CN113797732A - Preparation method of micro-nano zinc odor-removing spray for sheep farm - Google Patents

Preparation method of micro-nano zinc odor-removing spray for sheep farm Download PDF

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CN113797732A
CN113797732A CN202110752104.8A CN202110752104A CN113797732A CN 113797732 A CN113797732 A CN 113797732A CN 202110752104 A CN202110752104 A CN 202110752104A CN 113797732 A CN113797732 A CN 113797732A
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odor
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nano zinc
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CN113797732B (en
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查进
黄世伟
陈海亮
吴玄峰
刘慧梅
钱鹏
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Nanjing Kaichuang Xietong Nano Technology Co ltd
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Nanjing Kaichuang Xietong Nano Technology Co ltd
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Abstract

The invention provides a preparation method of a micro-nano zinc odor-removing spray for a sheep farm, which comprises the following steps: firstly, preparing a micro-nano zinc solution, adding dimethyldichlorosilane, water, hydrochloric acid and the micro-nano zinc solution into a stainless steel reaction kettle, stirring at constant temperature for hydrolysis, and then delivering a hydrolysate generated into a delayer for layering; taking the upper layer as hydrolysate, and washing, neutralizing, dehydrating and fractionating the hydrolysate after flowing out to obtain a dimethyl silicone polymer coordination zinc compound; adding a solubilizer into the dimethyl silicone polymer coordination zinc compound, and stirring to obtain dimethyl silicone polymer coordination zinc A; continuously adding a surfactant to obtain a polydimethylsiloxane coordination zinc solution B, and adding the dispersion liquid to obtain the micro-nano zinc odor-removing spray for the sheep farm; the invention can obviously reduce the odor concentration outside the sheep farm and improve the influence on the surrounding environment, is safe and nontoxic, meets the requirement of environmental protection, and has high cost performance.

Description

Preparation method of micro-nano zinc odor-removing spray for sheep farm
Technical Field
The invention relates to the technical field of micro-nano zinc odor-removing spray for sheep farms, in particular to a preparation method of micro-nano zinc odor-removing spray for sheep farms.
Background
Sheep are herbivorous animals, mainly use straw feed, and are matched with concentrated feed with comprehensive nutrition. The development of sheep raising industry can promote the adjustment of the structure of the breeding industry of the planting industry, plant grass to raise sheep, particularly low-yield farmlands, and promote land increment. The utilization rate of the crop straws is improved, waste is changed into valuable, the rising and the development of the processing industries of the crop straw micro-storage and the like, the feed processing industry and the feed additive industry are promoted, and the overall economic level of the region is improved.
However, the risks of sheep feeding are mainly due to natural disasters, diseases and pollution to the surrounding environment. Snow removing work of a sheep cot ceiling needs to be noticed when snow falls in winter, and loss caused by snow collapse of the sheep cot is avoided. The diseases of sheep mainly include fasciolopsis, foot rot, sheep plague, etc., and the prevention and treatment need to be carried out in time, and meanwhile, comprehensive veterinary hygiene measures must be carried out. However, the breeding industry is inevitably confronted with the problem of strong odor of the ammonia gas in the pen house, wherein the ammonia is derived from excrement, stomach and digestive matters and the like excreted by animals, the urea ammonia mainly exists in the form of urea and is easily hydrolyzed by urease to generate ammonia gas and carbon dioxide through catalysis, so that the odor of the whole pen house is difficult to control, and therefore, the method has the following effective methods for thoroughly removing the odor of the ammonia gas in the pen house:
deodorants are mainly of the following types: physical deodorant, chemical deodorant, microbial deodorant, etc.
Physical deodorants are deodorised by physical means, using the physical properties of the deodorant or malodour, without changing the malodour components, only by changing the local or relative concentration of the malodour.
The chemical deodorant is a deodorant substance that is converted from a malodorous substance generated by oxidation, reductive decomposition, neutralization, condensation, ion exchange, or the like, thereby eliminating the odor.
The microbial deodorant is characterized in that malodorous substances in dissolved water are absorbed into the bodies of microbes by the microbes, and the malodorous substances are explained by the metabolic activity of the microbes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the micro-nano zinc odor-removing spray for the sheep farm, which can obviously reduce the odor concentration outside the sheep farm, improve the influence on the surrounding environment, reduce the complaint of surrounding residents, is safe and nontoxic, meets the requirements of environmental protection and has high cost performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a micro-nano zinc odor-removing spray for a sheep farm is characterized by comprising two parts of preparing a micro-nano zinc solution and preparing a micro-nano zinc odor-removing spray for a sheep farm; the method comprises the following steps:
step 1: preparing a zinc particle solution by using a micro-emulsion method, wherein the particle size of zinc particles is 10nm-600 nm;
the step 1 specifically further comprises:
step 1.1, preparing the microemulsion to form a WPO (WPO) reverse microemulsion system: dissolving a surfactant in an organic solvent, mixing with a cosurfactant and deionized water, and stirring to prepare a WPO (waterborne polyurethane emulsion) reverse microemulsion system;
when the surfactant concentration exceeds the critical micelle concentration CMC, a liquid particle structure with hydrophilic polar heads inward and hydrophobic organic chains outward is formed, and the core thereof can solubilize water molecules or hydrophilic substances.
Further, in the step 1.1, the volume ratio of the total volume of the surfactant, the cosurfactant and the organic solvent to the deionized water is 1-4:1, and the volume ratio of the surfactant, the cosurfactant and the organic solvent is 1-5:1: 2-4;
wherein, the organic solvent is one or more of alkane and cyclane;
the surfactant is a nonionic surfactant; the nonionic surfactant is one or more of polyoxyethylene nonyl phenyl ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether or high-carbon fatty polyoxyethylene ether;
the cosurfactant is one or more of isoamyl alcohol, n-heptanol, n-octanol, n-nonanol, n-decanol or cetyl alcohol.
Step 1.2, preparation of zinc particle solution: respectively adding a zinc salt aqueous solution with the concentration of 400-600 g/L and a hydrazine hydrate solution into a WPO reverse microemulsion system, stirring and mixing, and reacting for 5-8h to obtain a zinc particle solution with the particle size of 10-600 nm.
Further, the reaction temperature in step 1.2 is 40-80 ℃, and the stirring speed is 2000-5000 rpm.
The volume ratio of the zinc salt aqueous solution to the hydrazine hydrate solution is 1:1, and the volume ratio of the hydrazine hydrate solution to the WPO reverse microemulsion system is 1: 3.5-4; the zinc salt is one or more of zinc sulfate, zinc nitrate, zinc citrate and zinc gluconate.
Step 2: transferring the prepared zinc particles to the next reaction kettle, and preparing the micro-nano zinc solution by utilizing the cavitation phenomenon.
The step 2 specifically further comprises:
step 2.1: transferring the zinc particle solution prepared in the step 1 to the next reaction kettle, stirring at 60 ℃, wherein the stirring speed is 2000-5000rpm, and simultaneously introducing high-speed air flow to form a cavitation phenomenon; fine liquid-gas interphase interfaces are formed by utilizing the processes of forming, developing, collapsing and rebounding of the liquid vacuoles, and the surfaces of the zinc particles are corroded by utilizing the micro-jet flow and the impact action generated when the vacuoles collapse;
step 2.2: reacting for 5 hours to prepare the micro-nano zinc solution.
And step 3: adding 10-80 parts by mass of dimethyl siloxane, 20-50 parts by mass of water, 1-20 parts by mass of hydrochloric acid and 1-35 parts by mass of micro-nano zinc solution into a reaction kettle for mixing, stirring at constant temperature for hydrolysis, and then sending the hydrolyzed product into a delayer for layering; taking the hydrolysate on the upper layer, and obtaining a dimethyl silicone polymer coordination zinc compound after washing, neutralizing, dehydrating and fractionating;
and 4, step 4: taking 100 parts by mass of a polydimethylsiloxane coordination zinc compound, adding 0.1-40 parts by mass of a solubilizer, and mixing to obtain a polydimethylsiloxane coordination zinc compound solution A;
and 5: taking 100 parts by mass of a polydimethylsiloxane coordination zinc compound solution A, adding 0.5-25 parts by mass of a surfactant, and mixing to obtain a polydimethylsiloxane coordination zinc compound solution B;
step 6: and adding 20-1500 parts by mass of dispersion liquid into 100 parts by mass of polydimethylsiloxane coordination zinc compound solution B, and mixing to obtain the micro-nano zinc odor-removing spray for the sheep farm.
Further, in the step 3, the stirring temperature is 30-90 ℃, and the stirring speed is 100-800 r/min.
Further, in step 4, the reaction conditions for mixing are as follows: and carrying out constant-temperature water bath at 50-90 ℃ for 30-90 min, wherein the mixing speed is 50-150 r/min.
Further, in the step 5, the rotation speed of mixing is 50-130 r/min, and the reaction time is 20-100 min; in the step 6, the stirring speed is 30-90 r/min, and the reaction time is 10-30 min.
Further, in the step 4, the solubilizer is any one or more of solubilizer CO40, benzalkonium chloride, citric acid and decamethylammonium chloride;
in the step 5, the surfactant is one or more of surfactant AES, surfactant LS30 and surfactant CAB 35;
in the step 6, the dispersion liquid is one or two of deionized water and ethanol.
When the micro-nano zinc is prepared, the surface of zinc particles is corroded by adopting a cavitation phenomenon to form an acute angle with an irregular shape, and the micro-nano zinc shows a positive charge effect when contacting bacteria or viruses and generates coulomb force with bacterial cell walls or virus cells showing a negative charge effect; the attraction of coulomb force and the edge of the spike can kill bacteria and viruses quickly, and the bacteria and the viruses can not be propagated or transferred continuously and die; the micro-nano zinc is not consumed in the process of killing bacteria or viruses, and can continuously cause the death of the bacteria and the viruses, so the micro-nano zinc can continuously and durably kill the bacteria and the viruses, and the defect of the nano zinc in the aspect of quick bactericidal performance is overcome.
The invention prepares the macromolecular long-chain compound-polydimethylsiloxane coordination zinc compound by firstly preparing Zn in the polydimethylsiloxane coordination zinc compound2+The adsorbed odor molecules are subjected to chemical reactions such as oxidation, catalysis, decomposition, complexation and the like (particularly by controlling the particle size of zinc ions), the carbon chain structure and the molecular structure of the odor molecules are destroyed, new tasteless and nontoxic chemical substances are generated again, and the odor molecules are thoroughly decomposed into N harmless to the environment2，CO2And H2And O. Secondly, the dimethyl silicone polymer coordination zinc compound adsorbs harmful micromolecular odor substances in the air, such as NH, through-O-capture in the long chain of the macromolecule3，H2S, dimethylamine and the like, and locks the micromolecule odor molecules on the long chain of the macromolecule, thereby thoroughly eliminating the micromolecule odor molecules. The surfactant in the formula can not only enable the synthesized polydimethylsiloxane coordination zinc compound to stably exist for a long time, but also form a synergistic effect with the polydimethylsiloxane coordination zinc compound, can better play a synergistic deodorization effect and can treat micromolecule NH in odor molecules3Dimethylamine and the like also have good removal effect and can more thoroughly remove all odor gas components.
Compared with the prior art, the invention has the following beneficial effects because the technology is adopted:
1. according to the micro-nano zinc odor-removing spray for the sheep farm, which is prepared by the invention, as zinc ions with more concentrated particle sizes are used, harmful gases in odor can be decomposed more rapidly and thoroughly, the odor concentration of the interior and exterior of the sheep farm is effectively reduced, and the odor-removing effect can be kept for a long time.
2. The micro-nano zinc odor-removing spray for the sheep farm prepared by the invention is made of green, environment-friendly, non-toxic and harmless materials, has no harm to sheep and surrounding environment, and is safe and reliable.
3. The micro-nano zinc odor-removing spray for the sheep farm, which is prepared by the invention, has high cost performance, can effectively remove harmful gas, does not increase the enterprise cost too much, and has great popularization prospect.
Drawings
FIG. 1 is a micro-structure diagram of micro-nano zinc with etching pits obtained by utilizing a cavitation effect;
FIG. 2 is a particle size distribution diagram of the micro-nano zinc.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the scope of the present invention.
Example 1 preparation of micro-nano Zinc solution and Performance Effect
(1) The preparation method of the micro-nano zinc comprises the following steps:
step 1.1: dissolving 50mL of nonylphenol polyoxyethylene ether and 30mL of n-octanol in 120mL of cyclohexane, and stirring with 20mL of isoamyl alcohol and 200mL of deionized water to prepare a WPO (waterborne polyurethane emulsion) reverse microemulsion system;
step 1.2: adding 1000mL of zinc salt aqueous solution (mixed solution of zinc citrate and zinc nitrate) with the concentration of 450g/L and 1000mL of hydrazine hydrate solution into 3600mL of HPO reverse microemulsion for mixing, and reacting for 6.5h at 65 ℃ and the rotating speed of 4600rpm to prepare zinc particle solution with the particle size of 10nm-600 nm;
step 2.1: transferring the prepared zinc particle solution into the next reaction kettle, stirring at 60 ℃, 4600rpm, and introducing high-speed air flow to form a cavitation phenomenon;
step 2.2: the reaction time is 5 hours, and the micro-nano zinc solution is prepared.
A TEM image of the prepared micro-nano zinc is shown in fig. 1.
As shown in fig. 2, the microemulsion method is used to prepare zinc with the particle size between micron and nanometer, and the reaction conditions are controlled to prepare zinc particles with the particle size:
Figure RE-GDA0003359115450000051
preferred results are:
Figure RE-GDA0003359115450000052
the zinc particles 1 account for 50% of the total number, and the particle diameter of the zinc particles 1
Figure RE-GDA0003359115450000053
Figure RE-GDA0003359115450000054
Accounting for 30% of the total.
The invention controls the reaction condition to prepare the product with the grain diameter of
Figure RE-GDA0003359115450000055
The micro-nano zinc and the cavitation effect are applied to form corrosion pits on the particle surfaces of zinc particles so as to improve the effect of quickly sterilizing and inactivating viruses.
It is recognized at home and abroad that the average diameter of the nano particles is
Figure RE-GDA0003359115450000056
When used, the particles are referred to as nanoparticles. The diameter of the prepared zinc particles is between nanometer and micrometer, so the micro-nano zinc is called micrometer nano zinc and is called micro-nano zinc for short.
(2) Micro-nano zinc solution sterilization effect
Preparing the micro-nano zinc solution prepared by the method into a micro-nano zinc aqueous solution with the concentration of 1000mg/kg, and then sequentially diluting the micro-nano zinc aqueous solution into a solution with the concentration of: the method comprises the following steps of sequentially marking micro-nano zinc aqueous solutions with the concentrations of 800mg/kg, 500mg/kg, 400mg/kg and 300mg/kg as a group 5, a group 4, a group 3, a group 2 and a group 1, measuring the sterilization rate of the micro-nano zinc aqueous solution according to a suspension quantitative method of disinfection technical specification, wherein test strains comprise escherichia coli, staphylococcus aureus, candida albicans and pseudomonas aeruginosa for 20s, 30s and 60 s; the test results are shown in table 1.
TABLE 1 Sterilization effect of micro-nano zinc solution under different time
Figure RE-GDA0003359115450000061
(3) Micro-nano zinc solution virus inactivation effect
(a) Preparing the micro-nano zinc solution prepared by the method into a micro-nano zinc aqueous solution with the concentration of 1000mg/kg, and then sequentially diluting the micro-nano zinc aqueous solution into a solution with the concentration of: the method comprises the following steps of sequentially marking micro-nano zinc aqueous solutions with the concentrations of 1000mg/kg, 800mg/kg, 500mg/kg, 400mg/kg and 300mg/kg as a group 5, a group 4, a group 3, a group 2 and a group 1, determining the virus inactivation rate of the micro-nano zinc aqueous solution according to disinfection technical specifications, testing the viruses to be poliovirus, influenza A virus H1N1, enterovirus and avian influenza virus H5N1 for 10s, 20s and 30 s; the test results are shown in table 2.
Virus inactivating effect of epidianano zinc solution in different time
Figure RE-GDA0003359115450000071
(b) Preparing the micro-nano zinc solution into an aqueous solution with the concentration of 1000mg/kg, diluting the micro-nano zinc aqueous solution by 10000 times to obtain the micro-nano zinc aqueous solution with the concentration of 100 mu g/kg,taking 5 replicates and labeling: group 1, group 2, group 3, group 4 and group 5, groups 1 to 5 respectively with a concentration of 106TCID50Mixing pseudorabies virus and coronavirus (PEDV) in a contact manner for 30min, and measuring the virus inactivation rate; the test results are shown in table 3.
TABLE 3 Virus inactivating effect of micro-nano zinc solution
Figure RE-GDA0003359115450000081
Example 2: preparation of micro-nano zinc odor-removing spray for sheep farm
And step 3: firstly, 50 parts by mass of dimethyl siloxane, 35 parts by mass of water, 10 parts by mass of hydrochloric acid and 5 parts by mass of the micro-nano zinc solution prepared in the embodiment 1 are added into a stainless steel reaction kettle, stirring and hydrolyzing are carried out at 50 ℃ at 500r/min, and then a hydrolyzed product is sent into a delayer for delaminating; taking the hydrolysate on the upper layer, and obtaining a dimethyl silicone polymer coordination zinc compound after washing, neutralizing, dehydrating and fractionating;
and 4, step 4: taking 100 parts by mass of the polydimethylsiloxane coordination zinc compound solution, adding 20 parts by mass of a solubilizer, mixing, and carrying out constant-temperature water bath at 60 ℃ for 30min at 100r/min to prepare the polydimethylsiloxane coordination zinc compound solution A.
And 5: and (3) taking 100 parts by mass of the polydimethylsiloxane coordination zinc compound solution A, adding 5 parts by mass of a surfactant into the solution A, and stirring the solution A at the speed of 80r/min for 40min to prepare a polydimethylsiloxane coordination zinc compound solution B.
Step 6: and adding 800 parts by mass of dispersion liquid into 100 parts by mass of polydimethylsiloxane coordination zinc compound solution B, mixing, stirring at room temperature for 20min at 60r/min, and finally preparing the micro-nano zinc odor-removing spray for the sheep farm.
In the step 4, the solubilizer is solubilizer CO 40;
in step 5, the surfactant is surfactant LS 30.
In step 6, the dispersion is deionized water.
Example 3: preparation of micro-nano zinc odor-removing spray for sheep farm
A preparation method of a micro-nano zinc odor-removing spray for a sheep farm comprises the following steps:
and step 3: firstly adding 65 parts by mass of dimethyl siloxane, 20 parts by mass of water, 5 parts by mass of hydrochloric acid and 10 parts by mass of the micro-nano zinc solution prepared in the example 1 into a stainless steel reaction kettle, stirring and hydrolyzing at 40 ℃ at 600r/min, and feeding a hydrolyzed product into a delayer for layering; taking the hydrolysate on the upper layer, and obtaining a dimethyl silicone polymer coordination zinc compound after washing, neutralizing, dehydrating and fractionating;
and 4, step 4: taking 100 parts by mass of the polydimethylsiloxane coordination zinc compound solution, adding 28 parts by mass of a solubilizer, mixing, and carrying out constant-temperature water bath at 80 ℃ for 50min at 80r/min to prepare the polydimethylsiloxane coordination zinc compound solution A.
And 5: and taking 100 parts by mass of the polydimethylsiloxane coordination zinc compound solution A, adding 13 parts by mass of a surfactant into the solution A, and stirring the solution A at the speed of 60r/min for 60min to prepare a polydimethylsiloxane coordination zinc compound solution B.
Step 6: and adding 600 parts by mass of dispersion liquid into 100 parts by mass of polydimethylsiloxane coordination zinc compound solution B, mixing, stirring at room temperature for 30min at 90r/min, and finally preparing the micro-nano zinc odor-removing spray for the sheep farm.
In the step 4, the solubilizer is a mixture of CO40 and benzalkonium chloride, and the mass ratio is 4: 1;
in the step 5, the surfactant is LS30 and CAB35, and the mass ratio is 3: 1.
in the step 6, the dispersion liquid is deionized water and ethanol, and the mass ratio is 4: 1.
Example 4: preparation of micro-nano zinc odor-removing spray for sheep farm
A preparation method of a micro-nano zinc odor-removing spray for a sheep farm comprises the following steps:
and step 3: adding 50 parts by mass of dimethyl siloxane, 40 parts by mass of water, 8 parts by mass of hydrochloric acid and 2 parts by mass of the micro-nano zinc solution prepared in the embodiment 1 into a stainless steel reaction kettle, stirring and hydrolyzing at 70 ℃ at 300r/min, and then sending a hydrolyzed product into a delayer for layering; taking the hydrolysate on the upper layer, and obtaining a dimethyl silicone polymer coordination zinc compound after washing, neutralizing, dehydrating and fractionating;
and 4, step 4: taking 100 parts by mass of the polydimethylsiloxane coordination zinc compound solution, adding 10 parts by mass of a solubilizer, mixing, and carrying out constant-temperature water bath at 70 ℃ for 70min at 60r/min to prepare the polydimethylsiloxane coordination zinc compound solution A.
And 5: and (3) taking 100 parts by mass of the polydimethylsiloxane coordination zinc compound solution A, adding 4 parts by mass of a surfactant into the solution A, and stirring the solution A at 70r/min for 40min to prepare a polydimethylsiloxane coordination zinc compound solution B.
Step 6: and adding 300 parts by mass of dispersion liquid into 100 parts by mass of polydimethylsiloxane coordination zinc compound solution B, mixing, stirring at room temperature for 25min at a speed of 80r/min, and finally preparing the micro-nano zinc odor-removing spray for the sheep farm.
In the step 4, the solubilizer is a mixture of decamethyl ammonium chloride and benzalkonium chloride, and the mass ratio is 1: 1;
in the step 5, the surfactant is surfactant AES and surfactant CAB35, and the mass ratio is 1: 1.
in step 6, the dispersion is deionized water.
The micro-nano zinc odor-removing spray for the sheep farm prepared in the example 2-4 is detected, and the result is as follows:
test example 1
The deodorizing effect is evaluated by an olfactory test, which is a method for evaluating the strength of odor and the suitability and discomfort according to the human olfactory sense, and measuring characteristic parameters (olfactory threshold value, concentration, sensory intensity, etc.) of the malodor.
An 8-person smell test group is established, wherein the panelists are 18-45 years old, do not smoke and have normal smell, and the effect evaluation indexes of the odorous gas after being treated by the micro-nano zinc smell-removing spray for the sheep farm prepared in the embodiment 2-4 are as follows: the test group is evaluated, more than 4 evaluation indexes can be used as a test conclusion, otherwise, the test group is evaluated again, and specific results are shown in the following table 4.
Table 4 odor evaluation results of simulated sheep farm deodorization test
Figure RE-GDA0003359115450000101
Figure RE-GDA0003359115450000111
As can be seen from the data in table 4, the micro-nano zinc odor-removing spray for sheep farms prepared in examples 2 to 4 can effectively deodorize, and the micro-nano zinc odor-removing spray for sheep farms prepared in example 3 can more effectively deodorize the air in the sheep farms.
Test example 2
Selecting 6 independent closed spaces, wherein each space is 1m3, introducing odorous gas with the same amount into each space, controlling the indoor temperature at 25-30 ℃, selecting 5 spaces as the micro-nano zinc odor-removing spray for the sheep farm prepared in the embodiment 2-4 for deodorization tests, directly spraying the micro-nano zinc odor-removing spray for the sheep farm in the closed space environment, and using no deodorant as a reference in the remaining space; after the micro-nano zinc odor-removing spray is sprayed in a sheep farm, the hydrogen sulfide concentration and the NH3 concentration in a room are detected every 14 days, the ammonia concentration and the hydrogen sulfide concentration removal rate are respectively calculated by taking a blank room as a reference, the monitoring time is 42 days, and the specific results are shown in the following table 5. The detection method comprises GB/T14678-1993 air quality-hydrogen sulfide and NH3 determination-gas chromatography, GB/T14675-199 air quality-malodor determination-three-point comparison type odor bag method.
Table 5 results of the deodorization test for simulated sheep farm
Figure RE-GDA0003359115450000112
As can be seen from the data in table 5, the micro-nano zinc odor-removing spray for sheep farms prepared in examples 2 to 4 has a good effect of removing hydrogen sulfide and NH3, and particularly, the micro-nano zinc odor-removing spray for sheep farms prepared in example 3 has the best effect of removing hydrogen sulfide and NH 3.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the preferred embodiments of the invention and described in the specification are only preferred embodiments of the invention and are not intended to limit the invention, and that various changes and modifications may be made without departing from the novel spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. A preparation method of a micro-nano zinc odor-removing spray for a sheep farm is characterized by comprising the following steps:
step 1: preparing a zinc particle solution by using a micro-emulsion method, wherein the particle size of zinc particles is 10nm-600 nm;
step 2: preparing a micro-nano zinc solution from the prepared zinc particle solution by utilizing a cavitation phenomenon;
and step 3: adding 10-80 parts by mass of dimethyl siloxane, 20-50 parts by mass of water, 1-20 parts by mass of hydrochloric acid and 1-35 parts by mass of micro-nano zinc solution into a reaction kettle, mixing, stirring at constant temperature for hydrolysis, and feeding the hydrolyzed product into a delayer for layering; taking the hydrolysate on the upper layer, and obtaining a dimethyl silicone polymer coordination zinc compound after washing, neutralizing, dehydrating and fractionating;
and 4, step 4: taking 100 parts by mass of a polydimethylsiloxane coordination zinc compound, adding 0.1-40 parts by mass of a solubilizer, and mixing to obtain a polydimethylsiloxane coordination zinc compound solution A;
and 5: taking 100 parts by mass of a polydimethylsiloxane coordination zinc compound solution A, adding 0.5-25 parts by mass of a surfactant, and mixing to obtain a polydimethylsiloxane coordination zinc compound solution B;
step 6: and adding 20-1500 parts by mass of dispersion liquid into 100 parts by mass of polydimethylsiloxane coordination zinc compound solution B, and mixing to obtain the micro-nano zinc odor-removing spray for the sheep farm.
2. The preparation method of the micro-nano zinc odor-removing spray for the sheep farm according to claim 1, which is characterized by comprising the following steps: in the step 3, the stirring temperature is 30-90 ℃, and the stirring speed is 100-800 r/min.
3. The preparation method of the micro-nano zinc odor-removing spray for the sheep farm according to claim 1, which is characterized by comprising the following steps: in step 4, the reaction conditions for mixing are as follows: and carrying out constant-temperature water bath at 50-90 ℃ for 30-90 min, wherein the mixing speed is 50-150 r/min.
4. The preparation method of the micro-nano zinc odor-removing spray for the sheep farm according to claim 1, which is characterized by comprising the following steps: in the step 5, the mixing speed is 50-130 r/min, and the reaction time is 20-100 min; in the step 6, the stirring speed is 30-90 r/min, and the reaction time is 10-30 min.
5. The preparation method of the micro-nano zinc odor-removing spray for the sheep farm according to claim 1, which is characterized by comprising the following steps:
in the step 4, the solubilizer is any one or more of solubilizer CO40, benzalkonium chloride, citric acid and decamethylammonium chloride;
in the step 5, the surfactant is one or more of surfactant AES, surfactant LS30 and surfactant CAB 35;
in the step 6, the dispersion liquid is one or two of deionized water and ethanol.
6. The preparation method of the micro-nano zinc odor-removing spray for the sheep farm according to claim 1, which is characterized by comprising the following steps: step 1 also comprises step 1.1, preparing the microemulsion to form a WPO reverse microemulsion system: dissolving a surfactant in an organic solvent, mixing with a cosurfactant and deionized water, and stirring to prepare a WPO (waterborne polyurethane emulsion) reverse microemulsion system;
step 1.2, preparation of zinc particle solution: respectively adding a zinc salt aqueous solution with the concentration of 400-600 g/L and a hydrazine hydrate solution into a WPO reverse microemulsion system, stirring and mixing, and reacting for 5-8h to obtain a zinc particle solution with the particle size of 10-600 nm.
7. The preparation method of the micro-nano zinc odor-removing spray for the sheep farm according to claim 6, which is characterized by comprising the following steps: in the step 1.1, the volume ratio of the total volume of the surfactant, the cosurfactant and the organic solvent to the deionized water is 1-4:1, and the volume ratio of the surfactant, the cosurfactant and the organic solvent is 1-5:1: 2-4;
wherein, the organic solvent is one or more of alkane and cyclane;
the surfactant is a nonionic surfactant; the nonionic surfactant is one or more of polyoxyethylene nonyl phenyl ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether or high-carbon fatty polyoxyethylene ether;
the cosurfactant is one or more of isoamyl alcohol, n-heptanol, n-octanol, n-nonanol, n-decanol or cetyl alcohol.
8. The preparation method of the micro-nano zinc odor-removing spray for the sheep farm according to claim 6, which is characterized by comprising the following steps: in the step 1.2, the reaction temperature is 40-80 ℃, and the stirring speed is 2000-5000 rpm.
9. The preparation method of the micro-nano zinc odor-removing spray for the sheep farm according to claim 6, which is characterized by comprising the following steps: in the step 1.2, the volume ratio of the zinc salt aqueous solution to the hydrazine hydrate solution is 1:1, and the volume ratio of the hydrazine hydrate solution to the WPO reverse microemulsion system is 1: 3.5-4; the zinc salt is one or more of zinc sulfate, zinc nitrate, zinc citrate and zinc gluconate.
10. The preparation method of the micro-nano zinc odor-removing spray for the sheep farm according to claim 1, which is characterized by comprising the following steps: the step 2 further comprises:
step 2.1: transferring the zinc particle solution prepared in the step 1 to the next reaction kettle, stirring at 60 ℃, wherein the stirring speed is 2000-5000rpm, and simultaneously introducing high-speed air flow to form a cavitation phenomenon;
step 2.2: reacting for 5 hours to prepare the micro-nano zinc solution.
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JP2003047647A (en) * 2001-08-06 2003-02-18 Nippon Zeon Co Ltd Deodorant and fiber product using it
CN102872852A (en) * 2012-10-31 2013-01-16 吉林大学 Supported zinc oxide photocatalyst and preparation method thereof
CN105214623A (en) * 2015-10-31 2016-01-06 仇颖超 A kind of preparation method of micro heavy Triafol T porous microsphere sorbent
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