali corrosion resistance and the like. The invention adopts alkali liquor to pretreat the halloysite nanotube so as to lead the halloysite nanotube to beA large number of active groups such as hydroxyl groups are formed on the surface of the rice tube, so that the subsequent in-situ deposition of magnetic ferroferric oxide is facilitated.
According to the method, ferroferric oxide serving as a ferromagnetic substance is generated by ferrous chloride and ferric chloride under the catalysis of ammonia water, so that the silver deposition modified magnetic halloysite nanotube in the prepared special-shaped environment pollution treatment agent has magnetism, and is convenient for magnet separation, and the silver deposition modified magnetic halloysite nanotube in the special-shaped environment pollution treatment agent can be recycled.
And then a polydopamine layer is deposited on the surface of the magnetic halloysite nanotube, wherein polydopamine has a mussel protein-like structure and super-strong adhesion and can almost form covalent or non-covalent interaction with any substrate. Meanwhile, the modified polyurethane has rich hydrophilic functional groups such as catechol, amino and the like, and can effectively enhance the hydrophilicity of the surface of a substrate. Therefore, after the polydopamine layer is deposited on the surface layer, the polydopamine layer is beneficial to the subsequent hydrogen bond linkage with the metal ion complex plant polyphenol complex and glucose, so that the metal ion complex plant polyphenol complex and glucose are stably fixed, and the glucose is fixed, so that silver ammino ions can be deposited in situ, and the silver deposition modified magnetic halloysite nanotube is prepared.
The plant polyphenol is a complex secondary metabolite in plants, the source is green and environment-friendly, the tea polyphenol consists of catechins, anthocyanidins, phenolic acids and depsipelas, is a broad-spectrum antibacterial agent, and has obvious inhibition effect on pathogenic bacteria such as coliform bacteria and pseudomonas in water. The tea polyphenol and apple polyphenol have a plurality of reactive groups and active sites in the molecular structure, and can generate various chemical reactions such as phenols, alcohols, acids and the like. The antioxidant has strong oxidation-reduction effect, and the special conjugated structure provides conditions for antioxidation, so the antioxidant can be used as an antioxidant. Tea polyphenols and apple polyphenols are highly sensitive to metal ions, and the phenolic hydroxyl groups in their structures can be bound to most metal ions (e.g. Ca 2+ 、Pb 2+ 、Zn 2+ 、Fe 3+ 、Al 3+ Etc.) undergo a complexation reaction.
Cu 2+ P-tea polyphenol complexThe combined modification can improve the antibacterial property of tea polyphenol, can influence the bacterial metabolic process by acting on bacterial genetic material, and simultaneously, the combination with cellular enzyme protein can reduce the enzyme activity, and the combination with membrane protein can influence the absorption of bacteria on nutrient substances. Zn (zinc) 2+ The complex formed by the complex and the tea polyphenol can cause structural change of the tea polyphenol, enhance the antioxidant capacity and antibacterial capacity of the tea polyphenol, and destroy the cell wall membrane structure by changing the normal form of bacteria, thereby playing a role in good antibacterial performance. Thus, cu is 2+ /Zn 2+ The complex modified plant polyphenol complex has good disinfection enhancement effect, and the combination of the complex modified plant polyphenol complex and the plant polyphenol has synergistic effect.
The invention also adds hydrogen peroxide, which can form a compound with a small amount of silver ions ionized by the silver deposition modified magnetic halloysite nanotube, overcomes the unstable characteristic of hydrogen peroxide, improves the disinfection capability of hydrogen peroxide, has strong and long-acting disinfection effect, has a killing effect on various bacteria such as escherichia coli, pseudomonas aeruginosa, staphylococcus aureus and the like, can completely decompose the compound, has no pollution to water and environment, can indirectly reflect the degree of organic pollution to water by oxygen consumption, and is a comprehensive index for evaluating the total organic pollution amount of the water.
The peracetic acid can realize sterilization through nascent oxygen, denature and coagulate bacterial proteins, damage active genes of enzyme proteins through oxidation-reduction reaction, inhibit the activity of enzymes, or inhibit the activity of enzymes by combining with enzymes in a competition or non-competition way due to the similarity of chemical structures and metabolic products. The byproducts are mainly carboxylic acid substances, and the byproducts are nontoxic and have low possibility of generating toxic substances through subsequent reaction in drinking water, so that the application of the peracetic acid is good, the toxicity is low, and the peracetic acid can be applied to the disinfection of drinking water of livestock.
According to the invention, two linear irregular polymer materials with opposite charges are added into the solution to serve as wall materials (gelatin is positively charged and Arabic gum is negatively charged), core materials (silver deposition modified magnetic halloysite nanotubes, peracetic acid and hydrogen peroxide solution) are dispersed in the wall material water solution, the pH of the system is changed to enable electrostatic interaction between polymer materials with opposite charges to be mutually attracted, the solubility is reduced, phase separation is generated, colloid is condensed from the solution, and a slow-release microcapsule structure is prepared, so that the special-shaped environment pollution treating agent prepared by the invention has a slow-release effect, can be separated by a magnet and reused on one hand, and can be slowly released on the other hand, and the service period is prolonged.
The special-shaped environment pollution treating agent prepared by the invention has excellent water treatment and disinfection effects, can well reduce COD and BOD, reduce metal ion pollution and the like, has almost no toxicity and easy decomposition of decomposition products, can be separated by magnets, can be repeatedly used, can be slowly released, prolongs the service period, and has wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is an SEM image of a special-shaped environmental pollution treatment agent of example 1 of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The halloysite nanotubes have a diameter of 50-300nm and a length of 1-10 μm and are available from Yuan Xin nanotechnology Co.
Example 1
The embodiment provides a preparation method of a special-shaped environment pollution treatment agent, which comprises the following steps:
s1, preprocessing halloysite nanotubes: immersing halloysite nanotubes in a 7wt% NaOH solution for treatment, wherein the solid-to-liquid ratio of the halloysite nanotubes to the 7wt% NaOH solution is 1:5g/mL, filtering, washing and drying to obtain pretreated halloysite nanotubes;
s2, magnetic modification: dissolving 5 parts by weight of ferric chloride and ferrous chloride in 100 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 20 parts by weight of the pretreated halloysite nanotube prepared in the step S1 into the water solution under the protection of nitrogen, dropwise adding 3 parts by weight of 22wt% ammonia water, stirring for reaction, separating by a magnet, washing and drying to obtain the magnetic halloysite nanotube;
S3, modifying polydopamine: adding 10 parts by weight of the magnetic halloysite nanotube prepared in the step S2 into 100 parts by weight of water, adding 12 parts by weight of dopamine hydrochloride and 1 part by weight of catalyst, heating to 40 ℃, stirring and reacting for 2 hours, separating by a magnet, washing and drying to prepare the polydopamine modified magnetic halloysite nanotube;
the catalyst was a catalyst containing 3wt% of CoCl 2 Tris-HCl solution at ph=5;
s4, complexing plant polyphenol with metal ions: dissolving 2 parts by weight of metal salt in 100 parts by weight of water, adding 15 parts by weight of plant polyphenol, and stirring and mixing for 20min to obtain a metal ion complexing plant polyphenol solution;
the metal salt is a mixture of copper chloride and zinc chloride, and the mass ratio is 3:7;
the plant polyphenol is a mixture of tea polyphenol and apple polyphenol, and the mass ratio is 7:3;
s5, composite modification: adding 12 parts by weight of the polydopamine modified magnetic halloysite nanotube prepared in the step S3 into 100 parts by weight of the metal ion complexing plant polyphenol solution prepared in the step S4, heating to 35 ℃, stirring and reacting for 30min, separating by a magnet, washing and drying to prepare the modified magnetic halloysite nanotube;
s6, silver deposition: adding 10 parts by weight of the modified magnetic halloysite nanotube prepared in the step S5 into 30 parts by weight of an aqueous solution containing 12wt% of glucose, dropwise adding 20 parts by weight of a silver ammino ion solution, heating to 90 ℃, stirring and reacting for 20min, separating by a magnet, washing, and drying to prepare a silver deposition modified magnetic halloysite nanotube;
The preparation method of the silver ammine ion solution comprises the following steps: dropwise adding 22wt% ammonia water into 1mol/L silver nitrate solution until the precipitate just disappears, so as to prepare a silver ammine ion solution;
s7, preparing a special-shaped environment pollution treating agent: dissolving gelatin and acacia in water to obtain gelatin-acacia solution, wherein the concentration of gelatin is 12wt% and the concentration of acacia is 15wt%, adding 12 parts by weight of silver deposition modified magnetic halloysite nanotube prepared in the step S6, 4 parts by weight of peracetic acid and 7 parts by weight of hydrogen peroxide solution into 100 parts by weight of gelatin-acacia solution, homogenizing for 5min at 12000r/min, regulating the pH value of the solution to be 4.1, stirring for 20min, regulating the pH value to be 6.1, adding 3 parts by weight of glutamine transaminase, stirring for 30min, separating by a magnet, washing and drying to obtain the special-shaped environment pollution treating agent, and obtaining an SEM image of the special-shaped environment pollution treating agent in the figure 1.
Example 2
The embodiment provides a preparation method of a special-shaped environment pollution treatment agent, which comprises the following steps:
s1, preprocessing halloysite nanotubes: immersing halloysite nanotubes in a 12wt% KOH solution for treatment, wherein the solid-to-liquid ratio of the halloysite nanotubes to the 12wt% KOH solution is 1:10g/mL, filtering, washing and drying to obtain pretreated halloysite nanotubes;
S2, magnetic modification: dissolving 7 parts by weight of ferric chloride and ferrous chloride in 100 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 25 parts by weight of the pretreated halloysite nanotube prepared in the step S1 into the aqueous solution under the protection of argon, dropwise adding 5 parts by weight of 25wt% ammonia water, stirring for reaction, separating by a magnet, washing and drying to obtain the magnetic halloysite nanotube;
s3, modifying polydopamine: adding 10 parts by weight of the magnetic halloysite nanotube prepared in the step S2 into 100 parts by weight of water, adding 15 parts by weight of dopamine hydrochloride and 2 parts by weight of catalyst, heating to 45 ℃, stirring and reacting for 3 hours, separating by a magnet, washing and drying to prepare the polydopamine modified magnetic halloysite nanotube;
the catalyst was a catalyst containing 5wt% of CoCl 2 Tris-HCl solution at ph=6;
s4, complexing plant polyphenol with metal ions: dissolving 3 parts by weight of metal salt in 100 parts by weight of water, adding 20 parts by weight of plant polyphenol, and stirring and mixing for 20min to obtain a metal ion complexing plant polyphenol solution;
the metal salt is a mixture of copper chloride and zinc chloride, and the mass ratio is 5:7;
the plant polyphenol is a mixture of tea polyphenol and apple polyphenol, and the mass ratio is 10:3;
S5, composite modification: adding 15 parts by weight of the polydopamine modified magnetic halloysite nanotube prepared in the step S3 into 100 parts by weight of the metal ion complexing plant polyphenol solution prepared in the step S4, heating to 45 ℃, stirring and reacting for 50min, separating by a magnet, washing and drying to prepare the modified magnetic halloysite nanotube;
s6, silver deposition: adding 10 parts by weight of the modified magnetic halloysite nanotube prepared in the step S5 into 50 parts by weight of an aqueous solution containing 20wt% of glucose, dropwise adding 25 parts by weight of a silver ammino ion solution, heating to 100 ℃, stirring and reacting for 30min, separating by a magnet, washing, and drying to prepare a silver deposition modified magnetic halloysite nanotube;
the preparation method of the silver ammine ion solution comprises the following steps: dropwise adding 25wt% ammonia water into 2mol/L silver nitrate solution until the precipitate just disappears, so as to prepare silver ammine complex ion solution;
s7, preparing a special-shaped environment pollution treating agent: and (3) dissolving gelatin and acacia in water to obtain gelatin-acacia solution, wherein the concentration of gelatin is 20wt% and the concentration of acacia is 17wt%, adding 15 parts by weight of silver deposition modified magnetic halloysite nanotube prepared in the step (S6), 7 parts by weight of peracetic acid and 10 parts by weight of hydrogen peroxide solution into 100 parts by weight of gelatin-acacia solution, homogenizing for 10min at 15000r/min, regulating the pH value of the solution to 4.3, stirring and reacting for 20min, regulating the pH value to 6.3, adding 5 parts by weight of glutamine transaminase, stirring and reacting for 30min, separating by using a magnet, washing and drying to obtain the special-shaped environment pollution treating agent.
Example 3
The embodiment provides a preparation method of a special-shaped environment pollution treatment agent, which comprises the following steps:
s1, preprocessing halloysite nanotubes: immersing halloysite nanotubes in a 10wt% NaOH solution for treatment, wherein the solid-to-liquid ratio of the halloysite nanotubes to the 10wt% NaOH solution is 1:7g/mL, filtering, washing and drying to obtain pretreated halloysite nanotubes;
s2, magnetic modification: dissolving 6 parts by weight of ferric chloride and ferrous chloride in 100 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 22 parts by weight of the pretreated halloysite nanotube prepared in the step S1 into the water solution under the protection of nitrogen, dropwise adding 4 parts by weight of 23.5wt% ammonia water, stirring for reaction, separating by a magnet, washing and drying to obtain the magnetic halloysite nanotube;
s3, modifying polydopamine: adding 10 parts by weight of the magnetic halloysite nanotube prepared in the step S2 into 100 parts by weight of water, adding 13.5 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 42 ℃, stirring and reacting for 2.5 hours, separating by a magnet, washing, and drying to prepare the polydopamine modified magnetic halloysite nanotube;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s4, complexing plant polyphenol with metal ions: dissolving 2.5 parts by weight of metal salt in 100 parts by weight of water, adding 17 parts by weight of plant polyphenol, and stirring and mixing for 20min to obtain a metal ion complexing plant polyphenol solution;
the metal salt is a mixture of copper chloride and zinc chloride, and the mass ratio is 4:7;
the plant polyphenol is a mixture of tea polyphenol and apple polyphenol, and the mass ratio is 8.5:3;
s5, composite modification: adding 13.55 parts by weight of the polydopamine modified magnetic halloysite nanotube prepared in the step S3 into 100 parts by weight of the metal ion complexing plant polyphenol solution prepared in the step S4, heating to 40 ℃, stirring and reacting for 40min, separating by a magnet, washing and drying to prepare the modified magnetic halloysite nanotube;
s6, silver deposition: adding 10 parts by weight of the modified magnetic halloysite nanotube prepared in the step S5 into 40 parts by weight of an aqueous solution containing 16wt% of glucose, dropwise adding 22 parts by weight of a silver ammino ion solution, heating to 95 ℃, stirring and reacting for 25min, separating by a magnet, washing, and drying to prepare a silver deposition modified magnetic halloysite nanotube;
the preparation method of the silver ammine ion solution comprises the following steps: dropwise adding 23.5wt% ammonia water into 1.5mol/L silver nitrate solution until the precipitate just disappears, so as to prepare silver ammino ion solution;
S7, preparing a special-shaped environment pollution treating agent: and (3) dissolving gelatin and acacia in water to obtain gelatin-acacia solution, wherein the concentration of gelatin is 16wt%, the concentration of acacia is 16wt%, 13.5 parts by weight of silver deposition modified magnetic halloysite nano tube prepared in the step (S6), 5 parts by weight of peracetic acid and 8.5 parts by weight of hydrogen peroxide solution are added into 100 parts by weight of gelatin-acacia solution, homogenizing for 7min at 13500r/min, regulating the pH value of the solution to 4.2, stirring and reacting for 20min, regulating the pH value to 6.2, adding 4 parts by weight of glutamine transaminase, stirring and reacting for 30min, separating by using a magnet, washing and drying to obtain the special-shaped environment pollution treating agent.
Example 4
The difference compared to example 3 is that the metal salt is a single copper chloride.
Example 5
The difference compared to example 3 is that the metal salt is a single zinc chloride.
Example 6
The difference compared to example 3 is that the plant polyphenol is a single tea polyphenol.
Example 7
The difference compared to example 3 is that the plant polyphenol is a single apple polyphenol.
Comparative example 1
In comparison with example 3, the difference is that step S1 is not performed.
The method comprises the following steps:
S1, magnetic modification: dissolving 6 parts by weight of ferric chloride and ferrous chloride in 100 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 22 parts by weight of halloysite nanotubes into the water solution under the protection of nitrogen, dropwise adding 4 parts by weight of 23.5wt% ammonia water, stirring for reaction, separating by a magnet, washing and drying to obtain the magnetic halloysite nanotubes;
s2, modifying polydopamine: adding 10 parts by weight of the magnetic halloysite nanotube prepared in the step S1 into 100 parts by weight of water, adding 13.5 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 42 ℃, stirring and reacting for 2.5 hours, separating by a magnet, washing, and drying to prepare the polydopamine modified magnetic halloysite nanotube;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s3, complexing plant polyphenol with metal ions: dissolving 2.5 parts by weight of metal salt in 100 parts by weight of water, adding 17 parts by weight of plant polyphenol, and stirring and mixing for 20min to obtain a metal ion complexing plant polyphenol solution;
the metal salt is a mixture of copper chloride and zinc chloride, and the mass ratio is 4:7;
the plant polyphenol is a mixture of tea polyphenol and apple polyphenol, and the mass ratio is 8.5:3;
S4, composite modification: adding 13.55 parts by weight of the polydopamine modified magnetic halloysite nanotube prepared in the step S2 into 100 parts by weight of the metal ion complexing plant polyphenol solution prepared in the step S3, heating to 40 ℃, stirring and reacting for 40min, separating by a magnet, washing and drying to prepare the modified magnetic halloysite nanotube;
s5, silver deposition: adding 10 parts by weight of the modified magnetic halloysite nanotube prepared in the step S4 into 40 parts by weight of an aqueous solution containing 16wt% of glucose, dropwise adding 22 parts by weight of a silver ammino ion solution, heating to 95 ℃, stirring and reacting for 25min, separating by a magnet, washing, and drying to prepare a silver deposition modified magnetic halloysite nanotube;
the preparation method of the silver ammine ion solution comprises the following steps: dropwise adding 23.5wt% ammonia water into 1.5mol/L silver nitrate solution until the precipitate just disappears, so as to prepare silver ammino ion solution;
s6, preparing a special-shaped environment pollution treating agent: and (2) dissolving gelatin and acacia in water to obtain gelatin-acacia solution, wherein the concentration of gelatin is 16wt%, the concentration of acacia is 16wt%, 13.5 parts by weight of silver deposition modified magnetic halloysite nano tube prepared in the step (S5), 5 parts by weight of peracetic acid and 8.5 parts by weight of hydrogen peroxide solution are added into 100 parts by weight of gelatin-acacia solution, homogenizing for 7min at 13500r/min, regulating the pH value of the solution to 4.2, stirring and reacting for 20min, regulating the pH value to 6.2, adding 4 parts by weight of glutamine transaminase, stirring and reacting for 30min, separating by using a magnet, washing and drying to obtain the special-shaped environment pollution treating agent.
Comparative example 2
In comparison with example 3, the difference is that step S3 is not performed.
The method comprises the following steps:
s1, preprocessing halloysite nanotubes: immersing halloysite nanotubes in a 10wt% NaOH solution for treatment, wherein the solid-to-liquid ratio of the halloysite nanotubes to the 10wt% NaOH solution is 1:7g/mL, filtering, washing and drying to obtain pretreated halloysite nanotubes;
s2, magnetic modification: dissolving 6 parts by weight of ferric chloride and ferrous chloride in 100 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 22 parts by weight of the pretreated halloysite nanotube prepared in the step S1 into the water solution under the protection of nitrogen, dropwise adding 4 parts by weight of 23.5wt% ammonia water, stirring for reaction, separating by a magnet, washing and drying to obtain the magnetic halloysite nanotube;
s3, complexing plant polyphenol with metal ions: dissolving 2.5 parts by weight of metal salt in 100 parts by weight of water, adding 17 parts by weight of plant polyphenol, and stirring and mixing for 20min to obtain a metal ion complexing plant polyphenol solution;
the metal salt is a mixture of copper chloride and zinc chloride, and the mass ratio is 4:7;
the plant polyphenol is a mixture of tea polyphenol and apple polyphenol, and the mass ratio is 8.5:3;
S4, composite modification: adding 13.55 parts by weight of the magnetic halloysite nanotube prepared in the step S2 into 100 parts by weight of the metal ion complexing plant polyphenol solution prepared in the step S4, heating to 40 ℃, stirring and reacting for 40min, separating by a magnet, washing and drying to prepare the modified magnetic halloysite nanotube;
s5, silver deposition: adding 10 parts by weight of the modified magnetic halloysite nanotube prepared in the step S4 into 40 parts by weight of an aqueous solution containing 16wt% of glucose, dropwise adding 22 parts by weight of a silver ammino ion solution, heating to 95 ℃, stirring and reacting for 25min, separating by a magnet, washing, and drying to prepare a silver deposition modified magnetic halloysite nanotube;
the preparation method of the silver ammine ion solution comprises the following steps: dropwise adding 23.5wt% ammonia water into 1.5mol/L silver nitrate solution until the precipitate just disappears, so as to prepare silver ammino ion solution;
s6, preparing a special-shaped environment pollution treating agent: and (2) dissolving gelatin and acacia in water to obtain gelatin-acacia solution, wherein the concentration of gelatin is 16wt%, the concentration of acacia is 16wt%, 13.5 parts by weight of silver deposition modified magnetic halloysite nano tube prepared in the step (S5), 5 parts by weight of peracetic acid and 8.5 parts by weight of hydrogen peroxide solution are added into 100 parts by weight of gelatin-acacia solution, homogenizing for 7min at 13500r/min, regulating the pH value of the solution to 4.2, stirring and reacting for 20min, regulating the pH value to 6.2, adding 4 parts by weight of glutamine transaminase, stirring and reacting for 30min, separating by using a magnet, washing and drying to obtain the special-shaped environment pollution treating agent.
Comparative example 3
The difference from example 3 is that no metal salt is added in step S4.
The method comprises the following steps:
s1, preprocessing halloysite nanotubes: immersing halloysite nanotubes in a 10wt% NaOH solution for treatment, wherein the solid-to-liquid ratio of the halloysite nanotubes to the 10wt% NaOH solution is 1:7g/mL, filtering, washing and drying to obtain pretreated halloysite nanotubes;
s2, magnetic modification: dissolving 6 parts by weight of ferric chloride and ferrous chloride in 100 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 22 parts by weight of the pretreated halloysite nanotube prepared in the step S1 into the water solution under the protection of nitrogen, dropwise adding 4 parts by weight of 23.5wt% ammonia water, stirring for reaction, separating by a magnet, washing and drying to obtain the magnetic halloysite nanotube;
s3, modifying polydopamine: adding 10 parts by weight of the magnetic halloysite nanotube prepared in the step S2 into 100 parts by weight of water, adding 13.5 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 42 ℃, stirring and reacting for 2.5 hours, separating by a magnet, washing, and drying to prepare the polydopamine modified magnetic halloysite nanotube;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s4, preparing a plant polyphenol solution: adding 19.5 parts by weight of plant polyphenol into 100 parts by weight of water, and stirring and mixing for 20min to obtain a plant polyphenol solution;
the plant polyphenol is a mixture of tea polyphenol and apple polyphenol, and the mass ratio is 8.5:3;
s5, composite modification: adding 13.55 parts by weight of the polydopamine modified magnetic halloysite nanotube prepared in the step S3 into 100 parts by weight of the plant polyphenol solution prepared in the step S4, heating to 40 ℃, stirring and reacting for 40min, separating by a magnet, washing and drying to prepare the modified magnetic halloysite nanotube;
s6, silver deposition: adding 10 parts by weight of the modified magnetic halloysite nanotube prepared in the step S5 into 40 parts by weight of an aqueous solution containing 16wt% of glucose, dropwise adding 22 parts by weight of a silver ammino ion solution, heating to 95 ℃, stirring and reacting for 25min, separating by a magnet, washing, and drying to prepare a silver deposition modified magnetic halloysite nanotube;
the preparation method of the silver ammine ion solution comprises the following steps: dropwise adding 23.5wt% ammonia water into 1.5mol/L silver nitrate solution until the precipitate just disappears, so as to prepare silver ammino ion solution;
s7, preparing a special-shaped environment pollution treating agent: and (3) dissolving gelatin and acacia in water to obtain gelatin-acacia solution, wherein the concentration of gelatin is 16wt%, the concentration of acacia is 16wt%, 13.5 parts by weight of silver deposition modified magnetic halloysite nano tube prepared in the step (S6), 5 parts by weight of peracetic acid and 8.5 parts by weight of hydrogen peroxide solution are added into 100 parts by weight of gelatin-acacia solution, homogenizing for 7min at 13500r/min, regulating the pH value of the solution to 4.2, stirring and reacting for 20min, regulating the pH value to 6.2, adding 4 parts by weight of glutamine transaminase, stirring and reacting for 30min, separating by using a magnet, washing and drying to obtain the special-shaped environment pollution treating agent.
Comparative example 4
In comparison with example 3, the difference is that no plant polyphenol is added in step S4.
The method comprises the following steps:
s1, preprocessing halloysite nanotubes: immersing halloysite nanotubes in a 10wt% NaOH solution for treatment, wherein the solid-to-liquid ratio of the halloysite nanotubes to the 10wt% NaOH solution is 1:7g/mL, filtering, washing and drying to obtain pretreated halloysite nanotubes;
s2, magnetic modification: dissolving 6 parts by weight of ferric chloride and ferrous chloride in 100 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 22 parts by weight of the pretreated halloysite nanotube prepared in the step S1 into the water solution under the protection of nitrogen, dropwise adding 4 parts by weight of 23.5wt% ammonia water, stirring for reaction, separating by a magnet, washing and drying to obtain the magnetic halloysite nanotube;
s3, modifying polydopamine: adding 10 parts by weight of the magnetic halloysite nanotube prepared in the step S2 into 100 parts by weight of water, adding 13.5 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 42 ℃, stirring and reacting for 2.5 hours, separating by a magnet, washing, and drying to prepare the polydopamine modified magnetic halloysite nanotube;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s4, preparing a metal ion solution: dissolving 19.5 parts by weight of metal salt in 100 parts by weight of water, stirring and mixing for 20min to obtain a metal ion solution;
the metal salt is a mixture of copper chloride and zinc chloride, and the mass ratio is 4:7;
s5, composite modification: adding 13.55 parts by weight of the polydopamine modified magnetic halloysite nanotube prepared in the step S3 into 100 parts by weight of the metal ion solution prepared in the step S4, heating to 40 ℃, stirring and reacting for 40min, separating by a magnet, washing, and drying to prepare the modified magnetic halloysite nanotube;
s6, silver deposition: adding 10 parts by weight of the modified magnetic halloysite nanotube prepared in the step S5 into 40 parts by weight of an aqueous solution containing 16wt% of glucose, dropwise adding 22 parts by weight of a silver ammino ion solution, heating to 95 ℃, stirring and reacting for 25min, separating by a magnet, washing, and drying to prepare a silver deposition modified magnetic halloysite nanotube;
the preparation method of the silver ammine ion solution comprises the following steps: dropwise adding 23.5wt% ammonia water into 1.5mol/L silver nitrate solution until the precipitate just disappears, so as to prepare silver ammino ion solution;
s7, preparing a special-shaped environment pollution treating agent: and (3) dissolving gelatin and acacia in water to obtain gelatin-acacia solution, wherein the concentration of gelatin is 16wt%, the concentration of acacia is 16wt%, 13.5 parts by weight of silver deposition modified magnetic halloysite nano tube prepared in the step (S6), 5 parts by weight of peracetic acid and 8.5 parts by weight of hydrogen peroxide solution are added into 100 parts by weight of gelatin-acacia solution, homogenizing for 7min at 13500r/min, regulating the pH value of the solution to 4.2, stirring and reacting for 20min, regulating the pH value to 6.2, adding 4 parts by weight of glutamine transaminase, stirring and reacting for 30min, separating by using a magnet, washing and drying to obtain the special-shaped environment pollution treating agent.
Comparative example 5
The difference from example 3 is that steps S4 and S5 are not performed.
The method comprises the following steps:
s1, preprocessing halloysite nanotubes: immersing halloysite nanotubes in a 10wt% NaOH solution for treatment, wherein the solid-to-liquid ratio of the halloysite nanotubes to the 10wt% NaOH solution is 1:7g/mL, filtering, washing and drying to obtain pretreated halloysite nanotubes;
s2, magnetic modification: dissolving 6 parts by weight of ferric chloride and ferrous chloride in 100 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 22 parts by weight of the pretreated halloysite nanotube prepared in the step S1 into the water solution under the protection of nitrogen, dropwise adding 4 parts by weight of 23.5wt% ammonia water, stirring for reaction, separating by a magnet, washing and drying to obtain the magnetic halloysite nanotube;
s3, modifying polydopamine: adding 10 parts by weight of the magnetic halloysite nanotube prepared in the step S2 into 100 parts by weight of water, adding 13.5 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 42 ℃, stirring and reacting for 2.5 hours, separating by a magnet, washing, and drying to prepare the polydopamine modified magnetic halloysite nanotube;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s4, silver deposition: adding 10 parts by weight of the polydopamine modified magnetic halloysite nanotube prepared in the step S3 into 40 parts by weight of an aqueous solution containing 16wt% of glucose, dropwise adding 22 parts by weight of a silver ammino ion solution, heating to 95 ℃, stirring and reacting for 25min, separating magnets, washing and drying to prepare a silver deposition modified magnetic halloysite nanotube;
the preparation method of the silver ammine ion solution comprises the following steps: dropwise adding 23.5wt% ammonia water into 1.5mol/L silver nitrate solution until the precipitate just disappears, so as to prepare silver ammino ion solution;
s5, preparing a special-shaped environment pollution treating agent: and (2) dissolving gelatin and acacia in water to obtain gelatin-acacia solution, wherein the concentration of gelatin is 16wt%, the concentration of acacia is 16wt%, 13.5 parts by weight of silver deposition modified magnetic halloysite nano tube prepared in the step (S4), 5 parts by weight of peracetic acid and 8.5 parts by weight of hydrogen peroxide solution are added into 100 parts by weight of gelatin-acacia solution, homogenizing for 7min at 13500r/min, regulating the pH value of the solution to 4.2, stirring and reacting for 20min, regulating the pH value to 6.2, adding 4 parts by weight of glutamine transaminase, stirring and reacting for 30min, separating by using a magnet, washing and drying to obtain the special-shaped environment pollution treating agent.
Comparative example 6
In comparison with example 3, the difference is that step S6 is not performed.
The method comprises the following steps:
s1, preprocessing halloysite nanotubes: immersing halloysite nanotubes in a 10wt% NaOH solution for treatment, wherein the solid-to-liquid ratio of the halloysite nanotubes to the 10wt% NaOH solution is 1:7g/mL, filtering, washing and drying to obtain pretreated halloysite nanotubes;
s2, magnetic modification: dissolving 6 parts by weight of ferric chloride and ferrous chloride in 100 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 22 parts by weight of the pretreated halloysite nanotube prepared in the step S1 into the water solution under the protection of nitrogen, dropwise adding 4 parts by weight of 23.5wt% ammonia water, stirring for reaction, separating by a magnet, washing and drying to obtain the magnetic halloysite nanotube;
s3, modifying polydopamine: adding 10 parts by weight of the magnetic halloysite nanotube prepared in the step S2 into 100 parts by weight of water, adding 13.5 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 42 ℃, stirring and reacting for 2.5 hours, separating by a magnet, washing, and drying to prepare the polydopamine modified magnetic halloysite nanotube;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
S4, complexing plant polyphenol with metal ions: dissolving 2.5 parts by weight of metal salt in 100 parts by weight of water, adding 17 parts by weight of plant polyphenol, and stirring and mixing for 20min to obtain a metal ion complexing plant polyphenol solution;
the metal salt is a mixture of copper chloride and zinc chloride, and the mass ratio is 4:7;
the plant polyphenol is a mixture of tea polyphenol and apple polyphenol, and the mass ratio is 8.5:3;
s5, composite modification: adding 13.55 parts by weight of the polydopamine modified magnetic halloysite nanotube prepared in the step S3 into 100 parts by weight of the metal ion complexing plant polyphenol solution prepared in the step S4, heating to 40 ℃, stirring and reacting for 40min, separating by a magnet, washing and drying to prepare the modified magnetic halloysite nanotube;
s6, preparing a special-shaped environment pollution treating agent: and (2) dissolving gelatin and acacia in water to obtain gelatin-acacia solution, wherein the concentration of gelatin is 16wt% and the concentration of acacia is 16wt%, adding 13.5 parts by weight of the modified magnetic halloysite nanotube prepared in the step (S5), 5 parts by weight of peracetic acid and 8.5 parts by weight of hydrogen peroxide solution into 100 parts by weight of gelatin-acacia solution, homogenizing for 7min at 13500r/min, regulating the pH value of the solution to 4.2, stirring for reacting for 20min, regulating the pH value to 6.2, adding 4 parts by weight of glutamine transaminase, stirring for reacting for 30min, separating by using a magnet, washing and drying to obtain the special-shaped environment pollution treating agent.
Comparative example 7
In comparison with example 3, the difference is that no gelatin-gum arabic embedding is used in step S7.
The method comprises the following steps:
s1, preprocessing halloysite nanotubes: immersing halloysite nanotubes in a 10wt% NaOH solution for treatment, wherein the solid-to-liquid ratio of the halloysite nanotubes to the 10wt% NaOH solution is 1:7g/mL, filtering, washing and drying to obtain pretreated halloysite nanotubes;
s2, magnetic modification: dissolving 6 parts by weight of ferric chloride and ferrous chloride in 100 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 22 parts by weight of the pretreated halloysite nanotube prepared in the step S1 into the water solution under the protection of nitrogen, dropwise adding 4 parts by weight of 23.5wt% ammonia water, stirring for reaction, separating by a magnet, washing and drying to obtain the magnetic halloysite nanotube;
s3, modifying polydopamine: adding 10 parts by weight of the magnetic halloysite nanotube prepared in the step S2 into 100 parts by weight of water, adding 13.5 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 42 ℃, stirring and reacting for 2.5 hours, separating by a magnet, washing, and drying to prepare the polydopamine modified magnetic halloysite nanotube;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s4, complexing plant polyphenol with metal ions: dissolving 2.5 parts by weight of metal salt in 100 parts by weight of water, adding 17 parts by weight of plant polyphenol, and stirring and mixing for 20min to obtain a metal ion complexing plant polyphenol solution;
the metal salt is a mixture of copper chloride and zinc chloride, and the mass ratio is 4:7;
the plant polyphenol is a mixture of tea polyphenol and apple polyphenol, and the mass ratio is 8.5:3;
s5, composite modification: adding 13.55 parts by weight of the polydopamine modified magnetic halloysite nanotube prepared in the step S3 into 100 parts by weight of the metal ion complexing plant polyphenol solution prepared in the step S4, heating to 40 ℃, stirring and reacting for 40min, separating by a magnet, washing and drying to prepare the modified magnetic halloysite nanotube;
s6, silver deposition: adding 10 parts by weight of the modified magnetic halloysite nanotube prepared in the step S5 into 40 parts by weight of an aqueous solution containing 16wt% of glucose, dropwise adding 22 parts by weight of a silver ammino ion solution, heating to 95 ℃, stirring and reacting for 25min, separating by a magnet, washing, and drying to prepare a silver deposition modified magnetic halloysite nanotube;
the preparation method of the silver ammine ion solution comprises the following steps: dropwise adding 23.5wt% ammonia water into 1.5mol/L silver nitrate solution until the precipitate just disappears, so as to prepare silver ammino ion solution;
S7, preparing a special-shaped environment pollution treating agent: adding 13.5 parts by weight of the silver deposition modified magnetic halloysite nanotube prepared in the step S6, 5 parts by weight of peracetic acid and 8.5 parts by weight of hydrogen peroxide solution into 100 parts by weight of water, homogenizing for 7min at 13500r/min, stirring and reacting for 30min, separating by a magnet, washing and drying to prepare the special-shaped environment pollution treating agent.
Comparative example 8
In comparison with example 3, the difference is that peracetic acid is not added in step S7.
The method comprises the following steps:
s1, preprocessing halloysite nanotubes: immersing halloysite nanotubes in a 10wt% NaOH solution for treatment, wherein the solid-to-liquid ratio of the halloysite nanotubes to the 10wt% NaOH solution is 1:7g/mL, filtering, washing and drying to obtain pretreated halloysite nanotubes;
s2, magnetic modification: dissolving 6 parts by weight of ferric chloride and ferrous chloride in 100 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 22 parts by weight of the pretreated halloysite nanotube prepared in the step S1 into the water solution under the protection of nitrogen, dropwise adding 4 parts by weight of 23.5wt% ammonia water, stirring for reaction, separating by a magnet, washing and drying to obtain the magnetic halloysite nanotube;
s3, modifying polydopamine: adding 10 parts by weight of the magnetic halloysite nanotube prepared in the step S2 into 100 parts by weight of water, adding 13.5 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 42 ℃, stirring and reacting for 2.5 hours, separating by a magnet, washing, and drying to prepare the polydopamine modified magnetic halloysite nanotube;
The catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s4, complexing plant polyphenol with metal ions: dissolving 2.5 parts by weight of metal salt in 100 parts by weight of water, adding 17 parts by weight of plant polyphenol, and stirring and mixing for 20min to obtain a metal ion complexing plant polyphenol solution;
the metal salt is a mixture of copper chloride and zinc chloride, and the mass ratio is 4:7;
the plant polyphenol is a mixture of tea polyphenol and apple polyphenol, and the mass ratio is 8.5:3;
s5, composite modification: adding 13.55 parts by weight of the polydopamine modified magnetic halloysite nanotube prepared in the step S3 into 100 parts by weight of the metal ion complexing plant polyphenol solution prepared in the step S4, heating to 40 ℃, stirring and reacting for 40min, separating by a magnet, washing and drying to prepare the modified magnetic halloysite nanotube;
s6, silver deposition: adding 10 parts by weight of the modified magnetic halloysite nanotube prepared in the step S5 into 40 parts by weight of an aqueous solution containing 16wt% of glucose, dropwise adding 22 parts by weight of a silver ammino ion solution, heating to 95 ℃, stirring and reacting for 25min, separating by a magnet, washing, and drying to prepare a silver deposition modified magnetic halloysite nanotube;
the preparation method of the silver ammine ion solution comprises the following steps: dropwise adding 23.5wt% ammonia water into 1.5mol/L silver nitrate solution until the precipitate just disappears, so as to prepare silver ammino ion solution;
S7, preparing a special-shaped environment pollution treating agent: and (3) dissolving gelatin and acacia in water to obtain gelatin-acacia solution, wherein the concentration of gelatin is 16wt% and the concentration of acacia is 16wt%, adding 13.5 parts by weight of silver deposition modified magnetic halloysite nanotube prepared in the step (S6) and 13.5 parts by weight of hydrogen peroxide solution into 100 parts by weight of gelatin-acacia solution, homogenizing for 7min at 13500r/min, regulating the pH value of the solution to be 4.2, stirring for reacting for 20min, regulating the pH value to be 6.2, adding 4 parts by weight of glutamine transaminase, stirring for reacting for 30min, separating by using a magnet, washing and drying to obtain the special-shaped environment pollution treating agent.
Comparative example 9
The difference from example 3 is that hydrogen peroxide is not added in step S7.
The method comprises the following steps:
s1, preprocessing halloysite nanotubes: immersing halloysite nanotubes in a 10wt% NaOH solution for treatment, wherein the solid-to-liquid ratio of the halloysite nanotubes to the 10wt% NaOH solution is 1:7g/mL, filtering, washing and drying to obtain pretreated halloysite nanotubes;
s2, magnetic modification: dissolving 6 parts by weight of ferric chloride and ferrous chloride in 100 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 22 parts by weight of the pretreated halloysite nanotube prepared in the step S1 into the water solution under the protection of nitrogen, dropwise adding 4 parts by weight of 23.5wt% ammonia water, stirring for reaction, separating by a magnet, washing and drying to obtain the magnetic halloysite nanotube;
S3, modifying polydopamine: adding 10 parts by weight of the magnetic halloysite nanotube prepared in the step S2 into 100 parts by weight of water, adding 13.5 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 42 ℃, stirring and reacting for 2.5 hours, separating by a magnet, washing, and drying to prepare the polydopamine modified magnetic halloysite nanotube;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s4, complexing plant polyphenol with metal ions: dissolving 2.5 parts by weight of metal salt in 100 parts by weight of water, adding 17 parts by weight of plant polyphenol, and stirring and mixing for 20min to obtain a metal ion complexing plant polyphenol solution;
the metal salt is a mixture of copper chloride and zinc chloride, and the mass ratio is 4:7;
the plant polyphenol is a mixture of tea polyphenol and apple polyphenol, and the mass ratio is 8.5:3;
s5, composite modification: adding 13.55 parts by weight of the polydopamine modified magnetic halloysite nanotube prepared in the step S3 into 100 parts by weight of the metal ion complexing plant polyphenol solution prepared in the step S4, heating to 40 ℃, stirring and reacting for 40min, separating by a magnet, washing and drying to prepare the modified magnetic halloysite nanotube;
s6, silver deposition: adding 10 parts by weight of the modified magnetic halloysite nanotube prepared in the step S5 into 40 parts by weight of an aqueous solution containing 16wt% of glucose, dropwise adding 22 parts by weight of a silver ammino ion solution, heating to 95 ℃, stirring and reacting for 25min, separating by a magnet, washing, and drying to prepare a silver deposition modified magnetic halloysite nanotube;
The preparation method of the silver ammine ion solution comprises the following steps: dropwise adding 23.5wt% ammonia water into 1.5mol/L silver nitrate solution until the precipitate just disappears, so as to prepare silver ammino ion solution;
s7, preparing a special-shaped environment pollution treating agent: dissolving gelatin and acacia in water to obtain gelatin-acacia solution, wherein the concentration of gelatin is 16wt% and the concentration of acacia is 16wt%, adding 22 parts by weight of silver deposition modified magnetic halloysite nanotubes prepared in the step S6 and 5 parts by weight of peracetic acid into 100 parts by weight of gelatin-acacia solution, homogenizing for 7min at 13500r/min, regulating the pH value of the solution to 4.2, stirring for reacting for 20min, regulating the pH value to 6.2, adding 4 parts by weight of glutamine transaminase, stirring for reacting for 30min, separating by a magnet, washing, and drying to obtain the special-shaped environment pollution treating agent.
Comparative example 10
The difference compared to example 3 is that no silver deposition modified magnetic halloysite nanotube is added in step S7.
The method comprises the following steps:
preparing a special-shaped environment pollution treating agent: dissolving gelatin and acacia in water to obtain gelatin-acacia solution, wherein the concentration of gelatin is 16wt%, the concentration of acacia is 16wt%, 5 parts by weight of peracetic acid and 22 parts by weight of hydrogen peroxide solution are added into 100 parts by weight of gelatin-acacia solution, 13500r/min is homogenized for 7min, the pH value of the solution is regulated to 4.2, stirring reaction is carried out for 20min, the pH value is regulated to 6.2, 4 parts by weight of glutamine transaminase is added, stirring reaction is carried out for 30min, magnet separation, washing and drying are carried out, and the special-shaped environment pollution treating agent is prepared.
Test example 1 acute oral toxicity test
102 SPF KM mice, 20-22g in each half, were selected and kept in an environment at 20-25deg.C and humidity of 50-60%. The abnormal environmental pollution treatments prepared in examples 1 to 7 and comparative examples 1 to 10 were formulated into 10g/L of sample suspension, and the samples were fasted overnight before the test, without limiting drinking water, and were fasted continuously for 3 hours after contamination, and animals were observed daily for 14 days continuously. The animals that were dead and the animals that were surviving after the end of the observation were observed in a general anatomy.
Test results: the infected animals do not have any toxic symptoms within 14 days of infection and the body weight of the dead animals without toxicity is not abnormal, and the animals are generally dissected after the experimental observation is finished.
Test example 2
Culturing Escherichia coli and Staphylococcus aureus in contaminated livestock drinking water, respectively adding the abnormal environmental pollution treating agents or chlorine dioxide sterilizing powder, povidone iodine and peracetic acid prepared in the same amount of examples 1-7 and comparative examples 1-10 after the bacterial amount reaches a certain value, respectively isolating and sealing water samples after the medicines are added, measuring the quantity of Escherichia coli and Staphylococcus aureus at regular intervals, and taking the quantity of raw water samples as a reference and a reference, and adding and calculating the killing rate. Wherein, the addition amount of the disinfectant is 0.5g/L.
The results are shown in Table 1.
TABLE 1
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As shown in the table above, the special-shaped environment pollution treatment agent prepared in the embodiments 1-3 has good sterilizing effect.
Test example 3
The mother cellar collected in rainy season is respectively put into the special-shaped environmental pollution treatment agents prepared in the same amount of examples 1-7 and comparative examples 1-10, the addition amount is 0.5g/L, water samples are respectively isolated and sealed for 30min after the addition of the agents, and the detection is carried out according to GB/T5750-2006, and the results are shown in Table 2.
TABLE 2
As shown in the table above, the special-shaped environmental pollution treatment agent prepared in the embodiments 1-3 has good purification and disinfection effects on water.
Examples 4 and 5 are compared with example 3, in which the metal salt is copper chloride or zinc chloride alone. Comparative example 3 in contrast to example 3, no metal salt was added in step S4. The disinfection and sterilization effect is reduced. Cu (Cu) 2+ The tea polyphenol is subjected to complexation modification, so that the antibacterial property of the tea polyphenol can be improved, bacterial metabolic processes can be influenced by acting on bacterial genetic materials, meanwhile, the combination of the tea polyphenol and cellular enzyme protein can reduce the enzyme activity, and the combination of the tea polyphenol and membrane protein can influence the absorption of bacteria to nutrient substances. Zn (zinc) 2+ The complex formed by the complex and the tea polyphenol can cause structural change of the tea polyphenol, enhance the antioxidant capacity and antibacterial capacity of the tea polyphenol, and destroy the cell wall membrane structure by changing the normal form of bacteria, thereby playing a role in good antibacterial performance. Thus, cu is 2+ /Zn 2+ The complex modified plant polyphenol complex has good disinfection enhancement effect, and the combination of the complex modified plant polyphenol complex and the plant polyphenol has synergistic effect.
Examples 6 and 7 compare with example 3, the plant polyphenol is a single tea polyphenol or apple polyphenol. The disinfection and sterilization effect is reduced, and the turbidity is improved. Comparative example 4 in contrast to example 3, no plant polyphenol was added in step S4. Plant polyphenol is a complex secondary metabolite in plants and is green in sourceThe tea polyphenol is composed of catechins, anthocyanidins, phenolic acids and depsipelas, is a broad-spectrum bacteriostatic agent, and has obvious inhibition effect on pathogenic bacteria such as coliform bacteria and pseudomonas in water. The tea polyphenol and apple polyphenol have a plurality of reactive groups and active sites in the molecular structure, and can generate various chemical reactions such as phenols, alcohols, acids and the like. The antioxidant has strong oxidation-reduction effect, and the special conjugated structure provides conditions for antioxidation, so the antioxidant can be used as an antioxidant. Tea polyphenols and apple polyphenols are highly sensitive to metal ions, and the phenolic hydroxyl groups in their structures can be bound to most metal ions (e.g. Ca 2+ 、Pb 2+ 、Zn 2+ 、Fe 3+ 、Al 3+ Etc.) undergo a complexation reaction.
Comparative example 5 compared to example 3, steps S4, S5 were not performed. The disinfection and sterilization effect is reduced and the turbidity is improved.
Comparative example 1 compared to example 3, step S1 was not performed. The disinfection and sterilization effect is slightly reduced, and the turbidity is slightly improved. Halloysite nanotubes are a natural aluminosilicate [ Al ] 2 Si 2 O 5 (OH) 4 ·nH 2 O]The nano tube is generally in a hollow nano tube structure, the outer wall of the nano tube is a Si-O-Si group, a large number of Al-OH groups are contained in the tube cavity, and Si-OH and Al-OH groups exist at the edge of the nano tube, so that the nano tube has the characteristics of wide distribution, abundant reserves, good biocompatibility, acid and alkali corrosion resistance and the like. According to the invention, the halloysite nanotube is pretreated by alkali liquor, so that a large number of hydroxyl and other active groups are formed on the surface of the halloysite nanotube, thereby facilitating the subsequent in-situ deposition of magnetic ferroferric oxide.
Comparative example 2 showed a decrease in the sterilizing effect and an increase in turbidity compared with example 3, without performing step S3. And then a polydopamine layer is deposited on the surface of the magnetic halloysite nanotube, wherein polydopamine has a mussel protein-like structure and super-strong adhesion and can almost form covalent or non-covalent interaction with any substrate. Meanwhile, the modified polyurethane has rich hydrophilic functional groups such as catechol, amino and the like, and can effectively enhance the hydrophilicity of the surface of a substrate. Therefore, after the polydopamine layer is deposited on the surface layer, the polydopamine layer is beneficial to the subsequent hydrogen bond linkage with the metal ion complex plant polyphenol complex and glucose, so that the metal ion complex plant polyphenol complex and glucose are stably fixed, and the glucose is fixed, so that silver ammino ions can be deposited in situ, and the silver deposition modified magnetic halloysite nanotube is prepared.
Comparative example 6 in comparison with example 3, step S6 was not performed. Comparative example 9 in contrast to example 3, no hydrogen peroxide was added in step S7. The disinfection and sterilization effect is reduced, the turbidity is improved, and the long-acting disinfection effect is reduced. The invention also adds hydrogen peroxide, which can form a compound with a small amount of silver ions ionized by the silver deposition modified magnetic halloysite nanotube, overcomes the unstable characteristic of hydrogen peroxide, improves the disinfection capability of hydrogen peroxide, has strong and long-acting disinfection effect, has a killing effect on various bacteria such as escherichia coli, pseudomonas aeruginosa, staphylococcus aureus and the like, can completely decompose the compound, has no pollution to water and environment, can indirectly reflect the degree of organic pollution to water by oxygen consumption, and is a comprehensive index for evaluating the total organic pollution amount of the water.
Comparative example 7 in contrast to example 3, no gelatin-gum arabic entrapment was used in step S7. The long-acting disinfection effect is reduced. According to the invention, two linear irregular polymer materials with opposite charges are added into the solution to serve as wall materials (gelatin is positively charged and Arabic gum is negatively charged), core materials (silver deposition modified magnetic halloysite nanotubes, peracetic acid and hydrogen peroxide solution) are dispersed in the wall material water solution, the pH of the system is changed to enable electrostatic interaction between polymer materials with opposite charges to be mutually attracted, the solubility is reduced, phase separation is generated, colloid is condensed from the solution, and a slow-release microcapsule structure is prepared, so that the special-shaped environment pollution treating agent prepared by the invention has a slow-release effect, can be separated by a magnet and reused on one hand, and can be slowly released on the other hand, and the service period is prolonged.
Comparative example 8 in contrast to example 3, no peroxyacetic acid was added in step S7. The disinfection and sterilization effect is reduced and the turbidity is improved. The peracetic acid can realize sterilization through nascent oxygen, denature and coagulate bacterial proteins, damage active genes of enzyme proteins through oxidation-reduction reaction, inhibit the activity of enzymes, or inhibit the activity of enzymes by combining with enzymes in a competition or non-competition way due to the similarity of chemical structures and metabolic products. The byproducts are mainly carboxylic acid substances, and the byproducts are nontoxic and have low possibility of generating toxic substances through subsequent reaction in drinking water, so that the application of the peracetic acid is good, the toxicity is low, and the peracetic acid can be applied to the disinfection of drinking water of livestock.
Comparative example 10 in comparison with example 3, no silver deposition modified magnetic halloysite nanotube was added in step S7. The disinfection and sterilization effect is obviously reduced, and the turbidity is obviously improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. The preparation method of the special-shaped environment pollution treating agent is characterized by comprising the following steps of:
S1, preprocessing halloysite nanotubes: immersing halloysite nanotubes in alkali liquor for treatment, filtering, washing and drying to obtain pretreated halloysite nanotubes;
s2, magnetic modification: dissolving ferric chloride and ferrous chloride in water, adding the pretreated halloysite nanotube prepared in the step S1 into water under the protection of inert gas, dropwise adding ammonia water, stirring for reaction, separating by a magnet, washing, and drying to obtain a magnetic halloysite nanotube;
s3, modifying polydopamine: adding the magnetic halloysite nanotube prepared in the step S2 into water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, separating a magnet, washing, and drying to prepare the polydopamine modified magnetic halloysite nanotube;
s4, complexing plant polyphenol with metal ions: dissolving metal salt in water, adding plant polyphenol, stirring and mixing to obtain metal ion complex plant polyphenol solution; the metal salt is a mixture of copper chloride and zinc chloride, and the mass ratio is 3-5:7; the plant polyphenol is a mixture of tea polyphenol and apple polyphenol, and the mass ratio is 7-10:3;
s5, composite modification: adding the polydopamine modified magnetic halloysite nanotube prepared in the step S3 into the metal ion complexing plant polyphenol solution prepared in the step S4, heating and stirring for reaction, separating by a magnet, washing and drying to prepare the modified magnetic halloysite nanotube;
S6, silver deposition: adding the modified magnetic halloysite nanotube prepared in the step S5 into an aqueous solution containing glucose, dropwise adding a silver ammino ion solution, heating and stirring for reaction, separating by a magnet, washing and drying to prepare a silver deposition modified magnetic halloysite nanotube;
s7, preparing a special-shaped environment pollution treating agent: dissolving gelatin and acacia in water to obtain gelatin-acacia solution, adding the silver deposition modified magnetic halloysite nanotube, peracetic acid and hydrogen peroxide solution prepared in the step S6 for homogenization, regulating the pH value of the solution to be a first pH value, stirring for reaction, regulating the pH value to be a second pH value, adding glutamine transaminase, stirring for reaction, separating by a magnet, washing and drying to obtain the special-shaped environment pollution treating agent.
2. The method according to claim 1, wherein the halloysite nanotube and the alkali solution in the step S1 have a solid-to-liquid ratio of 1:5-10g/mL, and the alkali solution is 7-12wt% NaOH or KOH solution.
3. The method according to claim 1, wherein the inert gas in step S2 is at least one selected from nitrogen, argon, helium, neon; the molar ratio of the ferric chloride to the ferrous chloride is 2:1; the mass ratio of the ferric chloride to the pretreated halloysite nanotube to the ammonia water is 5-7:20-25:3-5; the concentration of the ammonia water is 22-25wt%.
4. The preparation method according to claim 1, wherein the mass ratio of the magnetic halloysite nanotube, the dopamine hydrochloride and the catalyst in the step S3 is 10:12-15:1-2; the catalyst contains 3-5wt% of CoCl 2 Tris-HCl solution at ph=5-6; the temperature of the heating and stirring reaction is 40-45 ℃,the time is 2-3h.
5. The method according to claim 1, wherein the mass ratio of the metal salt, water and plant polyphenol in step S4 is 2-3:100:15-20.
6. The preparation method of claim 1, wherein in the step S5, the mass ratio of the polydopamine modified magnetic halloysite nanotubes to the metal ion complexing plant polyphenol solution is 12-15:100; the temperature of the heating and stirring reaction is 35-45 ℃ and the time is 30-50min.
7. The preparation method according to claim 1, wherein the preparation method of the silver ammine ion solution in step S6 is as follows: dropwise adding 22-25wt% ammonia water into 1-2mol/L silver nitrate solution until the precipitate just disappears, so as to obtain silver ammino ion solution; the content of glucose in the aqueous solution containing glucose is 12-20wt%; the mass ratio of the modified magnetic halloysite nanotube to the aqueous solution containing glucose to the silver ammino ion solution is 10:30-50:20-25; the temperature of the heating and stirring reaction is 90-100 ℃ and the time is 20-30min.
8. The method according to claim 1, wherein the concentration of gelatin in the gelatin-acacia solution in step S7 is 12-20wt%, and the concentration of acacia is 15-17wt%; the mass ratio of the gelatin-Arabic gum solution to the silver deposition modified magnetic halloysite nanotube to the peroxyacetic acid to the hydrogen peroxide to the glutamine transaminase is 100:12-15:4-7:7-10:3-5; the homogenizing condition is 12000-15000r/min for 5-10min; the first pH value is 4.1-4.3, and the second pH value is 6.1-6.3.
9. A special-shaped environmental pollution treatment agent produced by the production method according to any one of claims 1 to 8.
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| WO2013181331A2 (en) * | 2012-05-30 | 2013-12-05 | Ibh Ventures, Llc | Polyphenol-reactive oxygen species compositions and methods |
| CN103638944A (en) * | 2013-11-22 | 2014-03-19 | 江苏大学 | Preparation method of magnetic composite catalyst Ag/HNTs/Fe3O4 |
| CN107088398A (en) * | 2017-07-04 | 2017-08-25 | 扬州大学 | The preparation method of galapectite load aciculiform ferriferrous oxide nano composite |
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