High-efficiency environment-friendly medicament for aquaculture and preparation method thereof

Abstract

The present application relates to the technical field of water treatment, in particular to a kind of high-efficiency environmental protection medicament for aquaculture and a preparation method thereof, the high-efficiency environmental protection medicament for aquaculture, by weight percentage 100%, comprising the following raw materials: flocculant 61.5-66%, calcium supplement 3-3.5%, and the balance is modified medical stone powder.The high-efficiency environmental protection medicament for aquaculture prepared by the present application has good adsorption effect on ammonia nitrogen and nitrite nitrogen in aquaculture, and can improve the transparency of water.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of water treatment, in particular to a high-efficiency environmental protection agent for aquaculture and a preparation method thereof. BACKGROUND

[0002] In the process of the intensive and high-density development of the aquaculture industry, the pollution of the aquaculture water body has become the core problem restricting the healthy development of the industry. In the process of aquaculture, organic pollutants such as residual feed, excretion of aquatic organisms, and plant and animal residues continue to accumulate, combined with the input of external water source eutrophication, which leads to the rapid increase of the concentration of pollutants such as chemical oxygen demand (COD), ammonia nitrogen (NH3-N), and nitrite nitrogen (NO2 - -N) in the aquaculture water body, which may cause stress reaction, immune decline, and even large-scale death of the aquaculture organisms, resulting in huge economic losses.

[0003] The current water body treatment technology for aquaculture is divided into physical treatment technology and chemical treatment technology. The physical treatment technology usually uses sedimentation tanks, filter tanks, and the like to remove suspended particulate matter in the water body, but the removal rate of dissolved organic pollutants and nitrogen and phosphorus nutrients is insufficient, and frequent backwashing is required, which has high operation and maintenance costs. The chemical treatment technology often uses alum, polyaluminum chloride, and other inorganic flocculants to quickly reduce the turbidity of the water body. For example, patent CN106219705B discloses a method for improving the bottom of an aquaculture pond, specifically relates to a pure natural flocculant for improving the bottom of an aquaculture pond. The pure natural flocculant for improving the bottom of an aquaculture pond includes the following components in parts by weight: rice hull 30-40 parts, bean straw 21-27 parts, sweet potato leaf 21-28 parts, starch 20-25 parts, mulberry leaf 18-25 parts, waterweed 15-22 parts, banana peel 12-17 parts, galactomannan gum 12-18 parts, bentonite 11-18 parts, and zeolite powder 9-15 parts. The advantages of the invention are good bottom improvement effect, natural non-toxicity, and no secondary pollution. The formula contains as many natural raw materials as rice hull, bean straw, sweet potato leaf, and mulberry leaf. The source, season, place of origin, and treatment method of these raw materials will cause great differences in their components (such as cellulose, lignin, and soluble substance content). This leads to inconsistent effects of different batches of products, making it difficult to achieve standardized and stable bottom improvement effects.

[0004] Patent CN117446886B discloses a water quality improver for aquatic products and a preparation method thereof, wherein the water quality improver contains the following components by weight fraction: nano-silver: 10-20 parts; molasses: 0.5-1.8 parts; zinc oxide: 10-20 parts; humic acid: 1-5 parts; composite flocculant: 5-15 parts; selenium: 1-5 parts; modified straw: 10-20 parts. The application can have stronger adsorption performance and flocculation effect through hydroxylamino reaction of active amino and hydroxyl groups, and synergistic effect of nano-silver coated zinc oxide reaction; copper sulfate and yeast bacteria occur bridging reaction, so that they have stronger adsorption performance and flocculation effect, and the yeast bacteria can produce biologically active substances such as proteins through their own metabolism, and the proteins can have the ability to combine with copper ions to kill bacteria; further modification treatment makes it have high adsorption performance and high thermal stability. However, the nano-silver and zinc oxide in the formula have toxicity to the organs of crustaceans such as fish, shrimp and crab.

[0005] Therefore, there is an urgent need to develop a high-efficiency environmentally friendly pesticide with stable product effect for aquatic breeding. SUMMARY

[0006] In order to overcome the shortcomings of the prior art, the present application provides a high-efficiency environmentally friendly pesticide for aquatic breeding and a preparation method thereof, which has good adsorption effect on ammonia nitrogen and nitrite nitrogen in aquatic breeding and can improve water transparency.

[0007] In order to achieve the above purpose, the technical scheme adopted by the present application is:

[0008] The first aspect of the present application provides a high-efficiency environmentally friendly pesticide for aquatic breeding, which contains the following raw materials in 100% by weight: flocculant 61.5-66%, calcium supplement 3-3.5%, and the balance is modified maifanite powder.

[0009] In some embodiments, the flocculant is a mixture of polymeric ferric sulfate, iron hydroxide and polymeric aluminum ferric silicate.

[0010] In some embodiments, the mass ratio of polymeric ferric sulfate, iron hydroxide and polymeric aluminum ferric silicate is (12-13):(18-19):1.

[0011] In some embodiments, the calcium supplement is calcium sulfate dihydrate.

[0012] In some embodiments, the preparation method of the modified maifanite powder comprises the following steps:

[0013] (1) The ball of medical stone is ground and crushed, sieved, soaked in sodium hydroxide solution for 4-6h, washed to neutral, to obtain pretreated medical stone powder; the pretreated medical stone powder and silane coupling agent are added into methanol solution, stirred for 60-80min, then initiator and 2-phenyl acrylic acid are added, heated to 70-80℃ and stirred for 1-2h, washed and dried, to obtain silane modified medical stone powder;

[0014] (2) Zirconium tetrachloride and 2-amino terephthalic acid are added into a mixed solution of DMF and hydrochloric acid, ultrasonically treated, then the silane modified medical stone powder is added, heated at 115-125℃ for 24-36h, centrifuged, the solid is collected, washed, purified and dried, to obtain modified medical stone powder.

[0015] The traditional water purification material for aquaculture directly uses medical stone or is simply physically compounded. The adsorption capacity of the material for ammonia nitrogen, nitrite and other pollutants is limited mainly depending on the physical adsorption and ion exchange of medical stone. The modified medical stone powder has a multi-stage pore structure, can adsorb ammonia nitrogen, nitrite and other pollutants in water, and can effectively purify water. The possible reasons are as follows: firstly, the silane coupling agent is used to modify the surface of the pretreated medical stone, and the organic functional groups are firmly anchored on the surface of the medical stone. In the presence of the initiator, the functional groups undergo graft copolymerization with 2-phenyl acrylic acid, and a large number of carboxyl groups are introduced on the surface of the medical stone, which can coordinate with part of zirconium ions, and the pore structure formed can capture and lock the pollutants in the pore. At the same time, the medical stone slowly releases potassium, sodium, calcium, magnesium, silicon and other trace elements, providing essential mineral nutrients for aquaculture organisms and stabilizing the pH and hardness of the water. In addition, the modified medical stone powder obtained by the solvothermal method is connected by chemical bonds between monomers, which is not easy to fail under long-term water flow impact and long-term soaking, ensuring the durability of the function.

[0016] In some embodiments, the mass ratio of the pretreated medical stone powder to 2-phenyl acrylic acid in step (1) is 1:(0.1-0.4).

[0017] In some embodiments, the mass ratio of zirconium tetrachloride to 2-amino terephthalic acid in step (2) is 1:(0.4-0.6).

[0018] In some embodiments, the mass ratio of zirconium tetrachloride to silane modified medical stone powder in step (2) is 1:(10-13).

[0019] The second aspect of the present application provides a preparation method of an efficient and environmentally friendly medicament for aquaculture, comprising the following steps:

[0020] Under the condition that the environmental humidity is less than 60%, the flocculating agent, calcium supplement and modified medical stone powder are added into a mixing device and stirred to obtain the product.

[0021] In some embodiments, the stirring time is 15-30 min, and the rotation speed is 30-50 rpm.

[0022] Compared with the prior art, the present application has the following beneficial effects:

[0023] 1. The present application uses flocculants, calcium supplements and modified maifanite powder to prepare a high-efficiency environmentally friendly medicament for aquaculture, which can effectively absorb pollutants such as ammonia nitrogen and nitrite nitrogen in aquaculture, and improve water transparency.

[0024] 2. The present application first uses a silane coupling agent to modify the surface of the pretreated maifanite, firmly anchoring organic functional groups on the surface of the maifanite. In the presence of an initiator, these functional groups undergo graft copolymerization with 2-phenyl acrylic acid, introducing a large number of active sites such as carboxyl groups on the surface of the maifanite, solving the problem of limited adsorption capacity of traditional aquaculture water purification materials for ammonia nitrogen, nitrite and other pollutants.

[0025] 3. The prepared silane-modified maifanite powder can coordinate with part of zirconium ions, forming a pore structure that can capture and lock pollutants in the pores, while the maifanite slowly releases potassium, sodium, calcium, magnesium, silicon and other trace elements, providing essential mineral nutrients for cultured organisms and stabilizing the pH and hardness of the water. In addition, the modified maifanite powder obtained by the solvothermal method is connected by chemical bonds between monomers, which is not easy to fail under long-term water flow impact and long-term soaking, ensuring the durability of the function. DETAILED DESCRIPTION

[0026] The present application will be described below in conjunction with specific embodiments. It should be noted that the following examples of the examples and comparative examples are only used to illustrate the present application, but not to limit the present application. Other combinations and various modifications within the concept of the present application can be made without departing from the spirit or scope of the present application.

[0027] In order to facilitate the implementation of the present application by those skilled in the art, the following explains some of the raw materials and manufacturers of the examples and comparative examples:

[0028] The compounds and related reagents used in the following examples and comparative examples can be purchased from the market, among which the maifanite powder is purchased from the Lingshou County Malin Mineral Product Processing Factory; the polymeric ferric sulfate (content 22%) is purchased from Foshan Sanzhong Environmental Protection Technology Co., Ltd.; and the polymeric aluminum ferric silicate (content 46%) is purchased from Chengdu Lanji Technology Co., Ltd.

[0029] The post-treatment steps such as "washing", "drying", "purification", "centrifugation" and the detection methods of COD value, transparency, nitrite and ammonia nitrogen content used in the following description are the routine operations of the skilled in the art, which can be selected by the actual operation.

[0030] Preparation Example 1

[0031] The preparation method of modified zeolite powder-1 comprises the following steps:

[0032] (1) 200 g of zeolite was ground and sieved through a 325 mesh sieve, then soaked in 1 kg of 1 mol / L sodium hydroxide solution for 5 h, and washed until the pH was 7 to obtain pretreated zeolite powder; 100 g of the pretreated zeolite powder and 10 g of γ-glycidoxypropyltrimethoxysilane were added to 500 ml of 90 wt% methanol solution, stirred for 70 min, then 10 g of dibenzoyl peroxide and 25 g of 2-phenylacrylic acid were added, and the temperature was raised to 75°C and stirred for 1.5 h, then washed and dried to obtain silane-modified zeolite powder;

[0033] (2) 1 g of zirconium tetrachloride and 0.5 g of 2-amino terephthalic acid were added to a mixture of 500 ml of DMF and 40 ml of hydrochloric acid, and ultrasonically treated for 30 min, then 12 g of the silane-modified zeolite powder was added and heated at 120°C for 30 h, centrifuged, the solid was collected, washed, purified by a Soxhlet extraction device, and dried to obtain modified zeolite powder-1.

[0034] Preparation Example 2

[0035] The preparation method of modified zeolite powder-2 is the same as that of Preparation Example 1, except that the amount of 2-phenylacrylic acid added in step (1) is 45 g.

[0036] Preparation Example 3

[0037] The preparation method of modified zeolite powder-3 is the same as that of Preparation Example 1, except that the amount of 2-amino terephthalic acid added in step (2) is 7 g.

[0038] Preparation Example 4

[0039] The preparation method of modified zeolite powder-4 is the same as that of Preparation Example 1, except that the amount of silane-modified zeolite powder added in step (2) is 9 g.

[0040] Preparation Example 5

[0041] The preparation method of modified zeolite powder-5 comprises the following steps:

[0042] (1) 200g of the zeolite ball was ground and sieved through a 325 mesh sieve, then soaked in 1kg of 1mol / L sodium hydroxide solution for 5h, washed to pH=7 to obtain pretreated zeolite powder; 100g of the pretreated zeolite powder and 10g of γ-glycidoxypropyltrimethoxysilane were added to 500ml of 90wt% methanol solution, stirred for 70min, then 10g of dibenzoyl peroxide and 25g of 2-phenylacrylic acid were added, and the mixture was stirred at 75℃ for 1.5h, washed and dried to obtain modified zeolite powder-5.

[0043] Example 1

[0044] An efficient and environmentally friendly aquaculture agent, with a weight percentage of 100%, comprises the following raw materials: flocculant 64%, calcium sulfate dihydrate 3.3%, and the rest is modified zeolite powder-1.

[0045] The flocculant is a mixture of polymeric ferric sulfate, iron hydroxide and polymeric aluminum ferric silicate, and the mass ratio of the three is 12.5:18.5:1.

[0046] The preparation method of the efficient and environmentally friendly aquaculture agent in this embodiment comprises the following steps:

[0047] Under the condition of environmental humidity of 50%, the flocculant, calcium sulfate dihydrate and modified zeolite powder-1 are added to the mixing equipment and stirred at a speed of 40rpm for 20min to obtain the product.

[0048] Example 2

[0049] An efficient and environmentally friendly aquaculture agent, with a weight percentage of 100%, comprises the following raw materials: flocculant 61.5%, calcium sulfate dihydrate 3%, and the rest is modified zeolite powder-1.

[0050] The flocculant is a mixture of polymeric ferric sulfate, iron hydroxide and polymeric aluminum ferric silicate, and the mass ratio of the three is 12:18:1.

[0051] The preparation method of the efficient and environmentally friendly aquaculture agent in this embodiment comprises the following steps:

[0052] Under the condition of environmental humidity of 50%, the flocculant, calcium sulfate dihydrate and modified zeolite powder-1 are added to the mixing equipment and stirred at a speed of 30rpm for 30min to obtain the product.

[0053] Example 3

[0054] An efficient and environmentally friendly aquaculture agent, with a weight percentage of 100%, comprises the following raw materials: flocculant 66%, calcium sulfate dihydrate 3.5%, and the rest is modified zeolite powder-1.

[0055] The flocculating agent is a mixture of polymeric ferric sulfate, ferric hydroxide and polymeric aluminum ferric silicate, and the mass ratio of the three is 13:19:1.

[0056] The preparation method of the high-efficiency environmentally friendly medicament for aquaculture in the embodiment comprises the following steps:

[0057] The flocculating agent, calcium sulfate dehydrate and modified maifanite powder-1 are added into a mixing device under the condition of 50% environmental humidity, and stirred at a rotating speed of 50 rpm for 15 min, to obtain the product.

[0058] Example 4

[0059] The high-efficiency environmentally friendly medicament for aquaculture and the preparation method thereof are the same as those in Example 1, except that the modified maifanite powder-1 is replaced by an equal amount of modified maifanite powder-2.

[0060] Example 5

[0061] The high-efficiency environmentally friendly medicament for aquaculture and the preparation method thereof are the same as those in Example 1, except that the modified maifanite powder-1 is replaced by an equal amount of modified maifanite powder-3.

[0062] Example 6

[0063] The high-efficiency environmentally friendly medicament for aquaculture and the preparation method thereof are the same as those in Example 1, except that the modified maifanite powder-1 is replaced by an equal amount of modified maifanite powder-4.

[0064] Example 7

[0065] The high-efficiency environmentally friendly medicament for aquaculture and the preparation method thereof are the same as those in Example 1, except that the modified maifanite powder-1 is replaced by an equal amount of modified maifanite powder-5.

[0066] Comparative Example 1

[0067] The high-efficiency environmentally friendly medicament for aquaculture and the preparation method thereof are the same as those in Example 1, except that the modified maifanite powder-1 is replaced by an equal amount of pretreated maifanite powder, and the preparation method of the pretreated maifanite powder is the same as step (1) in Preparation Example 1.

[0068] Performance test

[0069] The experiment was carried out in a certain farm in Guangzhou. The size of the ponds was 6 mu of water surface area, and the average water depth of the ditches was 1 m. The ponds mainly cultivated grass carp. When the water color of the ponds was turbid, the bottom quality was poor, and foam appeared on the surface of the ponds from time to time, the medicaments obtained in the examples were added to 8 ponds, and the dosage was 300 g / mu. No medicament was added as a blank control. The COD value, transparency, nitrite and ammonia nitrogen content of the water body were tested after 2 days of using the medicament.

[0070] The experimental results are shown in Table 1:

[0071] Table 1

[0072]

[0073] It can be known from the comparison of the experimental data of Examples 1-3 in Table 1 that the high-efficiency environmental protection agent obtained has good water treatment effect; it can be known from the comparison of Example 4 and Example 1 that the change of the ratio of the pretreated medical stone powder and 2-phenylpropenoic acid may block the pore channel, resulting in the decrease of the water treatment effect of the high-efficiency environmental protection agent; it can be known from the comparison of Example 5 and Example 1 that the change of the ratio of zirconium tetrachloride and 2-amino terephthalic acid may affect the decrease of the coordination site of zirconium tetrachloride and silane modified medical stone powder, and further cause the decrease of the adsorption capacity of the modified medical stone powder, so that the water treatment effect of the obtained high-efficiency environmental protection agent is reduced; it can be known from the comparison of Example 6 and Example 1 that the change of the ratio of zirconium tetrachloride and silane modified medical stone powder may cause pore blockage, so that the pollutants cannot be locked in the pore channel, and the water treatment effect of the high-efficiency environmental protection agent is reduced; it can be known from the comparison of Example 7 and Comparative Example 1 and Example 1 that the use of silane modified medical stone powder or pretreated medical stone powder may cause the decrease of the water treatment effect of the water treatment agent due to the small number of adsorption sites.

[0074] The above is only the preferred embodiment of the present application, and does not limit the present application in any form. Although the present application has been disclosed as above with the preferred embodiment, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above disclosed technical content without departing from the technical solution of the present application, and any simple modification, equivalent change and modification of the above embodiment according to the technical essence of the present application are still within the scope of the technical solution of the present application.

Claims

1. An efficient and environmentally friendly medicament for aquaculture, characterized by, The flocculant is a mixture of polymeric ferric sulfate, ferric hydroxide and polymeric aluminum ferric silicate, and the modified medical stone powder is prepared by the following steps: The modified medical stone powder is prepared by the following steps: (1) After ball milling and crushing, the medical stone is sieved, soaked in sodium hydroxide solution for 4-6 h, washed to neutral, and then pretreated medical stone powder is obtained. The pretreated medical stone powder and silane coupling agent are added into methanol solution, stirred for 60-80 min, then initiator and 2-phenyl acrylic acid are added, heated to 70-80℃ and stirred for 1-2 h, washed, dried, and then silane modified medical stone powder is obtained; (2) Zirconium tetrachloride and 2-amino terephthalic acid are added into a mixed solution of DMF and hydrochloric acid, and then ultrasonic treatment is performed. After that, the silane modified medical stone powder is added and heated at 115-125℃ for 24-36 h. Centrifugation is performed, and then the solid is collected, washed, purified, dried, and then modified medical stone powder is obtained; The mass ratio of the pretreated medical stone powder to 2-phenyl acrylic acid in step (1) is 1:(0.1-0.4); The mass ratio of zirconium tetrachloride to 2-amino terephthalic acid in step (2) is 1:(0.4-0.6); The mass ratio of zirconium tetrachloride to silane modified medical stone powder in step (2) is 1:(10-13).

2. The high-efficiency environmentally friendly aquaculture drug according to claim 1, characterized in that, The mass ratio of polymeric ferric sulfate, ferric hydroxide and polymeric aluminum ferric silicate is (12-13):(18-19):

1.

3. The high-efficiency environmentally friendly aquaculture drug according to claim 1, characterized in that, The calcium supplement is calcium sulfate dehydrate.

4. A method for preparing the high-efficiency environmentally friendly aquaculture agent according to any one of claims 1 to 3, characterized in that, The preparation method comprises the following steps: The flocculant, calcium supplement and modified medical stone powder are added into a mixing device and stirred under the condition that the environmental humidity is less than 60%, and then the product is obtained.

5. The method for preparing the highly efficient and environmentally friendly aquaculture agent according to claim 4, characterized in that, The stirring time is 15-30 min, and the rotating speed is 30-50 rpm.

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