Calcium-containing growth protective agent for bagging-free fruits as well as preparation method and application of calcium-containing growth protective agent

Abstract

The invention discloses a calcium-containing growth protective agent for bagging-free fruits. The calcium-containing growth protective agent is prepared from the following raw materials in parts by mass: 1 to 20 parts of monodisperse micro-nano calcium carbonate filter cake, 0.01 to 0.9 part of ethyoxyl modified polytrisiloxane, 0 to 0.8 part of polyvinyl acetate emulsion, 0 to 0.9 part of glycerol, 0.01 to 0.8 part of modified casein, 0.01 to 0.8 part of enzyme, 0.01 to 0.9 part of sugar alcohol and 5 to 180 parts of water, wherein the polyvinyl acetate emulsion and the glycerol cannot be zero at the same time. The raw materials are mixed in two steps according to a certain sequence, stirred and dispersed to obtain the novel calcium-containing growth protective agent, and the novel calcium-containing growth protective agent is diluted with water until the solid content of calcium carbonate is 0.5%-6% and then is used for bagging-free planting of fruits. The growth protective agent is non-toxic, is sprayed on the surfaces of fruit crops during use, is used for bagging-free fruit planting, has a relatively good physical insect prevention effect and a relatively good repelling effect, can remarkably improve the disease resistance and insect prevention capability of fruits and reduce diseased fruits and insect fruits, does not influence the transmission of visible light, and can remarkably improve the taste and the quality of the fruits planted in a bagging manner compared with the fruits planted in a bagging manner.

Description

Technical Field

[0001] The invention belongs to the field of plant growth agents, and in particular relates to a calcium-containing growth protectant for bag-free fruits and application thereof in bag-free fruit planting. Background Art

[0002] Due to the huge threat of insect pests, current fruit planting generally uses paper bags or plastic bags to cover the fruits for bagging. This physical protection method can effectively prevent insects from harming fruits and is used on a large scale, but it also greatly increases the labor cost in the fruit planting process. Bagging will also affect the photosynthesis of the fruit, causing the taste and nutritional value of the fruit to decline. Therefore, there is an urgent need for an effective bag-free fruit planting method.

[0003] At present, there are a variety of plant growth agents and protective agents on the market, such as gibberellic acid, fresh amino acid ester, anti-drop agent, benzyl aminopurine, etc. for increasing production; amino acid water-soluble fertilizers for cold resistance; lime milk whitening agent for high temperature resistance, etc. The use of these plant growth agents can play a certain role in promoting growth or protecting the growth of crops, fruits, vegetables, etc. However, some of these plant growth agents have complicated preparation methods. For example, the production of gibberellic acid for increasing production requires multiple processes such as strain culture, fermentation, extraction and purification; some components are expensive and the cost of use is high, such as amino acid water-soluble fertilizers; some often have problems such as sedimentation and agglomeration during use, such as lime milk whitening agent; and even some products can cause soil environmental damage. More importantly, these growth agents generally have the problem of single function, often emphasizing the role of production promotion and weak protection against pests and diseases, and cannot replace the function of fruit bagging. Therefore, it is urgent to develop a plant protection product that can effectively protect fruits from pests and diseases, provide certain nutritional support for plant growth, and have low cost of use. Summary of the invention

[0004] In view of the above-mentioned deficiencies of the prior art, the present invention provides a calcium-containing growth protectant for bag-free fruits. The calcium-containing growth protectant is non-toxic and can be directly sprayed onto the surface of fruit crops when used, and can replace traditional fruit bags for bag-free fruit planting. It has good physical insect prevention and repellent effects, can significantly improve the disease resistance and insect resistance of fruits, and reduce diseased and worm-infested fruits.

[0005] The technical solution adopted by the present invention to achieve the above-mentioned purpose is:

[0006] A calcium-containing growth protectant for bag-free fruits, wherein the raw materials thereof are calculated by weight and include: 1 to 20 parts of monodisperse micro-nano calcium carbonate filter cake, 0.01 to 0.9 parts of ethoxy-modified polytrisiloxane, 0 to 0.8 parts of polyvinyl acetate emulsion, 0 to 0.9 parts of glycerol, 0.01 to 0.8 parts of modified casein, 0.01 to 0.8 parts of enzyme, 0.01 to 0.9 parts of sugar alcohol, and 5 to 180 parts of water; wherein the polyvinyl acetate emulsion and the glycerol are not zero at the same time.

[0007] Preferably, the calcium-containing growth protectant for bag-free fruits has raw materials, calculated by weight, comprising: 1 to 20 parts of monodisperse micro-nano calcium carbonate filter cake, 0.05 to 0.5 parts of ethoxy-modified polytrisiloxane, 0.02 to 0.9 parts of polyvinyl acetate emulsion, 0 to 0.9 parts of glycerol, 0.01 to 0.8 parts of modified casein, 0.01 to 0.5 parts of enzyme, 0.01 to 0.9 parts of sugar alcohol, and 5 to 180 parts of water.

[0008] Furthermore, the mass of the monodisperse micro-nano calcium carbonate filter cake is 15 to 75 times, preferably 15 to 40 times, that of the ethoxy-modified polytrisiloxane.

[0009] Furthermore, the mass of water is 3 to 12 times, preferably 5 to 9 times, that of the monodisperse micro-nano calcium carbonate filter cake.

[0010] Furthermore, the mass of the monodisperse micro-nano calcium carbonate filter cake is 15 to 200 times, preferably 18.75 to 50 times, that of the polyvinyl acetate emulsion.

[0011] Furthermore, the mass of the monodisperse micro-nano calcium carbonate filter cake is 25 to 100 times that of the modified casein.

[0012] Furthermore, the mass of the monodisperse micro-nano calcium carbonate filter cake is preferably 25 to 100 times that of the enzyme.

[0013] Furthermore, the mass of the monodisperse micro-nano calcium carbonate filter cake is 15 to 200 times, preferably 50 to 100 times, that of the sugar alcohol.

[0014] According to the above scheme, the characteristics of the monodisperse micro-nano calcium carbonate filter cake are as follows: the moisture content of the filter cake is 35% to 40%, the calcium carbonate particles are cubic or nearly spherical, the average particle size is between 50 and 200 nm, and the particles with a particle size greater than 200 nm are less than 5%; the particle surface is clean, in a monodisperse state, has a small surface energy, and its specific surface area is less than 20m 2 / g, the specific surface area is preferably 16 to 18m 2 / g; the content of harmful metal elements such as cadmium in calcium carbonate is less than 200ppm; the monodisperse micro-nano calcium carbonate filter cake can be stirred and dispersed in an aqueous solution without adding any chemical dispersant, and can remain stably suspended. Specifically, the monodisperse micro-nano calcium carbonate filter cake is dispersed in water to obtain a suspension; when the solid content of the suspension is 2%, it can be stably suspended for more than 2 hours; when the solid content of the suspension is 5% to 30%, it can be stably suspended for more than 14 hours.

[0015] According to the above scheme, the method for preparing the monodisperse micro-nano calcium carbonate filter cake comprises the following steps:

[0016] S1. Prepare calcium carbonate slurry by calcination, digestion, carbonization and other processes. The calcination process is as follows: select limestone with uniform grain size and harmful heavy metal content of less than 400ppm such as cadmium, lead and chromium as raw material, adopt calcination temperature matching the grain size, and obtain quicklime with ideal activity. The activity of quicklime is between 250 and 300mL (4mol / L HCl, 40±1℃, 10min), and the uniformity and consistency are good; the digestion process is as follows: digest the quicklime obtained by the above calcination in hot water at 50 to 90℃ to obtain lime milk; the aging and impurity removal process is as follows: age the lime milk slurry obtained by digestion for 24 to 48h, and obtain refined raw slurry after filtering and impurity removal; the carbonization process is as follows: add water to the refined raw slurry to adjust the solid content to 5% to 12%, and then carbonize it. The starting temperature of carbonization is 10 to 30℃, and the CO2 content is 20% to 40%. Carbonize until the slurry pH reaches 7.5 to 9.0, end carbonization, and obtain calcium carbonate slurry;

[0017] The calcium carbonate particles in the calcium carbonate cooked slurry are nearly spherical or chain-shaped in shape, the average particle size of the nearly spherical particles is 30 to 100 nm, and the average width (lateral dimension) of the chain-shaped particles is 30 to 100 nm;

[0018] S2. Add inorganic salt crystal surface reconstructor and organic crystal surface reconstructor to the calcium carbonate slurry obtained in S1, and then keep it warm at 140-200°C for 1.0-4.0h to obtain a calcium carbonate suspension. Among them, the inorganic crystal surface reconstructor is one or more inorganic salts such as sodium silicate, sodium chloride, aluminum chloride, zinc sulfate, etc., and the amount used is 0.5% to 3% of the dry mass of calcium carbonate; the organic crystal surface reconstructor is one or more organic substances such as ethanol, polyethylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, sodium dodecylbenzene sulfonate, hexadecyltrimethylammonium bromide, sodium dodecyl sulfate, disodium ethylenediaminetetraacetic acid, etc., and the amount used is 1% to 5% of the dry mass of calcium carbonate;

[0019] S3. The calcium carbonate suspension obtained in S2 is filtered and dehydrated to obtain a calcium carbonate filter cake, and the moisture content of the filter cake is controlled between 35% and 40%, that is, a monodisperse micro-nano calcium carbonate filter cake. At this time, it meets the requirements of "the calcium carbonate particles are cubic or nearly spherical, the average particle size is between 50 and 200nm, and the particles with a particle size greater than 200nm are less than 5%; the particle surface is clean, in a monodisperse state, with a small surface energy, and a specific surface area of ​​less than 20m 2 / g; the content of harmful metal elements such as cadmium in calcium carbonate is less than 200ppm; it can be dispersed after stirring in an aqueous solution without adding any chemical dispersant and remain stably suspended.

[0020] According to the above scheme, the sugar alcohol includes one or more of xylitol, ribitol, mannitol, sorbitol, maltitol, erythritol and lactitol.

[0021] According to the above scheme, the modified casein is a milky white viscous liquid with a solid content of 15% to 25%, a viscosity (20° C.) greater than 100 mPa·s, and a pH value (10% aqueous solution) of 7 to 8.

[0022] According to the above scheme, the enzyme is a commercially available agricultural enzyme, which contains agricultural biological agents, polysaccharides, amino acids and other ingredients.

[0023] The method for preparing the calcium-containing growth protectant for bag-free fruits comprises the following steps:

[0024] (1) According to the raw materials of the calcium-containing growth protective agent of the present invention and their mass proportions, 1 to 20 parts of monodisperse micro-nano calcium carbonate filter cake, 0.01 to 0.9 parts of ethoxy-modified polytrisiloxane, 0 to 0.8 parts of polyvinyl acetate emulsion, 0 to 0.9 parts of glycerol, 0.01 to 0.8 parts of modified casein, 0.01 to 0.8 parts of enzyme, 0.01 to 0.8 parts of sugar alcohol, and 5 to 180 parts of clean water are prepared;

[0025] (2) placing the monodisperse micro-nano calcium carbonate filter cake in a small amount of clean water at a temperature of 5 to 30° C. (the weight of the “small amount of clean water” here is 1 to 2 times the weight of the monodisperse micro-nano calcium carbonate filter cake in the formula), and dispersing it in a high-speed disperser at room temperature at a linear speed of 80 to 120 m / min for 15 to 40 min;

[0026] (3) After the stirring in step (2) is completed, the remaining other raw materials and the excess water are added, and the mixture is dispersed in a high-speed disperser at a linear speed of 80 to 120 m / min for 15 to 30 min to obtain the calcium-containing growth protective agent for bag-free fruits of the present invention.

[0027] The calcium-containing growth protectant for bag-free fruits of the present invention can be further diluted according to different application scenarios when used. When used to prevent fruit cracking and improve coloring effect, it is diluted with water to a solid content of calcium carbonate of 0.5% to 2% before spraying; when used to prevent insect pests and reduce fruit drop, the optimal solid content of calcium carbonate is 1% to 3% before diluting with water and spraying.

[0028] According to the above scheme, the bag-free fruits described in the present invention include apples, citrus, pears, plums, mangoes, cherry tomatoes, grapes, pitaya, oranges, loquats, apricots, kiwis, grapefruits, pomegranates, green dates, guavas, peaches, etc.

[0029] The calcium-containing growth protectant of the present invention can be used for bag-free fruit planting, and the application method is as follows: in rainless and dry weather, the growth protectant of the present invention is diluted and sprayed on the surface of the fruit without avoiding branches and leaves. Depending on the type of fruit, it is necessary to spray 2 to 4 times during the ripening process of the fruit; when it rains for more than 5 days within less than 24 hours after spraying, and the total rainfall reaches 250 mm or more, it is necessary to spray once more after the rain.

[0030] The present invention selects limestone with uniform grain size and harmful heavy metal content of less than 400ppm such as cadmium, lead, chromium, etc. as the raw material for preparing monodisperse micro-nano calcium carbonate filter cake, and then adopts a calcination temperature matching the grain size to obtain quicklime with moderate and uniform activity, which is digested and carbonized to obtain calcium carbonate slurry. The limestone with uniform grain size is used to adjust the lime activity through the limestone calcination process to avoid partial raw burning and partial overburning caused by porphyritic grains; the lime with good uniformity and moderate activity is conducive to the control of the digestion reaction, and the uniform lime milk with controllable properties is obtained, and then the control of the later carbonization process is realized, so as to obtain calcium carbonate slurry with expected particle size and grain morphology. The content of harmful heavy metals such as cadmium, lead, chromium, etc. in the limestone is less than 400ppm, which can ensure that the content of harmful heavy metals in the prepared monodisperse micro-nano calcium carbonate filter cake is less than 200ppm.

[0031] After the carbonization is completed, there is a process step of reconstructing the surface of the grains, which is to promote the reconstruction of the surface of the grains by adding inorganic surface reconstruction agents and organic surface reconstruction agents and keeping them warm at a certain temperature, so as to make the crystals more complete, the particle surface smoother, and reduce the surface energy, which is conducive to dispersion. Among them, the role of the inorganic surface reconstruction agent is to promote crystal development, repair defects, and make the crystals more complete; the role of the organic surface reconstruction agent is to adjust the surface potential of the particles, control the mutual repulsion of the grains in water, and avoid adhesion during the crystal repair process. The present invention controls the average particle size of the calcium carbonate particles to 50-200nm by controlling the temperature and time of the grain surface reconstruction, and is in a highly monodisperse state. This form of calcium carbonate particles can ensure visible light diffraction and transmission, so it does not affect the photosynthesis of the fruit and the surface coloring, and can effectively absorb ultraviolet light that is harmful to plants (for example, the calcium-containing growth protectant of the present invention is diluted to a solid content of calcium carbonate of 2% and sprayed to form a film, and the absorption of ultraviolet rays can reach more than 85%, and the absorption of visible light is less than 15%). The monodisperse micro-nano calcium carbonate slurry obtained by reconstructing the surface of the crystal grains is then subjected to filter pressing or centrifugation to obtain a monodisperse micro-nano calcium carbonate filter cake of the desired particle size. Filter pressing and centrifugation can discharge excess water to form a monodisperse micro-nano calcium carbonate filter cake, which is beneficial to the processing and transportation of calcium carbonate, and also rapidly reduces other soluble ions present in the solution during the production process, so as to achieve the effect of not affecting and interfering with the use and performance of the calcium-containing growth protective agent of the present invention.

[0032] On the basis of the above, the present invention uses the monodisperse micro-nano calcium carbonate filter cake as the main raw material, and is compounded with other raw materials and dispersed in clear water, thereby obtaining the calcium-containing growth protectant for bag-free fruits of the present invention. The monodisperse micro-nano calcium carbonate filter cake maintains 35% to 40% of water, and maintains a water film and a double electric layer structure between the solid calcium carbonate particles, which can ensure that the surface state and repulsion of the calcium carbonate particles are not destroyed to the greatest extent, and no agglomeration occurs, so that it can be quickly redispersed in the aqueous solution when the disperser assists in stirring, and maintains a stable suspension.

[0033] The calcium-containing growth protective agent for bag-free fruits of the present invention can be sprayed on the surface of the fruit to quickly form a light white protective film, which effectively resists damage by pests and diseases; due to the special particle size and dispersibility design of calcium carbonate, the protective film does not affect the transmission of visible light, and thus does not affect the photosynthesis of the fruit; the present invention utilizes the ultraviolet light absorption and infrared radiation characteristics of calcium carbonate, combined with the particle size design of the present invention, can effectively reduce the temperature of the fruit, and form effective physical and optical protection.

[0034] The invention adds modified casein as a film-forming agent with good air permeability and strong adhesiveness, and at the same time, the main component casein can promote the growth and development of plants, improve fertilizer efficiency and yield, and is beneficial to the later yield increase of crops.

[0035] The present invention can effectively prevent and control insect pests by adding enzymes; in addition, it contains components such as polysaccharides and amino acids, which can be used in combination with calcium carbonate to improve the level of plant absorption of micro-nano calcium carbonate.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] 1. The growth protectant of the present invention is safe and non-toxic, can replace bagging, and is used for bag-free fruit planting. When used, it is directly sprayed on the surface of fruit crops, has good physical insect prevention effect, can replace bagging, significantly improve the disease resistance and insect resistance of fruit trees, and reduce diseased and insect-infested fruits;

[0038] 2. The growth protectant of the present invention is sprayed on the surface of the fruit to meet the calcium demand of the fruit crops during their growth, effectively inhibit fruit cracking and fruit drop, increase the fullness of the fruit, and improve the calcium content of the fruit. At the same time, it can increase the yield compared to bagged fruits, and significantly improve the taste and quality of the fruit;

[0039] 3. The growth protectant of the present invention can effectively absorb ultraviolet rays, radiate infrared rays, and reduce the temperature of the fruit surface. It does not affect the passage of visible light and does not interfere with the normal photosynthesis of fruit crops. It is used for bag-free fruit planting and can significantly improve the taste and quality of fruits compared to bag-planted fruits. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is a scanning electron microscope photograph of calcium carbonate particles in the calcium carbonate slurry prepared in Example 1;

[0041] Figure 2 This is a scanning electron microscope photo of the micro-nano calcium carbonate prepared in Example 1;

[0042] Figure 3 This is a diagram showing the effect of using the growth protection agent prepared in Example 1 on apples;

[0043] Figure 4 This is a scanning electron microscope photograph of calcium carbonate particles in the calcium carbonate slurry prepared in Example 2;

[0044] Figure 5 This is a scanning electron microscope photo of the micro-nano calcium carbonate prepared in Example 2;

[0045] Figure 6 This is a diagram showing the effect of using the growth protectant prepared in Example 2 on pears;

[0046] Figure 7 This is a scanning electron microscope photograph of calcium carbonate particles in the calcium carbonate slurry prepared in Example 3;

[0047] Figure 8 This is a scanning electron microscope photo of the micro-nano calcium carbonate prepared in Example 3;

[0048] Fig. 9 This is a diagram showing the effect of using the growth protection agent prepared in Example 3 on Prunus mume;

[0049] Fig.10 This is a comparison of the effects of spraying the growth protectant prepared in Example 3 on the ripened fruits of Nai Plum with those of bagging;

[0050] Fig.11 This is the situation of fruit fly infestation and fruit rot when the unsprayed Nai Plum fruit is ripe;

[0051] Fig.12 This is a scanning electron microscope photograph of calcium carbonate particles in the calcium carbonate slurry prepared in Example 4;

[0052] Fig.13 This is a scanning electron microscope photo of the micro-nano calcium carbonate prepared in Example 4;

[0053] Fig.14 This is a scanning electron microscope photograph of calcium carbonate particles in the calcium carbonate slurry prepared in Example 5;

[0054] Fig.15 This is a scanning electron microscope photo of the micro-nano calcium carbonate obtained in Example 5;

[0055] Fig.16 This is a scanning electron microscope photograph of the calcium carbonate prepared in Comparative Example 1;

[0056] Fig.17 The figure is a comparison of the effects of calcium carbonate prepared in the embodiment and the comparative example dispersed in water;

[0057] Fig.18 The effect diagram of the growth protection agent made of calcium carbonate in comparative example 1 on apples and the comparison diagram of the coloration of the ripened fruits with that in example 1;

[0058] Fig.19 This is a scanning electron microscope photograph of calcium carbonate obtained in Comparative Example 2;

[0059] Fig. 20 The effect diagram of using the growth protectant made of calcium carbonate in Comparative Example 2 on pears;

[0060] Fig.21 This is a diagram showing the effect of using the growth protectant made of calcium carbonate in Comparative Example 3 on Prunus mume;

[0061] Fig. 22 This is a diagram showing the effect of using the growth protection agent made of calcium carbonate in Comparative Example 4 on apples;

[0062] Fig.23 This is a diagram showing the effect of using the growth protectant made from calcium carbonate in Comparative Example 5 on pears. Specific implementation methods

[0064] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0065] In the following examples, the ethoxy-modified polytrisiloxane is a commercially available product purchased from GE Silicones USA, model Silwet, with an active ingredient content of more than 98%.

[0066] In the following examples, the polyvinyl acetate emulsion is a commercially available reagent, also known as polyvinyl acetate, CAS No.: 9003-20-7.

[0067] In the following examples, the glycerol is a commercially available reagent with CAS number: 56-81-5.

[0068] In the following examples, the modified casein is a commercially available product, which is a milky white viscous liquid in appearance, has a solid content of 20.0±2.0%, a viscosity (20° C.) greater than 100 mPa·s, and a pH value (10% aqueous solution) of 7-8.

[0069] In the following examples, the enzyme is a commercially available agricultural enzyme, the main component of which is an agricultural biological agent, and also contains polysaccharides, amino acids and other ingredients, purchased from Jining Alida Bioengineering Co., Ltd., model: MLQ-Plant Enzyme.

[0070] The following examples include one or more of xylitol, ribitol, mannitol, sorbitol, maltitol, erythritol and lactitol; the sugar alcohols are all commercially available products, and the effective ingredients are greater than 70%.

[0071] Example 1

[0072] The present embodiment provides a calcium-containing growth protectant for bag-free fruits, which is prepared from the following raw materials in parts by weight: 1 part of monodisperse micro-nano calcium carbonate filter cake, 0.05 part of ethoxy-modified polytrisiloxane, 0.02 part of polyvinyl acetate emulsion, 0.01 part of glycerol, 0.01 part of modified casein, 0.01 part of enzyme, 0.01 part of maltitol, and 5 parts of water.

[0073] The preparation method of the calcium-containing growth protective agent for bag-free fruits described in this embodiment is as follows: according to the above raw materials and mass fractions, 1 part of monodisperse micro-nano calcium carbonate filter cake is placed in 2 parts of water, and stirred for 40 minutes with a high-speed disperser at a stirring line speed of 80m / min, and then 0.05 parts of ethoxy-modified polytrisiloxane, 0.02 parts of polyvinyl acetate emulsion, 0.01 parts of glycerol, 0.01 parts of modified casein, 0.01 parts of enzymes, 0.01 parts of maltitol and the remaining 3 parts of water are added according to the above formula, and stirring is continued at a stirring line speed of 80m / min for 20 minutes to obtain the growth protective agent described in this embodiment, and the solid content of calcium carbonate is about 10%.

[0074] In this embodiment, the monodisperse micro-nano calcium carbonate filter cake used is prepared in the following steps:

[0075] S1. Prepare calcium carbonate slurry by calcination, digestion, carbonization and other processes. The calcination process is as follows: select limestone with a grain size of 0.2-0.5 mm and a content of harmful heavy metals such as cadmium, lead, chromium and less than 400 ppm as raw material, adopt a calcination temperature of 900°C, calcine for 2 hours, and obtain quicklime with ideal activity; the digestion process is as follows: digest the quicklime obtained by the above calcination with water at 90°C to obtain lime milk, and then remove impurities after aging for 24 hours to obtain refined raw slurry; the carbonization process is as follows: add water to the refined raw slurry obtained by digestion to adjust the solid content to 6%, and then carbonize it. The starting temperature of carbonization is 10°C, the CO2 content is 40%, and the slurry is carbonized until the pH value reaches 8.5-9.0, then the carbonization is terminated to obtain calcium carbonate slurry;

[0076] From the scanning electron microscope photos (see Figure 1 ) It can be observed that the calcium carbonate particles in the obtained cooked slurry are nearly spherical particles with an average particle size of about 23nm;

[0077] S2. Add 0.5% aluminum chloride, 0.5% polyvinyl pyrrolidone, 2.5% sodium lauryl sulfate and 2.0% polyvinyl alcohol to the calcium carbonate slurry obtained in S1, and heat at 140°C for 2.0h to obtain a calcium carbonate suspension;

[0078] S3. The calcium carbonate suspension obtained in S2 is filtered and dehydrated to obtain a calcium carbonate filter cake. The moisture content of the filter cake is controlled between 35% and 40%, that is, monodisperse micro-nano calcium carbonate. At this time, an appropriate amount of the filter cake is dried at 105°C and then tested and analyzed for composition, specific surface area, micromorphology and particle size. The composition and specific surface area tests are carried out according to the "Calcium Carbonate Analysis Method" (GB / T19281-2014) standard, and the micromorphology and particle size tests are carried out according to the "Nano Calcium Carbonate" (GB / T 19590-2023) standard. The contents of harmful impurities such as cadmium, lead, barium, mercury, and arsenic in the obtained monodisperse micro-nano calcium carbonate are all less than 0.0002%, and the total content of harmful impurities is less than 200ppm; the specific surface area is about 19.89m 2 / g; from the scanning electron microscope photo (see Figure 2 ) It can be clearly seen that the average particle size of the monodisperse micro-nano calcium carbonate particles obtained is about 65nm, the particles are cubic, and the surface is flat and clean. The monodisperse micro-nano calcium carbonate filter cake is dispersed in clean water to obtain a suspension with a solid content of 2%, and then the suspension effect is observed after standing for 2 hours. It can still be stably suspended (see Fig.17 ).

[0079] When used for apple spraying: before the apple fruit expansion period, the growth protection agent prepared in this embodiment is diluted 10 times (solid content of calcium carbonate is about 1%) and sprayed on the surface of apple fruit. There is no need to avoid the leaves and branches of the fruit trees during the spraying process. After spraying, the growth status of the whole apple tree is recorded by taking pictures. Thereafter, regular observation is made every week. During the apple ripening process, it is necessary to spray 2 to 3 times. If there is continuous rainfall for more than 5 days and the total rainfall reaches 250mm or more, it is necessary to spray once more after the rain. The spraying orchards are Jinyuan Garden, Huaibai Base Garden and Nanhesu Garden.

[0080] The effect of using the growth protection agent of this embodiment on apples is shown in the figure below. Figure 3 shown.

[0081] The effects of spraying the growth protectant of this embodiment on apples (set) and bagging (ck) are shown in Table 1. As can be seen from the table, spraying the growth protectant of this embodiment can improve the growth potential of the tree. In the experiment, the fresh weight of the stalks of Jinyuan Garden increased by 2.24%, the dry weight of the stalks decreased by 1.46%, and the thickness of the stalks increased by 1.17%; the fresh weight of the stalks of Huaibai Base Garden increased by 5.22%, the dry weight of the stalks increased by 3.54%, and the thickness of the stalks increased by 3.95%; the fresh weight of the stalks of Nanhesu Garden increased by 6.17%, the dry weight of the stalks increased by 3.04%, and the thickness of the stalks increased by 8.637%.

[0082] Table 1 Comparison of tree vigor indicators

[0083]

[0084] Table 2 shows the effects of spraying the growth protectant of this embodiment on apples (set) and bagging (ck). As can be seen from the table, spraying the growth protectant of this embodiment has little effect on the fruit shape index of the fruit, but can improve the brightness and color of the fruit. The brightness of the fruit in Jinyuan Garden increased by 9.9%, the redness increased by 19.8%, and the yellowness decreased by 31.8%; the brightness of the fruit in Huaibai Base Garden increased by 5.5%, the redness increased by 18.7%, and the yellowness decreased by 28.6%; the brightness of the fruit in Nanhesu Garden increased by 19.6%, the redness increased by 43.5%, and the yellowness decreased by 10.8%.

[0085] Table 2 Comparison of fruit appearance indicators

[0086]

[0087] (Note: 0.6<Fruit Shape Index≤0.8 means the fruit is oblate, 0.8<Fruit Shape Index≤0.9 means the fruit is round or nearly round; L represents the lightness value.)

[0088] Table 3 shows the effect of spraying the growth protectant of this embodiment on apples (set) and bagging (ck). As can be seen from the table, the growth protectant of this embodiment can improve the intrinsic quality of the fruit. In the experiment, the weight of a single fruit in Jinyuan Garden increased by 1.68%, the hardness increased by 2.3%, the soluble solids increased by 2.2%, the titratable acid increased by 23.9%, and the solid-acid ratio decreased by 17.5%; the weight of a single fruit in Huaibai Base Garden increased by 6.1%, the hardness increased by 0.6%, the soluble solids increased by 3.2%, the titratable acid increased by 2.2%, and the solid-acid ratio decreased by 1.0%; the weight of a single fruit in Nanhesu Garden increased by 9.5%, the hardness increased by 0.2%, the soluble solids increased by 4.0%, the titratable acid increased by 14.3%, and the solid-acid ratio decreased by 9.0%. Apple bagging affects the intrinsic quality of the fruit, causing the fruit weight, hardness, sugar, acid, VC and other contents to decrease, and the flavor to become lighter. The growth protectant of this embodiment can increase the calcium content in the fruit. The calcium content in the peel of the Jinyuan Garden increased by 12.4%, and the calcium content in the pulp increased by 49.8%; the calcium content in the peel of the Huaibai Base Garden increased by 16.4%, and the calcium content in the pulp increased by 16.1%; the calcium content in the peel of the Nanhesu Garden increased by 14.0%, and the calcium content in the pulp increased by 5.7%.

[0089] Table 3 Comparison of fruit internal quality

[0090]

[0091] The price of the growth protection agent of this embodiment has been calculated in detail, and the cost per mu of land per year is only about 330 yuan. The specific cost calculation is as follows: there are about 100 fruit trees in one mu of land, and the annual fruit production is about 2500 kg. The amount of growth protection agent is calculated at 25 kg / mu at one time, and the unit price of bag-free growth protection agent is about 5 yuan / kg. The plant protection machine is used for spraying, and the machine rental fee (including labor cost) is about 40 yuan / mu·time. The cost of spraying twice a year on one mu of land is 330 yuan (2*25*5+2*40); the cost of bagging is calculated as follows: one mu of land requires about 10,000 bags / mu, and the cost of manual bagging is about 0.24 yuan / piece, so the cost of manual bagging is 2,400 yuan / mu (10,000*0.24). Spraying the growth protection agent of this embodiment can save 2,070 yuan per mu compared to manual bagging, which greatly improves the economic benefits and has a broad market prospect.

[0092] Example 2

[0093] The present embodiment provides a calcium-containing growth protectant for bag-free fruits, which is prepared in the following weight ratios: 10 parts of monodisperse micro-nano calcium carbonate filter cake, 0.4 parts of ethoxy-modified polytrisiloxane, 0.05 parts of polyvinyl acetate emulsion, 0.9 parts of glycerol, 0.1 parts of modified casein, 0.05 parts of enzyme, 0.1 parts of mannitol, and 115 parts of water.

[0094] The preparation method of the calcium-containing growth protective agent for bag-free fruits described in this embodiment is as follows: according to the above raw materials and mass fractions, 10 parts of monodisperse micro-nano calcium carbonate filter cake are placed in 15 parts of water, and stirred for 15 minutes with a high-speed disperser at a stirring line speed of 120m / min, and then 0.4 parts of ethoxy-modified polytrisiloxane, 0.05 parts of polyvinyl acetate emulsion, 0.9 parts of glycerol, 0.1 parts of modified casein, 0.05 parts of enzyme, 0.1 parts of mannitol and the remaining 100 parts of water are added according to the above formula, and stirring is continued at a stirring line speed of 90m / min for 30 minutes to obtain the growth protective agent described in this embodiment, and the solid content of calcium carbonate is about 5%. Among them, the preparation steps of the monodisperse micro-nano calcium carbonate filter cake are different from those in Example 1 in that the digestion temperature in step S1 is 70°C, the aging time is 35h, the solid content of the refined raw pulp during the carbonization process is 8%, the carbonization starting temperature is 22°C, the CO2 content is 30%, and the carbonization is terminated when the pH reaches 8.0-8.5. After the carbonization is completed, the microscopic morphology of the calcium carbonate particles in the obtained cooked pulp is characterized, and it can be observed that the calcium carbonate particles are nearly spherical, with an average particle size of about 70nm (see Figure 4 ); Step S2: During the grain surface reconstruction process, 0.5% sodium silicate, 1.5% aluminum chloride and 2% polyethylene glycol were added based on the dry mass of calcium carbonate and kept warm at 140°C for 4h.

[0095] The same test method as in Example 1 was used to test and analyze the composition, specific surface area, microscopic morphology and particle size of the monodisperse micro-nano calcium carbonate filter cake obtained in this example. The contents of harmful impurities such as cadmium, lead, barium, mercury and arsenic in the monodisperse micro-nano calcium carbonate were all less than 0.0002%, and the total content of harmful impurities was less than 200 ppm; the specific surface area was about 18.53 m 2 / g; From the SEM photos (see Figure 5 ) It can be clearly seen that the average particle size of the monodisperse micro-nano calcium carbonate particles is about 110nm, the particles are cubic, and the surface is flat and clean. The monodisperse micro-nano calcium carbonate filter cake is dispersed in clean water to obtain a suspension with a solid content of 2%, and then the suspension effect is observed after standing for 2 hours. It can still be stably suspended (see Fig.17 ).

[0096] When used for spraying pears: before the pears are about to expand, dilute the calcium growth protectant for bag-free fruits by 2 times (solid content of calcium carbonate is about 2.5%) and spray it on the surface of the pear fruit. After spraying, take photos to record the growth status of the whole pear tree, and observe it regularly once a week thereafter. Spray 1 to 2 times during the ripening process of the pears. If there is continuous rainfall for more than 5 days and the total rainfall reaches 250mm or more, it is necessary to spray once after the rain. Before spraying, make sure there will be no rainfall for 24 hours.

[0097] The effect of using the growth protection agent prepared in this embodiment on pears is shown in the figure below: Figure 6 As shown, the protective agent can spread quickly and evenly adhere to the fruit surface.

[0098] Spraying the growth protectant prepared in this example can provide good protection for pears and significantly reduce the fruit drop rate. Specific data are shown in Table 4.

[0099] Table 4 Comparison of the effect of preventing pear fruit drop and insect fruit

[0100]

[0101] Note: 20 pear trees in the same orchard were randomly selected for comparison.

[0102] The price of the product of this embodiment is calculated in detail, and the cost per mu of land is only about 700 yuan per year. The specific calculation of the cost is as follows: there are about 100 trees in one mu of land, and the annual fruit production is about 3000 kg. The dosage of the growth agent is 100 kg / mu at a time, and the unit price of the growth protection agent is about 2.5 yuan / kg. The manual spraying operation is adopted, and the labor cost is about 100 yuan / mu·time. The cost of spraying one mu of land twice a year is 700 yuan (2*100*2.5+2*100); the bagging cost is calculated as follows: one mu of land requires about 10,000 bags / mu, and the cost of manual bagging is about 0.13 yuan / piece, so the cost of manual bagging is 1,300 yuan / mu (10000*0.13). Spraying the growth protection agent of this embodiment can save 600 yuan per mu compared with manual bagging, improves economic benefits, and has a broad market prospect.

[0103] Example 3

[0104] The present embodiment provides a calcium-containing growth protectant for bag-free fruits, which is prepared from the following raw materials in parts by weight: 15 parts of monodisperse micro-nano calcium carbonate filter cake, 0.2 parts of ethoxy-modified polytrisiloxane, 0.8 parts of polyvinyl acetate emulsion, 0.2 parts of modified casein, 0.5 parts of enzyme, 0.9 parts of ribitol, and 45 parts of water.

[0105] The preparation method of the calcium-containing growth protectant for bag-free fruits described in this embodiment is as follows: according to the above raw materials and mass fractions, 15 parts of monodisperse micro-nano calcium carbonate filter cake are placed in 20 parts of clean water, and stirred for 30 minutes with a high-speed disperser at a stirring line speed of 90m / min, and then 0.2 parts of ethoxy-modified polytrisiloxane, 0.8 parts of polyvinyl acetate emulsion, 0.2 parts of modified casein, 0.5 parts of enzyme, 0.9 parts of ribitol and the remaining 25 parts of water are added according to the above formula, and stirring is continued at a stirring line speed of 110m / min for 25 minutes to obtain the growth protectant described in this embodiment, and the solid content of calcium carbonate is about 15%. Among them, the preparation steps of the monodisperse micro-nano calcium carbonate filter cake are different from those in Example 1 in that the digestion temperature in step S1 is 80°C, the aging time is 30h, the solid content of the refined raw pulp during the carbonization process is 5%, the carbonization starting temperature is 30°C, the CO2 content is 20%, and the carbonization is terminated when the pH reaches 8.0-9.0. After the carbonization is completed, the microscopic morphology of the calcium carbonate particles in the obtained cooked pulp is characterized, and it can be observed that the calcium carbonate particles are short-chain with an average width of about 61nm (see Figure 7 ); Step S2: During the grain surface reconstruction process, 0.2% zinc sulfate, 0.5% sodium silicate, 1.4% polyethylene glycol and 0.6% hexadecyltrimethylammonium bromide were added to the dry basis of calcium carbonate and kept at 180°C for 2.5h.

[0106] The same test method as in Example 1 was used to test and analyze the composition, specific surface area, microscopic morphology and particle size of the monodisperse micro-nano calcium carbonate filter cake obtained in this example. The contents of harmful impurities such as cadmium, lead, barium, mercury and arsenic in the monodisperse micro-nano calcium carbonate were all less than 0.0002%, and the total content of harmful impurities was less than 200 ppm; the specific surface area was about 17.26 m 2 / g; From the SEM photos (see Figure 8 ) It can be clearly seen that the average particle size of the monodisperse micro-nano calcium carbonate particles obtained is about 150nm, the particles are cubic, and the surface is flat and clean. The monodisperse micro-nano calcium carbonate filter cake is dispersed in clean water to obtain a suspension with a solid content of 2%, and then the suspension effect is observed after standing for 2 hours. It can still be stably suspended (see Fig.17 ).

[0107] When used for the cultivation of plums: During the plum fruit expansion period, choose a sunny day and use a conventional sprayer to dilute the growth protectant 5 times (the solid content of calcium carbonate is about 3%) and spray it on the surface of the plum fruit. There is no need to avoid the leaves and branches of the fruit trees. After spraying, take photos to record the growth status of the whole plum tree, and observe it regularly once a week thereafter. If there is continuous rainfall for more than 5 days and the total rainfall reaches 250mm or more, it is necessary to spray again after the rain. If there is no rainfall before picking, no additional spraying is required.

[0108] The effect of using the growth protection agent prepared in this example on Prunus mume is shown in the figure below: Fig. 9 As shown in the figure, the growth protection agent is evenly attached to the fruit and leaves of the plum tree, forming a thin and uniform protective film.

[0109] After spraying the growth protection agent prepared in this embodiment on the surface of the nai plum, the ripe nai plum fruit and the bagged ripe nai plum are as follows: Fig.10 As shown. The bagging blocks the sunlight, the chlorophyll on the peel is less, and it is light yellow when ripe; at the same time, due to the weak photosynthesis, the sugar content, vitamins, proteins and other substances in the fruit are reduced accordingly, the sweetness is poor and lacks fruity aroma. However, the plum sprayed with the growth protection agent of this embodiment is light yellow-green when ripe, with a crisp and sweet taste and rich fruity aroma.

[0110] The nai plums sprayed with the growth protection agent prepared in this example had no fruit fly pests, while the natural fruits without treatment had more fruit fly eggs and rotten cores (see Fig.11 The comparison of the fruit fly pest prevention effect of spraying the growth protectant prepared in this example with bagging and no treatment is shown in Table 5. The fruit fly prevention effect of the plum sprayed with the growth protectant prepared in this example is much higher than that of no treatment, and is equal to the effect of bagging.

[0111] Table 5 Comparison of the effect of preventing fruit fly pests

[0112] Protection method No treatment Bagging Spray the growth protection agent of this embodiment Number of plums with fruit fly eggs 32 0 0

[0113] Note: 100 nai plums from 10 nai plum trees in the same orchard were randomly selected for comparison.

[0114] The price of the product of this embodiment is calculated in detail, and the cost per mu of land per year is only about 950 yuan. The specific calculation of the cost is as follows: there are about 100 trees in one mu of land, and the annual fruit production is about 3,000 jin. The dosage of the growth agent is 50 kg / mu at a time, and the unit price of the growth protection agent is about 7.5 yuan / kg. The manual spraying operation is adopted, and the labor cost is about 100 yuan / mu. The cost of spraying one mu of land twice a year is 950 yuan (2*50*7.5+2*100); the bagging cost is calculated as follows: one mu of land requires about 20,000 bags / mu, and the cost of manual bagging is about 0.1 yuan / piece, so the cost of manual bagging is 2,000 yuan / mu (20,000*0.1). Spraying the growth protection agent of this embodiment can save 1,050 yuan per mu compared to manual bagging, improves economic benefits, and has a broad market prospect.

[0115] Example 4

[0116] The present embodiment provides a calcium-containing growth protectant for bag-free fruits, which is prepared from the following raw materials in parts by weight: 5 parts of monodisperse micro-nano calcium carbonate filter cake, 0.3 parts of ethoxy-modified polytrisiloxane, 0.2 parts of polyvinyl acetate emulsion, 0.1 parts of modified casein, 0.2 parts of enzyme, 0.1 parts of lactitol, and 25 parts of water.

[0117] The preparation method of the calcium-containing growth protective agent for bag-free fruits described in this embodiment is as follows: according to the above raw materials and mass fractions, 8 parts of monodisperse micro-nano calcium carbonate filter cake are placed in 8 parts of water, and stirred for 20 minutes with a high-speed disperser at a stirring line speed of 110m / min, and then 0.3 parts of ethoxy-modified polytrisiloxane, 0.2 parts of polyvinyl acetate emulsion, 0.1 parts of modified casein, 0.2 parts of enzyme, 0.1 parts of lactitol and the remaining 17 parts of water are added according to the above formula, and stirring is continued at a stirring line speed of 80m / min for 30 minutes to obtain the growth protective agent described in this embodiment, and the solid content of calcium carbonate is about 10%. Among them, the preparation steps of the monodisperse micro-nano calcium carbonate filter cake are different from those in Example 1 in that the digestion temperature in step S1 is 60°C, the aging time is 40h, the solid content of the refined raw pulp during the carbonization process is 12%, the carbonization starting temperature is 10°C, the CO2 content is 35%, and the carbonization is terminated when the pH reaches 8.0-8.5. After the carbonization is completed, the microscopic morphology of the calcium carbonate particles in the obtained cooked pulp is characterized, and it can be observed that the calcium carbonate particles are nearly spherical, with an average particle size of about 53nm (see Fig.12 ); Step S2: During the grain surface reconstruction process, 1% sodium silicate, 1.5% polyvinyl alcohol and 1.5% sodium dodecylbenzene sulfonate were added to the dry mass of calcium carbonate and kept at 200°C for 1h.

[0118] The same test method as in Example 1 was used to test and analyze the composition, specific surface area, microscopic morphology and particle size of the monodisperse micro-nano calcium carbonate filter cake obtained in this example. The contents of harmful impurities such as cadmium, lead, barium, mercury and arsenic in the monodisperse micro-nano calcium carbonate were all less than 0.0002%, and the total content of harmful impurities was less than 200 ppm; the specific surface area was about 18.24 m 2 / g; From the SEM photos (see Fig.13 ) It can be clearly seen that the average particle size of the monodisperse micro-nano calcium carbonate particles obtained is about 120nm, the particles are cubic, and the surface is flat and clean. The monodisperse micro-nano calcium carbonate filter cake is dispersed in clean water to obtain a suspension with a solid content of 2%, and then the suspension effect is observed after standing for 2 hours. It can still be stably suspended (see Fig.17 ).

[0119] When used for guava planting: one month after the fruit sets, when the longitudinal diameter of the young fruit reaches 3-4cm and the fruit begins to droop, choose a sunny day and use a conventional sprayer to dilute the growth protectant 10 times (the solid content of calcium carbonate is about 1%) and spray it on the surface of the guava fruit. There is no need to avoid the leaves and branches of the fruit tree. After spraying, take photos to record the growth status of the guava tree, and observe it regularly once a week thereafter. If there is continuous rainfall for more than 5 days and the total rainfall reaches 250mm or more, it is necessary to spray again after the rain. Before the fruit matures, it is generally sprayed once in mid-August each year.

[0120] The guava sprayed with the growth protectant prepared in this example had no fruit fly pests, while the natural fruit without treatment had more fruit fly eggs and rotten cores. The fruit fly pest prevention effect of spraying the growth protectant prepared in this example with bagging and without treatment is shown in Table 6. The fruit fly prevention effect of guava sprayed with the growth protectant prepared in this example is much higher than that of the fruit without treatment, and is basically the same as the bagging effect.

[0121] Table 6 Comparison of the effect of preventing fruit fly pests

[0122] Protection method No treatment Bagging Spray the growth protection agent of this embodiment Number of guavas with fruit fly eggs 186 0 2

[0123] Note: 400 guavas (20 guavas from each tree) from 20 guava trees in the same orchard were randomly selected for comparison.

[0124] The price of the product of this embodiment is calculated in detail, and the cost per mu of land per year is only about 700 yuan. The specific calculation of the cost is as follows: the annual fruit yield of one mu of land is about 3000 kg, the growth agent dosage is 50 kg / mu once, the unit price of the growth protection agent is about 5 yuan / kg, and the manual spraying operation is adopted, the labor cost is about 100 yuan / mu·time, and the cost of spraying one mu of land twice a year is 700 yuan (2*50*5+2*100); the bagging cost is calculated as follows: one mu of land requires about 8000 bags / mu, and the cost of manual bagging is about 0.16 yuan / piece, so the cost of manual bagging is 1280 yuan / mu (8000*0.16). Spraying the growth protection agent of this embodiment can save 580 yuan per mu compared with manual bagging, improves economic benefits, and has broad market prospects.

[0125] Example 5

[0126] The present embodiment provides a calcium-containing growth protectant for bag-free fruits, which is prepared from the following raw materials in parts by weight: 20 parts of monodisperse micro-nano calcium carbonate filter cake, 0.5 parts of ethoxy-modified polytrisiloxane, 0.9 parts of polyvinyl acetate emulsion, 0.2 parts of glycerol, 0.8 parts of modified casein, 0.2 parts of enzyme, 0.1 parts of sorbitol, and 180 parts of water.

[0127] The preparation method of the calcium-containing growth protective agent for bag-free fruits described in this embodiment is as follows: according to the above raw materials and mass fractions, 3 parts of monodisperse micro-nano calcium carbonate filter cake are placed in 30 parts of water, and stirred for 40 minutes with a high-speed disperser at a stirring line speed of 80m / min, and then 0.5 parts of ethoxy-modified polytrisiloxane, 0.9 parts of polyvinyl acetate emulsion, 0.2 parts of glycerol, 0.8 parts of modified casein, 0.2 parts of enzyme, 0.1 parts of sorbitol and the remaining 150 parts of water are added according to the above formula, and stirring is continued at a stirring line speed of 80m / min for 30 minutes to obtain the growth protective agent described in this embodiment, and the solid content of calcium carbonate is about 6%.

[0128] Among them, the preparation steps of the monodisperse micro-nano calcium carbonate filter cake are different from those in Example 1 in that the digestion temperature in step S1 is 50°C, the aging time is 48h, the solid content of the refined raw pulp during the carbonization process is 10%, the carbonization starting temperature is 25°C, the CO2 content is 33%, and the carbonization is terminated when the pH reaches 7.5 to 8.5. After the carbonization is completed, the microscopic morphology of the calcium carbonate particles in the obtained cooked pulp is characterized, and it can be observed that the calcium carbonate particles are chain-shaped with an average width of about 68nm (see Fig.14 ); Step S2: during the grain surface reconstruction process, 1.5% sodium chloride, 0.5% sodium silicate, 1% zinc sulfate, 0.5% ethanol and 0.5% disodium ethylenediaminetetraacetate were added to the dry basis mass of calcium carbonate and kept warm at 190°C for 3h.

[0129] The same test method as in Example 1 was used to test and analyze the composition, specific surface area, microscopic morphology and particle size of the monodisperse micro-nano calcium carbonate filter cake obtained in this example. The contents of harmful impurities such as cadmium, lead, barium, mercury and arsenic in the monodisperse micro-nano calcium carbonate were all less than 0.0002%, and the total content of harmful impurities was less than 200 ppm; the specific surface area was about 16.92 m 2 / g; From the SEM photos (see Fig.15 ) It can be clearly seen that the average particle size of the monodisperse micro-nano calcium carbonate particles obtained is about 195nm, the particles are cubic, and the surface is flat and clean. The monodisperse micro-nano calcium carbonate filter cake is dispersed in clean water to obtain a suspension with a solid content of 2%, and then the suspension effect is observed after standing for 2 hours. It can still be stably suspended (see Fig.17 ).

[0130] When used for honey pomelo planting: When the fruit diameter reaches 3-5cm, choose a sunny day, use a conventional sprayer to dilute the growth protectant 3 times (the solid content of calcium carbonate is about 2%) and spray it directly on the surface of the honey pomelo fruit, without avoiding the leaves and branches of the fruit tree. After spraying, take photos to record the growth status of the whole honey pomelo tree, and observe it regularly once a week thereafter. If there is continuous rainfall for more than 5 days and the total rainfall reaches 250mm or more, it is necessary to spray again after the rain. If there is no rainfall before picking, no additional spraying is required.

[0131] The honey pomelo sprayed with the growth protection agent prepared in this example had basically no fruit borers, borers and other insect pests, while the natural fruit without treatment had more insect-infested fruit and cracked fruit, and there was more dry water in the flesh near the fruit stem in the fruit. The comparison of the insect pest and fruit crack prevention of the honey pomelo sprayed with the growth protection agent prepared in this example and the bagging and no treatment is shown in Table 7. The insect pest and fruit crack prevention effect of the honey pomelo sprayed with the growth protection agent of this example is much higher than that of the no treatment, and is basically the same as the bagging effect.

[0132] Table 7 Comparison of pest control and fruit drop prevention effects

[0133] Protection method No treatment Bagging Spray the growth protection agent of this embodiment Number of honey pomelo with insect-infested fruit 52 0 1 Number of honey pomelo with cracked fruit 21 0 1

[0134] Note: 200 pomelo fruits from the same orchard were randomly selected for comparison.

[0135] The price of the product of this embodiment is calculated in detail, and the cost per mu of land per year is only about 600 yuan. The specific calculation of the cost is as follows: the annual fruit yield of one mu of land is about 5000 kg, the growth agent dosage is 100 kg / mu once, the unit price of the growth protection agent is about 2 yuan / kg, and the manual spraying operation is adopted, the labor cost is about 100 yuan / mu·time, and the cost of spraying one mu of land twice a year is 700 yuan (2*100*2+2*100); the bagging cost is calculated as follows: one mu of land requires about 5000 bags / mu, and the cost of manual bagging is about 0.3 yuan / piece, so the cost of manual bagging is 1500 yuan / mu (5000*0.3). Spraying the growth protection agent of this embodiment can save 900 yuan per mu compared with manual bagging, improves economic benefits, and has broad market prospects.

[0136] Comparative Example 1

[0137] Comparative Example 1 has the same formula as Example 1, except that no inorganic grain surface reconstructor is added in the preparation method of calcium carbonate. The microscopic morphology of the obtained product is shown in FIG. Fig.16 .

[0138] In Comparative Example 1, because no inorganic crystal surface reconstructor was added, the surface of the calcium carbonate crystals was rough, the dispersion between the particles was relatively poor, and the particles were connected to each other, resulting in reduced dispersion stability in water. Fig.17 As shown. And because the particles are hard and agglomerated, the film formed on the apple surface after spraying is uneven (see Fig.18 Left), it cannot achieve good protection, and the coloring of the apple surface is uneven after ripening (see Fig.18 right).

[0139] Comparative Example 2

[0140] Comparative Example 2 has the same formula as Example 2, except that no organic crystal surface reconstruction agent is added in the preparation method of calcium carbonate. The microscopic morphology of the obtained product is shown in FIG. Fig.19 .

[0141] In Comparative Example 2, since no organic crystal surface reconstructor was added, the surface of the calcium carbonate crystals was clean, but the dispersion between the particles was still relatively poor, and connections were formed between the particles, resulting in reduced dispersion stability in water. Fig.17 As shown. And because the particles are hard and agglomerated, the film formed on the pear surface after spraying is uneven (see Fig. 20 ), it is not possible to achieve good protection, and many spots appear on the fruit surface.

[0142] Comparative Example 3

[0143] The preparation method of calcium carbonate in Comparative Example 3 is the same as that in Example 3, except that auxiliary materials such as ethoxy-modified polytrisiloxane and polyvinyl acetate emulsion-modified casein are not added in the formula.

[0144] In Comparative Example 3, because no auxiliary materials were added, the growth protection agent did not infiltrate the surface of the plum fruit during the spraying process, resulting in the failure of the growth protection agent to be sprayed successfully. Fig.21 shown.

[0145] Comparative Example 4

[0146] The formula of Comparative Example 4 is the same as that of Example 1, except that in the preparation method of calcium carbonate, filter pressing is not performed to obtain a monodisperse calcium carbonate filter cake of a special form, but the slurry obtained after the surface of the grains is directly formulated according to the proportions described in Example 1.

[0147] In Comparative Example 4, because no filtration was performed to remove the soluble ions in the slurry, the harmful ions were sprayed on the apple surface, and the surface of the fruit was affected. After ripening, there were many spots on the surface, such as Fig. 22 shown.

[0148] Comparative Example 5

[0149] Comparative Example 5 has the same formula as Example 2, except that the preparation method of the growth protectant is not carried out according to the two-step dispersion step, but 10 parts of monodisperse micro-nano calcium carbonate filter cake are directly added to 115 parts of clean water, and stirred for 15 minutes at a stirring line speed of 120 m / min using a high-speed disperser. After stirring evenly, ethoxy-modified polytrisiloxane, polyvinyl acetate emulsion, glycerol, modified casein, enzyme and mannitol are added according to the ingredient relationship, and stirring is continued at a stirring line speed of 100 m / min for 15 minutes.

[0150] In Comparative Example 5, because there is no high-concentration stirring step, the dispersion effect of calcium carbonate is poor. When sprayed on the pear fruit surface, the slurry cannot form a film on the fruit surface well, there are local differences in density, and more accumulation is on the fruit pedicle, resulting in more spots on the fruit surface after ripening, and a high fruit drop rate. Fig.23 shown.

[0151] Comparative Example 6

[0152] The preparation method of calcium carbonate in Comparative Example 6 is the same as that in Example 1, except that modified casein, enzyme and maltitol are not added in the formula.

[0153] Because no auxiliary materials were added to Comparative Example 6, when used for bag-free apple cultivation, the calcium supplement and insect control effects were poor. Compared with the effect of spraying Example 1, the calcium content of the fruit pulp in Jinyuan Garden decreased by 19.5%, the calcium content of the fruit pulp in Huaibai Base Garden decreased by 6.7%, and the calcium content of the fruit pulp in Nanhesu Garden decreased by 4.5%.

[0154] The above is only a preferred embodiment of the present invention. It should be pointed out that a person skilled in the art can make several improvements and changes without departing from the creative concept of the present invention, which all belong to the protection scope of the present invention.

Claims

1. A calcium-containing growth protectant for bag-free fruits, characterized in that: The raw material composition includes, by weight: 1 to 20 parts of monodisperse micro-nano calcium carbonate filter cake, 0.01 to 0.9 parts of ethoxy-modified polytrisiloxane, 0 to 0.8 parts of polyvinyl acetate emulsion, 0 to 0.9 parts of glycerol, 0.01 to 0.8 parts of modified casein, 0.01 to 0.8 parts of enzyme, 0.01 to 0.9 parts of sugar alcohol, and 5 to 180 parts of water; wherein the polyvinyl acetate emulsion and glycerol are not zero at the same time; The water content of the monodisperse micro-nano calcium carbonate filter cake is 35% to 40%, the average particle size of the calcium carbonate particles is between 50 and 200 nm, the particles with a particle size greater than 200 nm are less than 5%, and the specific surface area is less than 20 m 2 / g; and, the monodisperse micro-nano calcium carbonate filter cake is stirred and dispersed in the aqueous solution without adding any chemical dispersant, and remains stably suspended.

2. The calcium-containing growth protectant for bag-free fruits according to claim 1, characterized in that: The raw materials are calculated by weight and include: 1 to 20 parts of monodisperse micro-nano calcium carbonate filter cake, 0.05 to 0.5 parts of ethoxy-modified polytrisiloxane, 0.02 to 0.9 parts of polyvinyl acetate emulsion, 0 to 0.9 parts of glycerol, 0.01 to 0.8 parts of modified casein, 0.01 to 0.5 parts of enzyme, 0.01 to 0.9 parts of sugar alcohol, and 5 to 180 parts of water; the monodisperse micro-nano calcium carbonate filter cake is dispersed in water to obtain a suspension; when the solid content of the suspension is 5% to 30%, it can be stably suspended for more than 14 hours.

3. The calcium-containing growth protectant for bag-free fruits according to claim 1, characterized in that: The method for preparing the monodisperse micro-nano calcium carbonate filter cake comprises the following steps: S1. Prepare calcium carbonate pulp by processes including calcination, digestion and carbonization; S2. Adding an inorganic salt grain surface reconstruction agent and an organic grain surface reconstruction agent to the calcium carbonate slurry obtained in S1, and then keeping the mixture at 140 to 200° C. for 1.0 to 4.0 h to obtain a calcium carbonate suspension; S3. The calcium carbonate suspension obtained in S2 is dehydrated by hydraulic filtration to obtain a calcium carbonate filter cake, wherein the water content of the filter cake is controlled between 35% and 40%, i.e., a monodisperse micro-nano calcium carbonate filter cake.

4. The calcium-containing growth protectant for bag-free fruits according to claim 3, characterized in that: The calcination process is as follows: limestone with uniform grain size and harmful heavy metal content less than 400ppm is selected as raw material, and calcined to obtain quicklime, the activity of which is in the range of 250 to 300mL; The digestion process is as follows: the quicklime obtained by calcination is digested in hot water at 50-90°C to obtain lime milk, which is then aged for 24-48 hours, and refined raw pulp is obtained after filtering and removing impurities; The carbonization process is as follows: add water to the refined raw pulp to adjust the solid content to 5% to 12%, and then carbonize it. The starting temperature of carbonization is 10 to 30°C, the CO2 content is 20% to 40%, and the carbonization is performed until the pH of the pulp reaches 7.5 to 9.

0. Then the carbonization is terminated to obtain calcium carbonate cooked pulp.

5. The calcium-containing growth protectant for bag-free fruits according to claim 3, characterized in that: The inorganic grain surface reconstruction agent is one or more of sodium silicate, sodium chloride, aluminum chloride, and zinc sulfate, and the dosage is 0.5% to 3% of the dry basis mass of calcium carbonate; the organic grain surface reconstruction agent is one or more of ethanol, polyethylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, sodium dodecylbenzene sulfonate, hexadecyltrimethylammonium bromide, sodium dodecyl sulfate, and disodium ethylenediaminetetraacetate, and the dosage is 1% to 5% of the dry basis mass of calcium carbonate.

6. The calcium-containing growth protectant for bag-free fruits according to claim 1, characterized in that: The sugar alcohol includes one or more of xylitol, ribitol, mannitol, sorbitol, maltitol, erythritol and lactitol; and the enzyme is a commercially available agricultural enzyme.

7. The method for preparing the calcium-containing growth protectant for bag-free fruits according to any one of claims 1 to 6, characterized in that: The steps include: (1) According to the raw materials and their weight proportions, 1 to 20 parts of monodisperse micro-nano calcium carbonate filter cake, 0.01 to 0.9 parts of ethoxy-modified polytrisiloxane, 0 to 0.8 parts of polyvinyl acetate emulsion, 0 to 0.9 parts of glycerol, 0.01 to 0.8 parts of modified casein, 0.01 to 0.8 parts of enzyme, 0.01 to 0.9 parts of sugar alcohol, and 5 to 180 parts of water are prepared, and the polyvinyl acetate emulsion and glycerol are not zero at the same time; (2) placing the monodisperse micro-nano calcium carbonate filter cake in a portion of water at a temperature of 5 to 30° C. and dispersing it in a high-speed disperser at a linear speed of 80 to 120 m / min for 15 to 40 min; (3) After the stirring in step (2) is completed, other raw materials and the remaining amount of water are added, and the mixture is dispersed in a high-speed disperser at a linear speed of 80 to 120 m / min for 15 to 30 min to obtain the calcium-containing growth protective agent for bag-free fruits.

8. The method for preparing the calcium-containing growth protectant for bag-free fruits according to claims 1 to 7, characterized in that: In step (2), the amount of water used to disperse the monodisperse micro-nano calcium carbonate filter cake is 1 to 2 times the weight of the monodisperse micro-nano calcium carbonate filter cake.

9. The method for applying the calcium-containing growth protectant for bag-free fruits according to any one of claims 1 to 7, characterized in that: When used to prevent fruit cracking and improve coloring effect, the calcium-containing growth protectant for bag-free fruits is diluted with water to a solid content of calcium carbonate of 0.5% to 2% and then sprayed; when used to prevent insect pests and reduce fruit drop, the calcium-containing growth protectant for bag-free fruits is diluted with water to a solid content of calcium carbonate of 1% to 3% and then sprayed.

10. The method for applying the calcium-containing growth protectant for bag-free fruits according to claim 9, characterized in that: In rainless and dry weather, the calcium-containing growth protectant is diluted and sprayed on the surface of the fruit without avoiding branches and leaves. It is necessary to spray 2 to 4 times during the fruit ripening process. If it rains for more than 5 days within less than 24 hours after spraying, and the total rainfall reaches 250 mm or more, it is necessary to spray again after the rain.

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