CN111717980A - Sustained-release oxygen increasing agent and preparation method and application thereof - Google Patents
Sustained-release oxygen increasing agent and preparation method and application thereof Download PDFInfo
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- CN111717980A CN111717980A CN202010565169.7A CN202010565169A CN111717980A CN 111717980 A CN111717980 A CN 111717980A CN 202010565169 A CN202010565169 A CN 202010565169A CN 111717980 A CN111717980 A CN 111717980A
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000001301 oxygen Substances 0.000 title claims abstract description 125
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 125
- 230000001965 increasing effect Effects 0.000 title claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 67
- 238000013268 sustained release Methods 0.000 title claims abstract description 38
- 239000012730 sustained-release form Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 61
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 58
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 150000002148 esters Chemical class 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 12
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 12
- 238000009360 aquaculture Methods 0.000 claims abstract description 8
- 244000144974 aquaculture Species 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 14
- 239000012670 alkaline solution Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 4
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 238000006213 oxygenation reaction Methods 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000033116 oxidation-reduction process Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 241001465754 Metazoa Species 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004343 Calcium peroxide Substances 0.000 description 3
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 3
- 235000019402 calcium peroxide Nutrition 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- HUPXVBJTMJUPEX-UHFFFAOYSA-L disodium hydrogen peroxide hydrogen sulfate chloride Chemical compound [Cl-].[Na+].OO.S(=O)(=O)([O-])O.[Na+] HUPXVBJTMJUPEX-UHFFFAOYSA-L 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007891 compressed tablet Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K61/00—Culture of aquatic animals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Animal Husbandry (AREA)
- Zoology (AREA)
- Marine Sciences & Fisheries (AREA)
- Medicinal Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a slow-release oxygen increasing agent and a preparation method and application thereof, belonging to the technical field of aquatic products. The invention provides a sustained-release oxygen increasing agent which is prepared from the following raw materials in parts by weight: 0.2-2 parts of acrylic resin solution by mass of acrylic resin solid; 20 parts of hydrogen peroxide; 5-15 parts of urea and 0.1-2.5 parts of sodium chloride; 2-5 parts of sodium sulfate; the acrylic resin solution is prepared from an acrylic monomer raw material, wherein the acrylic monomer comprises a fat-soluble ester monomer and a water-soluble acid monomer. The slow-release oxygen increasing agent is mainly used in the technical field of aquatic products, is easy to obtain preparation raw materials, simple to operate, high in oxygen content, stable in property, slow in oxygen release, safe, environment-friendly and convenient to use, can be used in a powder form and a tabletting form, and can be effectively used for increasing oxygen in aquaculture water.
Description
Technical Field
The invention belongs to the technical field of aquatic products, and particularly relates to a slow-release oxygen increasing agent as well as a preparation method and application thereof.
Background
With the rapid development of aquaculture industry, high-density culture is inevitable, and the problems follow are that the eutrophication of water bodies causes the deterioration of water quality and the increase of oxygen consumption of culture water. In addition, in the growing period of aquatic animals, the natural dissolved oxygen of the water body can not meet the requirement of the aquatic animals on quick growth, and the oxygen increasing with lasting effect is also necessary. Therefore, the research on the persistent oxygen increasing method has important practical value.
The existing oxygenation methods include physical oxygenation, chemical oxygenation and biological oxygenation. Among them, chemical oxygen increasing is widely used because of its convenience. Common chemical oxygen increasing agents generally comprise hydrogen peroxide, sodium percarbonate, peroxyacetic acid, sodium chloride-sodium sulfate-hydrogen peroxide adduct, urea peroxide, calcium peroxide and the like. The hydrogen peroxide is liquid, needs to be diluted when in use, and is inconvenient to store, transport and use. Sodium percarbonate and peroxyacetic acid easily cause the change of the pH value of the water body. The sodium chloride-sodium sulfate-hydrogen peroxide adduct is more stable but contains less oxygen. The urea peroxide has a high oxygen content but relatively poor stability. The speed of decomposing and releasing oxygen of calcium peroxide is slightly slower than that of sodium percarbonate, but the calcium peroxide has poor solubility and is not suitable for multiple purposes, and a solid film is easily formed on the surface of the water body to isolate the natural fusion of air oxygen into the water body. Therefore, the chemical oxygen increasing agent is difficult to satisfy the requirements of lasting effect and stable oxygen increasing in the culture water body.
Disclosure of Invention
The invention provides a slow-release oxygen increasing agent, a preparation method and application thereof, the slow-release oxygen increasing agent has stable property and high oxygen content, can increase oxygen continuously, is suitable for increasing oxygen continuously for aquaculture water in a growth period when aquatic animals have more oxygen demand, and has no obvious influence on the pH value and the oxidation-reduction potential of a water body.
The invention provides a sustained-release oxygen increasing agent which is prepared from the following raw materials in parts by weight:
0.2-2 parts of acrylic resin solution by mass of acrylic resin solid; 20 parts of hydrogen peroxide; 5-15 parts of urea and 0.1-2.5 parts of sodium chloride; 2-5 parts of sodium sulfate; the acrylic resin solution is prepared from an acrylic monomer raw material, wherein the acrylic monomer comprises a fat-soluble ester monomer and a water-soluble acid monomer.
Further, the mass ratio of the fat-soluble ester monomer to the water-soluble acid monomer is (8.5-7.5): (1.5-2.5).
Further, the fat-soluble ester monomer comprises at least one of butyl acrylate, butyl methacrylate and methyl methacrylate;
the water-soluble acid monomer comprises at least one of acrylic acid and methacrylic acid.
Further, the concentration of the acrylic resin solution is 16-25 wt%;
the concentration of the hydrogen peroxide is 30-32 wt%.
Further, the acrylic resin solution is prepared by the following steps:
mixing 100 parts of acrylic acid monomer, 200 parts of distilled water, 500 parts of emulsifier, 0.5-3 parts of initiator and 0.05-0.5 part of initiator, stirring and heating for refluxing for 2 hours at 80 ℃, cooling, and adding alkaline solution for neutralization to obtain acrylic resin solution with the concentration of 16-25 wt%.
Further, the emulsifier comprises at least one of fatty alcohol-polyoxyethylene ether AEO-7, polyethylene glycol PEG-400 and peregal O-10;
the initiator comprises at least one of potassium persulfate, ammonium persulfate and perbenzoic acid.
Further, the concentration of the alkaline solution is 5-8 wt%;
the alkaline solution includes at least one of sodium hydroxide or potassium hydroxide.
Further, the oxygen increasing agent is present in the form of powder or compressed tablet.
The invention also provides a preparation method of the sustained-release oxygen increasing agent, which comprises the following steps:
mixing hydrogen peroxide and acrylic resin solution; adding urea, sodium chloride and sodium sulfate, and mixing; drying at constant temperature of 30-60 ℃ to obtain the slow-release oxygen increasing agent.
The invention also provides the application of the sustained-release oxygen increasing agent in aquaculture.
The invention has the following advantages:
the resin clathrate slow-release oxygen-increasing agent for aquatic products is prepared from an acrylic resin solution, hydrogen peroxide, urea and an inorganic salt. The acrylic resin solution is obtained by scientifically compounding a fat-soluble ester monomer and a water-soluble acid monomer according to a certain proportion, the water-soluble solubility of the obtained acrylic resin is slightly soluble, and the acrylic resin is difficult to dissolve in water after being dried, so that the hydrogen peroxide is convenient to stabilize. Meanwhile, functional atoms and groups (such as ester groups) in the resin obtained by polymerization also have a stabilizing effect on hydrogen peroxide. In addition, the acrylic resin is directly used in the form of solution after being synthesized, so that the reduction of the solubility of the resin after being dried is avoided.
The method has the advantages of easily available raw materials, simple operation, high oxygen content, stable property, slow oxygen release, safety, environmental protection and convenient use, can be used in a powder form and a tabletting form, and can be effectively used for oxygenation of aquaculture water.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
One embodiment of the invention provides a sustained-release oxygen increasing agent, which is prepared from the following raw materials:
0.2-2 parts of acrylic resin solution by mass of acrylic resin solid; 20 parts of hydrogen peroxide; 5-15 parts of urea and 0.1-2.5 parts of sodium chloride; 2-5 parts of sodium sulfate; the acrylic resin solution is prepared from an acrylic monomer raw material, wherein the acrylic monomer comprises a fat-soluble ester monomer and a water-soluble acid monomer.
The slow-release oxygen increasing agent provided by the embodiment of the invention is prepared from an acrylic resin solution, hydrogen peroxide, urea and an inorganic salt. The resin inclusion compound can stabilize hydrogen peroxide to release oxygen, has slightly soluble solubility in water, can be used for aquaculture, and realizes continuous long-term stable oxygenation. The oxygen increasing agent has the advantages of cheap and easily available raw materials, high oxygen content, stable property, slow oxygen release, safety, environmental protection and convenient use.
In an embodiment of the present invention, the mass ratio of the fat-soluble ester monomer to the water-soluble acid monomer is (8.5-7.5): (1.5-2.5). The solubility of the prepared polymeric acrylic resin outside the proportion range is not favorable for stabilizing hydrogen peroxide, thereby influencing the slow release effect of the slow release oxygen increasing agent.
In an embodiment of the present invention, the suitable fat-soluble ester monomer includes at least one of butyl acrylate, butyl methacrylate, and methyl methacrylate.
In one embodiment of the present invention, the water-soluble acid monomer includes at least one of acrylic acid and methacrylic acid.
In one embodiment of the present invention, the concentration of the acrylic resin solution is 16 to 25 wt%. 0.2 to 2g of the acrylic resin solution, wherein 0.2 to 2g is calculated by the solid mass of the acrylic resin.
In one embodiment of the invention, the concentration of the hydrogen peroxide is 30-32 wt%.
It should be noted that, in one embodiment of the present invention, the oxygenator may be in a solid form, for example, in the form of powder or tablet. The powder acrylic resin inclusion compound slow-release oxygen increasing agent is in a micro-dispersion state in water, so that the oxygen can be released continuously, and the storage, the transportation and the use are convenient.
In one embodiment of the present invention, a suitable acrylic resin solution is prepared by the steps of:
mixing 100 parts of acrylic acid monomer, 200 parts of distilled water, 500 parts of emulsifier, 0.5-3 parts of initiator and 0.05-0.5 part of initiator, stirring and heating for refluxing for 2 hours at 80 ℃, cooling, and adding alkaline solution for neutralization to obtain acrylic resin solution with the concentration of 16-25 wt%.
Specifically, 75-85 parts of fat-soluble ester monomer, 15-25 parts of water-soluble acid monomer, 500 parts of distilled water 200-containing organic solvent, 0.5-3 parts of emulsifier and 0.05-0.5 part of initiator are mixed in parts by weight, stirred, heated and refluxed for 2 hours at the temperature of 80 ℃, cooled and added into alkaline solution for neutralization to obtain acrylic resin solution with the concentration of 16-25 wt%.
The suitable fat-soluble ester monomers and water-soluble acid monomers are as described above.
In the embodiment of the invention, fat-soluble ester monomers and water-soluble acid monomers react under the action of an initiator and an emulsifier, and alkali is added for neutralization to obtain an acrylic resin solution. The obtained acrylic resin solution, hydrogen peroxide, urea, sodium chloride and sodium sulfate are utilized to form a resin inclusion compound, so that the sustained-release oxygen increasing agent which can increase oxygen durably and stably and has no influence on the pH and the potential of a water body is obtained. The amount of the acrylic resin is known from the amount of the acrylic monomer added, and the mass concentration of the acrylic resin solution is determined by adding the alkaline solution. The acrylic resin solution in the concentration range is beneficial to preparing the inclusion compound, and the drying time is moderate. In addition, the acrylic resin is directly used in the form of solution after being synthesized, so that the reduction of the solubility of the resin after being dried is avoided.
In one embodiment of the invention, the suitable emulsifier comprises at least one of fatty alcohol-polyoxyethylene ether AEO-7, polyethylene glycol PEG-400 and peregal O-10.
In one embodiment of the present invention, suitable initiators include at least one of potassium persulfate, ammonium persulfate, and perbenzoic acid.
In one embodiment of the present invention, the concentration of the alkaline solution is 5-8 wt%.
In one embodiment of the present invention, the alkaline solution comprises at least one of sodium hydroxide or potassium hydroxide.
The following also provides a preparation method of any oxygen increasing agent provided by the above embodiment of the invention.
In one embodiment of the present invention, a method for preparing a sustained-release oxygen-increasing agent is provided, which comprises the following steps:
mixing hydrogen peroxide and acrylic resin solution; adding urea, sodium chloride and sodium sulfate, and drying at constant temperature of 30-60 ℃ to obtain the product.
Specifically, the acrylic resin solution is slowly added into hydrogen peroxide under stirring; continuously stirring, sequentially adding urea, sodium chloride and sodium sulfate, and mixing; drying at constant temperature of 30-60 ℃ to obtain the slow-release oxygen increasing agent.
The method has easily obtained raw materials and simple operation. The oxygen increasing agent obtained by the method has high oxygen content, stable property, slow oxygen release, safety, environmental protection and convenient use. The method can obtain solid oxygen increasing agent, and is convenient for storage and use.
The embodiment of the invention also provides application of any one of the sustained-release oxygen increasing agents in aquaculture of aquatic products, in particular to the growth period of aquatic animals.
The oxygen increasing agent provided by the present invention, the preparation method and the application thereof will be further explained in detail with reference to the specific examples.
Example 1Preparation of acrylic resin solution
Into a round-bottomed flask were charged 5g of butyl acrylate, 3g of butyl methacrylate, 2g of acrylic acid, 30g of distilled water, 0.2g of AEO-7 and 0.02g of potassium persulfate. Heated to reflux for 2h at 80 ℃ with stirring. After cooling, the resulting mixture was neutralized with 10mL of 5.5 wt% sodium hydroxide solution under stirring to give a 20 wt% polyacrylic resin solution, which was then stored in a sealed container.
Example 2Preparation of acrylic resin solution
Into a round-bottomed flask were charged 40g of butyl acrylate, 40g of butyl methacrylate, 20g of methacrylic acid, 300g of distilled water, 2g of PEG-400, and 0.1g of potassium persulfate. The mixture was heated under reflux for 2h at 85 ℃ with stirring. After cooling, the resulting mixture was neutralized with 124mL of 6 wt% sodium hydroxide solution under stirring to give a solution of a polyacrylic resin having a concentration of 19 wt%, and the solution was stored under sealed conditions.
Example 3Preparation of acrylic resin solution
Into a round-bottomed flask were charged 50g of butyl acrylate, 30g of methyl methacrylate, 2g of methacrylic acid, 18g of acrylic acid, 400g of distilled water, 1g of O-10 and 0.1g of potassium persulfate. Heated to reflux at 90 ℃ for 1.5h with stirring. After cooling, the resulting mixture was neutralized with 86mL of 7 wt% sodium hydroxide solution under stirring to obtain a 17 wt% polyacrylic resin solution, which was then stored in a sealed state.
Example 4Preparation of slow-release oxygen increasing agent
20mL of 30% hydrogen peroxide was added to a beaker, and 0.2g (based on the acrylic resin solids) of the acrylic resin solution obtained in example 1 was added with stirring, and after dispersion, stirring was continued, 10g of urea, 1g of sodium chloride, and 3g of sodium sulfate were added in this order. After complete dissolution, the mixture was heated at a constant temperature of 45 ℃ to a constant weight to give 20g of a solid.
Crushed or ground into white powder, and potassium permanganate is used for titrimetric analysis to contain 30.5 wt% of hydrogen peroxide.
Example 5Preparation of slow-release oxygen increasing agent
20mL of 30 wt% hydrogen peroxide was added to a beaker, and 1.2g (based on the acrylic resin solids) of the acrylic resin solution obtained in example 2 was added with stirring, and after dispersion, stirring was continued, and 10g of urea, 1.4g of sodium chloride, and 3g of sodium sulfate were added in this order. After complete dissolution, the mixture was heated at a constant temperature of 40 ℃ to a constant weight to give 21.5g of a solid. The resin content was 5.5 wt%.
Crushed or ground into white powder, and potassium permanganate is used for titrimetric analysis to contain 29.5 wt% of hydrogen peroxide.
Example 6Preparation of slow-release oxygen increasing agent
20mL of 30 wt% hydrogen peroxide was added to a beaker, and 1.8g (based on the acrylic resin solids) of the acrylic resin solution obtained in example 1 was added with stirring, and after dispersion, stirring was continued, 7g of urea, 1g of sodium chloride, and 3g of sodium sulfate were added in this order. After complete dissolution, the mixture was heated at 50 ℃ to constant weight to give 19g of a solid. The resin content was 9.4 wt%.
Crushed or ground into white powder, and potassium permanganate is used for titrimetric analysis to contain 31.7 wt% of hydrogen peroxide.
Comparative example 1Preparation of slow-release oxygen increasing agent
In the same manner as in example 4, an acrylic resin solution was prepared as in example 1, except that the ratio of the fat-soluble ester monomer to the water-soluble acid monomer was different from that in example 1, specifically: 5g of butyl acrylate and 4g of butyl methacrylate; acrylic acid 1 g.
Comparative example 2Preparation of slow-release oxygen increasing agent
In the same manner as in example 5, an acrylic resin solution was prepared as in example 1, except that the ratio of the fat-soluble ester monomer to the water-soluble acid monomer was different from that in example 1, specifically: 5g of butyl acrylate and 4g of butyl methacrylate; acrylic acid 1 g.
Test example 1Experiment of oxygen release effect of sustained-release oxygen increasing agent
1g of the powder of the sustained-release oxygen increasing agent (resin content: 1% by weight) obtained in example 4 was put into a beaker containing 500mL of water, stirred with a glass rod, and dissolved oxygen was measured with an oxygen dissolution apparatus. The theoretical total oxygen increasing amount of the oxygen increasing agent is about 140mg/g, the actually measured dissolved oxygen increasing speed of the dissolved oxygen instrument is 5.57 mg/L.h, the theoretical oxygen increasing time is 2.2d, the actually continuously oxygen releasing time is about 2d (the measurement is carried out by adopting an electronic dissolved oxygen instrument), and the pH value and the oxidation-reduction potential of the water body have no obvious change.
Test example 2Experiment of oxygen release effect of sustained-release oxygen increasing agent
1g of the powder of the sustained-release oxygen increasing agent (resin content: 5.5% by weight) obtained in example 5 was put into a beaker containing 500mL of water, stirred with a glass rod, and dissolved oxygen was measured with an oxygen dissolution apparatus. The actual measurement of the dissolved oxygen increasing speed of the dissolved oxygen instrument is 2.84 mg/L.h, the theoretical oxygen increasing is 4.1d, the actual continuous oxygen release is about 4d, and the pH value and the oxidation-reduction potential of the water body have no obvious change.
Test example 3Experiment of oxygen release effect of sustained-release oxygen increasing agent
1g of the powder of the sustained-release oxygen increasing agent (resin content: 9.4% by weight) obtained in example 6 was put into a beaker containing 500mL of water, stirred with a glass rod, and dissolved oxygen was measured with an oxygen dissolution apparatus. The actually measured increase speed of dissolved oxygen of the dissolved oxygen instrument is 1.45 mg/L.h, the theoretical oxygenation is 8.0d, the actually sustained oxygen release is about 7d, and the pH value and the oxidation-reduction potential of the water body have no obvious change.
Test example 4Application of sustained-release oxygen increasing agent
1g of the powder of the sustained-release oxygen increasing agent (resin content: 1% by weight) obtained in comparative example 1 was put into a beaker containing 500mL of water, stirred with a glass rod, and dissolved oxygen was measured with an oxygen dissolution apparatus. The actually measured increase speed of dissolved oxygen of the dissolved oxygen instrument is 7.48 mg/L.h, the theoretical oxygenation is 1.6d, the actual continuous oxygen release is about 1.0d, and the pH value and the oxidation-reduction potential of the water body have no obvious change.
Test example 5Application of sustained-release oxygen increasing agent
1g of the powder of the sustained-release oxygen increasing agent (resin content: 5.5% by weight) obtained in comparative example 2 was put into a beaker containing 500mL of water, stirred with a glass rod, and dissolved oxygen was measured with an oxygen dissolution apparatus. The actually measured increase speed of dissolved oxygen of the dissolved oxygen instrument is 7.23 mg/L.h, the theoretical oxygenation is 1.6d, the actual continuous oxygen release is about 1.0d, and the pH value and the oxidation-reduction potential of the water body have no obvious change.
In experimental examples 1 to 3, the sustained-release oxygen increasing agent obtained in examples 4 to 6 was used, and the sustained-release effect was good, the sustained-release time was 2 to 7 days, and the specific duration of sustained-release oxygen release was related to the amount of resin used.
The test example 4 is a slow-release oxygen increasing agent prepared from the acrylic resin solution obtained in the comparative example 1, wherein the monomer ratio of the slow-release oxygen increasing agent is not within the range of the application, and the slow-release oxygen increasing agent is a water-insoluble solid after polymerization and proper neutralization, and the water-insoluble solid is different from the water-soluble solid obtained in the example 1, so that the effect of the slow-release oxygen increasing agent prepared in the example 4-6 is obviously lower than that of the slow-release oxygen increasing agent prepared in the invention, and the actual oxygen is continuously released for about 1 d.
Experimental example 5 with the sustained-release oxygen increasing agent prepared in comparative example 2, the content of the acrylic resin is increased compared with that of the acrylic resin in comparative example 1, and the sustained-release oxygen increasing effect is not well relieved, so that the monomer ratio has a certain influence on the solubility of the acrylic resin solution obtained by polymerization, and further influences the sustained-release effect of the sustained-release oxygen increasing agent.
Test example 6Stability experiment of acrylic resin inclusion compound slow-release oxygen increasing agent
The sustained-release oxygen increasing agent prepared in the embodiments 4 to 6 is sealed in a plastic bag, stored for 3 months at the temperature of 25 to 40 ℃, and the content of hydrogen peroxide is not obviously changed through titration analysis.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The sustained-release oxygen increasing agent is characterized by being prepared from the following raw materials in parts by weight:
0.2-2 parts of acrylic resin solution by mass of acrylic resin solid; 20 parts of hydrogen peroxide; 5-15 parts of urea and 0.1-2.5 parts of sodium chloride; 2-5 parts of sodium sulfate; the acrylic resin solution is prepared from an acrylic monomer raw material, wherein the acrylic monomer comprises a fat-soluble ester monomer and a water-soluble acid monomer.
2. The sustained-release oxygen increasing agent according to claim 1,
the mass ratio of the fat-soluble ester monomer to the water-soluble acid monomer is (8.5-7.5): (1.5-2.5).
3. The sustained-release oxygen increasing agent according to claim 1,
the fat-soluble ester monomer comprises at least one of butyl acrylate, butyl methacrylate and methyl methacrylate;
the water-soluble acid monomer comprises at least one of acrylic acid and methacrylic acid.
4. The sustained-release oxygen increasing agent according to claim 1,
the concentration of the acrylic resin solution is 16-25 wt%;
the concentration of the hydrogen peroxide is 30-32 wt%.
5. The sustained-release oxygen increasing agent according to claim 1,
the acrylic resin solution is prepared by the following steps:
mixing 100 parts of acrylic acid monomer, 200 parts of distilled water, 500 parts of emulsifier, 0.5-3 parts of initiator and 0.05-0.5 part of initiator, stirring and heating for refluxing for 2 hours at 80 ℃, cooling, and adding alkaline solution for neutralization to obtain acrylic resin solution with the concentration of 16-25 wt%.
6. The sustained-release oxygen increasing agent according to claim 5,
the emulsifier comprises at least one of fatty alcohol-polyoxyethylene ether AEO-7, polyethylene glycol PEG-400 and peregal O-10;
the initiator comprises at least one of potassium persulfate, ammonium persulfate and perbenzoic acid.
7. The sustained-release oxygen increasing agent according to claim 5,
the concentration of the alkaline solution is 5-8 wt%;
the alkaline solution includes at least one of sodium hydroxide or potassium hydroxide.
8. The sustained-release oxygen increasing agent according to claim 1,
the oxygen increasing agent is in powder or sheet shape.
9. The method for preparing a sustained-release oxygen increasing agent according to any one of claims 1 to 8, characterized by comprising the steps of:
slowly adding an acrylic resin solution into hydrogen peroxide while stirring; continuously stirring, sequentially adding urea, sodium chloride and sodium sulfate, and mixing; drying at constant temperature of 30-60 ℃ to obtain the slow-release oxygen increasing agent.
10. Use of the slow release oxygen increasing agent according to any one of claims 1 to 8 in aquaculture.
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Cited By (1)
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| CN114271408A (en) * | 2021-12-14 | 2022-04-05 | 珠海天凯生物科技有限公司 | Fish preservative and preparation method thereof |
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