Controlled-release hydrogen capsule fertilizer and its preparation method

Abstract

The present invention discloses a controllable hydrogen-release capsule fertilizer and a preparation method thereof. The hydrogen-release capsule is used to protect the active metal or hydride, and then combined with plant nutrient raw materials, so as to act on plants in a dual-layer manner, promoting the growth and development of plants. During the preparation process of the hydrogen-release capsule, antioxidants and desiccants are added to prevent the hydrogen donor from being oxidized or reacting with water, improving the stability of the hydrogen-release capsule during storage and ensuring the stability of the fertilizer. According to different usage scenarios, the fertilizer is designed to be solid or liquid to meet different usage requirements.

Description

Technical Field

[0001] The invention relates to the technical field of fertilizers, and in particular to a controlled-release hydrogen capsule fertilizer and a preparation method thereof. Background Art

[0002] Hydrogen is one of the 17 essential nutrients for plants. Only very rare free hydrogen exists on Earth and in the Earth's atmosphere. In the past 20 years, research on the role of hydrogen has been mainly focused on medicine, energy and other aspects, and has achieved certain results. In the past 10 years, agricultural science and technology workers in some scientific research institutes have also been studying the role and application of hydrogen in agriculture. They found that hydrogen can improve plant stress resistance, regulate the effects of plant hormones, and promote plant growth. It is also considered to be a potential substitute for pesticides and fertilizers. However, since most scientific and technological workers in scientific research institutes only conduct research in laboratories, they have not fully considered the complexity of the production process of hydrogen-containing fertilizers, production costs, difficulty in storage and transportation, promotion applicability, safety and convenience of farmers' use, and integration with modern water and fertilizer application facilities. As a result, the application and promotion of hydrogen fertilizers are still hindered.

[0003] At present, the experimental research basically involves passing hydrogen gas in aluminum cans or alloy steel bottles into water to form hydrogen-rich water of different saturations for irrigation of crops, so as to induce plants to produce antioxidant enzymes, reduce oxidative stress damage and reactive oxygen levels, and enhance plant resistance and promote growth. However, at this stage, these technologies still have constraints such as high cost, complex application methods, and easy gas escape, which greatly reduces the utilization rate. At the same time, it is unrealistic to rely on the method of making hydrogen-rich water for irrigation, which requires a large amount of water resources, which is difficult to be widely used in field production activities.

[0004] For example, the Chinese invention patent "A hydrogen-rich liquid plant growth regulator and its preparation method and application" (CN201210154005.0) discloses that hydrogen is introduced into water or nutrient solution to obtain a hydrogen-rich plant growth regulator to promote plant growth and development and morphological construction, and enhance plant metabolic capacity. This supply method of hydrogen dissolved in liquid solves the problem that hydrogen can be directly used for paddy field production, but not all plants need to be watered in large quantities; at the same time, the hydrogen in the hydrogen-rich plant growth regulator prepared by this method is difficult to preserve and easily escapes; therefore, this method has certain limitations.

[0005] For example, in the Chinese invention patent "Preparation Method and Application of Slowly / controlled-release Hydrogen Fertilizer or Compound Hydrogen Fertilizer (CN201610747544.3)", the invention is prepared by adding one or more hydrogen production or hydrogen storage materials, with or without adding substances such as clay, fertilizers, pesticides, etc. in a certain proportion, using a granulator to make compressed particles of a certain size, and then coating with inorganic or organic polymer waterproof materials. In order to achieve a certain purpose, during the production process, the hydrogen production / storage materials are mixed with various substances, and are extremely susceptible to the influence of water, temperature, pH, oxidants, etc., resulting in a series of reactions, gas swelling phenomena, and problems such as reducing the functionality of the hydrogen production / storage materials.

[0006] For fertilizers, it is not only required to be simple and convenient to use, but also to meet the transportation and storage requirements. However, the existing technologies related to hydrogen-containing fertilizers have various problems, which pose obvious technical obstacles to the popularization and use of hydrogen fertilizers. Therefore, how to solve these problems and make hydrogen fertilizers widely used is a difficult problem we are currently facing. Summary of the Invention

[0007] In view of the deficiencies in the above technologies, the present invention provides a controlled-release hydrogen capsule fertilizer and its preparation method. By using the combination of hydrogen release capsules and plant nutrient raw materials, after use, the hydrogen release capsules release hydrogen to regulate plant growth, while the plant nutrient raw materials provide the necessary nutrients for plant growth, thereby promoting plant growth and development while reducing costs.

[0008] To achieve the above object, the present invention discloses a controlled-release hydrogen capsule fertilizer, which is composed of a plant nutrient raw material and a hydrogen release capsule. Calculated by mass percentage, the content of each component is as follows: plant nutrient raw material: 70 - 90%; hydrogen release capsule 10 - 30%.

[0009] Preferably, the plant nutrient raw material is prepared by mixing 20 - 50% of nitrogen fertilizer, 5 - 30% of phosphate fertilizer, 5 - 30% of potassium fertilizer, and 0.2 - 2% of trace elements.

[0010] The preparation method of the controlled-release hydrogen capsule fertilizer includes the following steps:

[0011] S1. Weigh each substance according to the required weight parts.

[0012] S2. Put the weight parts of the hydrogen release capsule and the plant nutrient raw material into a reaction kettle, stir at a rate of 100 - 300 r / min under the condition of 15°C - 40°C, and after stirring evenly, perform sealed bagging or sealed barreling to obtain a solid controlled-release hydrogen capsule fertilizer.

[0013] The present invention discloses a controllable hydrogen - releasing capsule fertilizer, which includes plant nutrient raw materials, hydrogen - releasing capsules, and also includes calcium alginate, a dispersant, and a fermentation broth. By mass percentage, the proportions of each substance are as follows: plant nutrient raw materials: 50 - 70%; hydrogen - releasing capsules: 10 - 30%; sodium alginate: 5 - 10%; 5% calcium salt solution: 0.5 - 2%; dispersant: 1 - 10%; fermentation broth: 5 - 20%.

[0014] Preferably, the dispersant is one or a mixture of acrylate sodium, rhamnolipid, sucrose ester, or phosphatidylcholine, and the fermentation broth is an industrial and agricultural waste organic resource such as molasses alcohol waste liquid, yeast waste liquid, or monosodium glutamate waste liquid.

[0015] The preparation method of the above - mentioned controllable hydrogen - releasing capsule fertilizer includes the following steps:

[0016] S1: Weigh each substance according to the required weight parts;

[0017] S2: Put the hydrogen - releasing capsules and sodium alginate into a rolling disc, rotate the disc to wrap the sodium alginate on the surface of the hydrogen - releasing capsules, then roll - spray the 5% calcium salt solution, transfer it to a reaction kettle after standing for 10 - 20 min, and add plant nutrient raw materials, a dispersant, and a fermentation broth for stirring;

[0018] S3: After stirring for 1 - 2 hours, seal and store to obtain a liquid controllable hydrogen - releasing capsule fertilizer.

[0019] Preferably, the stirring temperature is controlled at 15℃ - 40℃; the stirring speed of the rolling disc is 10 - 100 r / min; when stirring, it is necessary to measure the density of the whole solution so that the density is controlled between 1.20 - 1.55 g / cm 3 ³

[0020] Preferably, the preparation process of the hydrogen - releasing capsule is as follows: Weigh 15 parts of olive oil, 20 parts of hydrogenated palm oil, 20 parts of a modifier, 2 parts of calcium hydride, 1 part of antioxidant THBQ, and 2 parts of lipophilic dispersant polyacrylate sodium as the core material; successively add olive oil, hydrogenated palm oil, modifier, THBQ, calcium hydride, and polyacrylate sodium, stir at 30℃ for 2 h, with a rotation speed of 200 r / min to obtain material A; then weigh 10 parts of glycerol, 20 parts of carrageenan, 10 parts of propylene glycol alginate, and 15 parts of deionized water as the shell; stir glycerol and deionized water at 50 - 60℃ for 30 min, with a rotation speed of 250 r / min, then add carrageenan and gelatin and stir for 30 min, keep warm and stand for 30 min to remove bubbles to obtain material B. Press material B into a shell layer under a film - pressing machine, then fill in material A, and press the upper and lower films to form a primary capsule; then enter a rolling dryer and quickly dry and form at a temperature of 60℃ for 30 min, and ventilate and dry at a temperature of 40℃ for 6 h.

[0021] Preferably, during the pressing and forming process of Material B, the thickness of the outer shell layer is controlled within 0.5 - 1.0 mm; during the drying and forming process in a rolling dryer, the particle size of the hydrogen-release capsules is controlled within 2 - 5 mm, and the particle weight is 0.05 - 0.15 g.

[0022] The beneficial effects of the present invention are as follows: Compared with the prior art, the controlled hydrogen-release capsule fertilizer provided by the present invention protects the active metal or hydride through the hydrogen-release capsules, and then mixes with the plant nutrient raw materials, thus acting on plants in a dual manner to promote the growth and development of plants. During the preparation process of the hydrogen-release capsules, antioxidants and desiccants are added to prevent the hydrogen donor from being oxidized or reacting with water, improving the stability of the hydrogen-release capsules during storage and ensuring the stability of the fertilizer; according to different usage scenarios, the fertilizer is designed to be solid or liquid to meet different usage requirements. Brief Description of the Drawings

[0023] Figure 1 It is a process flow chart of the present invention. Detailed Embodiments

[0024] The following will describe the implementation schemes of the present invention in detail in combination with the embodiments and examples. However, those skilled in the art will understand that the following embodiments and examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the scope of protection of the present invention.

[0025] Please refer to Figure 1 , the present invention provides a controlled hydrogen-release capsule fertilizer, which is composed of a plant nutrient raw material and hydrogen-release capsules. Calculated by mass percentage, the contents of each component are as follows: plant nutrient raw material: 70 - 90%; hydrogen-release capsules 10 - 30%. In this embodiment, by mixing the plant nutrient raw material with the hydrogen-release capsules, the plant nutrient substances provide nutrients for the growth and development of plants, and the hydrogen released by the hydrogen-release capsules acts on the plants to promote plant growth. Thus, under the dual action, it is ensured that the plants can obtain a better growth state.

[0026] To achieve the above scheme, the plant nutrient raw material is prepared by mixing 20 - 50% of nitrogen fertilizer, 5 - 30% of phosphate fertilizer, 5 - 30% of potassium fertilizer, and 0.2 - 2% of trace elements.

[0027] The preparation process of the hydrogen release capsule is as follows: Weigh 15 parts of olive oil, 20 parts of hydrogenated palm oil, 20 parts of modifier, 2 parts of calcium hydride, 1 part of antioxidant THBQ, and 2 parts of lipophilic dispersant sodium polyacrylate as the core material; Add olive oil, hydrogenated palm oil, modifier, THBQ, calcium hydride, and sodium polyacrylate in sequence, and stir at 30 °C for 2 h with a rotation speed of 200 r / min to obtain Material A; Then weigh 10 parts of glycerol, 20 parts of carrageenan, 10 parts of propylene glycol alginate, and 15 parts of deionized water as the outer shell; Among them, glycerol and deionized water are stirred at 50 - 60 °C for 30 min with a rotation speed of 250 r / min, then add carrageenan and gelatin and stir for 30 min, keep warm and stand still to remove bubbles for 30 min to obtain Material B. Press Material B into the outer shell layer under a film press, then fill in Material A, and press the upper and lower films to form the initial capsule; Then enter a rolling dryer and quickly dry and form at a temperature of 60 °C for 30 min, and dry ventilated at a temperature of 40 °C for 6 h. The modifier is an alkaline ionic liquid, which is prepared from a methanol solution of potassium hydroxide, imidazole, and [Bmim]Br. More specifically, the potassium hydroxide - methanol solution and imidazole are reacted at a molar ratio of 1:1 at 25 - 30 °C for 30 - 40 min, then add the same molar amount of [Bmim]Br at 25 - 30 °C and stir magnetically at 180 r / min for 2 - 3 h, then add an appropriate amount of anhydrous ether and react at 25 - 30 °C for 15 - 20 h, filter and evaporate 2 - 5 times in cycles, and finally place it in a vacuum drying oven at 50 - 60 °C and dry for 18 - 24 h. During the process of pressing and forming Material B, the thickness of the outer shell layer is controlled at 0.5 - 1.0 mm; During the process of drying and forming in a rolling dryer, the particle size of the hydrogen release capsule is controlled at 2 - 5 mm, and the particle weight is 0.05 - 0.15 g.

[0028] In the specific implementation process, hydrogen is generated by the reaction of active metals or hydrides with water. Olive oil and hydrogenated palm oil are antioxidant / reducing, medium - basic, and hydrophobic liquids. Under the action of a solvent, the functionality of the hydrogen donor can be well guaranteed. At the same time, olive oil and hydrogenated palm oil are dried at 45 - 55 °C, which solves the problem that the hydrogen donor is prone to react with water, acids, oxidizing substances, etc. during storage and transportation, resulting in a reduction in its function. Water - soluble plant nutrient raw materials dissolve in water, can supply nutrients in a timely manner according to the needs of crops for nutrient elements, and have a quick effect. At the same time, the water - soluble plant nutrient raw materials are preferably non - oxidizing raw materials, and the hydrogen release capsule can coexist stably with the water - soluble plant nutrient raw materials in a solvent.

[0029] In this application, the hydride can obtain active hydrogen under normal temperature and pressure:

[0030] MH 2 +H 2 O≒M(OH) 2 +H 2 ↑

[0031] RBH 4 +2H 2 O≒KBO 2 +4H 2 ↑

[0032] Under alkaline conditions, the occurrence of this reaction can be slowed down, and the overflow rate of hydrogen molecules can be reduced. In addition, under alkaline conditions, the reduction of heavy metals can be accelerated, and the toxicity of heavy metals can be reduced:

[0033] Cu 2+ +H 2 =Cu+2H +

[0034] Pb 2+ +H 2 =Pb+2H +

[0035] At the same time, after the hydrogen-containing fertilizer is dissolved in water, due to the change of pH, the hydrogen release rate is accelerated, and hydrogen-rich water with different saturations can be obtained quickly. The hydrogen molecules in the hydrogen-rich water are highly dense, enhancing the activity of hydrogen molecules. Under alkaline conditions, the hydrogen molecules are further activated, thereby reducing heavy metal ions:

[0036] Cu 2+ +H 2 +2OH - =Cu+2H 2 O

[0037] Pb 2+ +H 2 +2OH - =Pb+2H 2 O

[0038] That is, activated hydrogen molecules are obtained under alkaline conditions to simply and efficiently reduce heavy metal ions.

[0039] Therefore, in the present invention, by adding a modifier to the capsule, which has the characteristics of alkaline ionic liquid, it plays a role in stabilizing and hydrogen-binding; during the use process, when the shell is digested and the core material comes into contact with water in the external environment, the hydrogen storage material will react with water to generate hydrogen, and the oil-based substances will undergo hydrolysis under alkaline conditions to generate alcohols and carboxylates. However, since the hydrolysis of oil-based substances consumes hydroxide ions in the system rather than water, this reaction will promote the forward reaction of the hydrogen storage material to generate sufficient hydroxide ions. To avoid this situation, after the oil-based substances are hydrolyzed to generate alcohols in the early stage, under the catalytic action of the alkaline ionic liquid, alcoholysis reactions will occur, such as triglycerides being converted into diglycerides and monoglycerides. The obtained products can coat the surface of the hydrogen storage material, reducing the hydrogen overflow rate and improving the utilization rate of hydrogen, maximizing the functional use of hydrogen.

[0040] Since the states of fertilizers are generally divided into solid fertilizers and liquid fertilizers, in this application, for solid fertilizers, the plant nutrient raw materials can be directly mixed with the hydrogen-releasing capsules, and it is only necessary to ensure that the weight and particle size of the hydrogen-releasing capsules are close to those of the plant nutrient raw materials. Thus, when the two are mixed, when their particle sizes are close, it ensures more uniform mixing, and when their masses are close, it ensures that during the movement process, neither substance will sink to the bottom, ensuring more uniform mixing of the two. When using liquid fertilizers, calcium alginate, a dispersant, and a fermentation broth are additionally added. Calcium alginate is formed by cross-linking sodium alginate with a calcium salt to form a protective layer outside the hydrogen-releasing capsules. The presence of this protective layer can not only prevent the hydrogen-releasing capsules from being damaged during stirring but also prevent moisture and the like from entering the hydrogen-releasing capsules and reacting with the hydrides therein during the mixing process with other substances. The presence of the dispersant enables more uniform dispersion of each substance during mixing, and there will be no agglomeration. The fermentation broth provides relevant solvent support for the entire liquid system. At the same time, since the capsule shell can be slowly dissolved in an acidic solution, while calcium alginate is stably present in an acidic medium, this enables the hydrogen-releasing capsules to exist more stably in the liquid fertilizer. During the use of the fertilizer, calcium alginate can be decomposed by soil microorganisms and the like, thereby releasing the hydrogen in the capsules.

[0041] To achieve the above object, the liquid fertilizer includes plant nutrient raw materials, hydrogen-releasing capsules, and also includes calcium alginate, a dispersant, and a fermentation broth. By mass percentage, the proportions of each substance are as follows: plant nutrient raw materials: 50 - 70%; hydrogen-releasing capsules: 10 - 30%; sodium alginate: 5 - 10%; 5% calcium salt solution: 0.5 - 2%; dispersant: 1 - 10%; fermentation broth: 5 - 20%. The dispersant is one or a mixture of acrylate, rhamnolipid, sucrose ester, or phosphatidylcholine. The fermentation broth is an industrial and agricultural waste organic resource such as alcohol molasses waste liquid, yeast waste liquid, or monosodium glutamate waste liquid. In this embodiment, calcium alginate is formed by cross-linking sodium alginate with 5% calcium salt.

[0042] The present invention also discloses a preparation method of a controlled hydrogen-releasing capsule fertilizer, which includes the following steps:

[0043] S1: Weigh each substance according to the required weight parts; put the hydrogen-release capsule and sodium alginate into a rotating disc, rotate the disc to wrap the sodium alginate on the surface of the hydrogen-release capsule, then spray 5% calcium salt solution while rolling, let it stand for 10 - 20 min and then transfer it to a reaction kettle, and then add plant nutrient raw materials, dispersant and fermentation broth and stir; S3: After stirring for 1 - 2 hours, store it in a sealed manner to obtain a controlled hydrogen-release capsule fertilizer; the temperature of stirring is controlled at 15°C - 40°C; the stirring speed of the rotating disc is 10 - 100 r / min; when stirring, it is necessary to measure the density of the whole solution so that the density is controlled between 1.20 - 1.55 g / cm 3 Between; in this embodiment, the stirring rate and the stirring temperature affect the mixing process of the two. If the stirring rate is too slow, it may cause agglomeration of the mixture. If the stirring rate is too fast, it may cause damage to the hydrogen-release capsule by the stirring equipment. And for the mixing temperature, if the temperature is too high or too low, it will affect the active metals or hydrides in the hydrogen-release capsule. Therefore, it is very necessary to keep the temperature within a suitable range.

[0044] The present invention will be further described below through specific examples and comparative examples. However, it should be understood that these examples are only for more detailed description and should not be construed as limiting the present invention in any form.

[0045] Example 1:

[0046] Weigh 40 parts of urea, 20 parts of potassium dihydrogen phosphate, 25 parts of potassium sulfate, and 0.50 parts of trace elements (Zn, Fe, B); 14.5 parts of hydrogen-release capsules with a shell thickness of 0.75 mm; then put urea, potassium dihydrogen phosphate, potassium sulfate, trace elements and hydrogen-release capsules into a reaction kettle, and stir at a rate of 200 r / min under the condition of 20°C. After stirring evenly, store it in a sealed plastic bag or sealed barrel.

[0047] Example 2:

[0048] Weigh 40 parts of urea, 20 parts of potassium dihydrogen phosphate, 25 parts of potassium sulfate, and 0.50 parts of trace elements (Zn, Fe, B); 14.5 parts of hydrogen-release capsules with a shell thickness of 0.50 mm; then put urea, potassium dihydrogen phosphate, potassium sulfate, trace elements and hydrogen-release capsules into a reaction kettle, and stir at a rate of 100 r / min under the condition of 20°C. After stirring evenly, store it in a sealed plastic bag or sealed barrel.

[0049] Example 3:

[0050] Weigh 40 parts of urea, 20 parts of potassium dihydrogen phosphate, 25 parts of potassium sulfate, and 0.50 parts of trace elements (Zn, Fe, B); 14.5 parts of hydrogen-releasing capsules with a shell thickness of 1.0 mm; then put urea, potassium dihydrogen phosphate, potassium sulfate, trace elements, and hydrogen-releasing capsules into the reaction kettle, stir at a rate of 300 r / min under the condition of 20 °C, and after stirring evenly, conduct sealed bagging or sealed barreling.

[0051] Conduct relevant experiments on the fertilizers obtained from the above three examples:

[0052] Test fertilizers: Hydrogen-releasing capsule fertilizers provided by Example 1, Example 2, and Example 3.

[0053] Test crops: Hongyan strawberries.

[0054] Experimental design

[0055] This experiment has 4 treatments, and the area of each plot is 30 m 2 , and each treatment has 6 replicates. Each plot is randomly arranged with isolation rows, and shallow trench burying is adopted between plots. Except for the different test fertilizer products among treatments, the rest are all managed according to the local farmers' conventional cultivation. The specific experimental design is as follows:

[0056] Treatment 1: Conventional basal fertilization + fertilizer without hydrogen-releasing capsules (the difference from Example 1 is that hydrogen-releasing capsules are not added) 30 kg / mu;

[0057] Treatment 2: Conventional basal fertilization + fertilizer provided by Example 1 30 kg / mu;

[0058] Treatment 3: Conventional basal fertilization + fertilizer provided by Example 2 30 kg / mu;

[0059] Treatment 4: Conventional basal fertilization + fertilizer provided by Example 3 30 kg / mu;

[0060] Among them, the conventional basal fertilization is to apply 80 kg of biological organic fertilizer and 40 kg of 16-16-16 compound fertilizer per mu, and deeply plow and fertilize evenly.

[0061] Fertilization method: Apply in three times, 10 kg / mu is applied at the seedling stage, flowering stage, and fruit swelling stage respectively.

[0062] Sampling method and determination items: Each plot is harvested separately and the yield is measured separately. The yield results are shown in Table 1.

[0063] Table 1 Strawberry fresh weight (kg / mu) after different treatments

[0064]

[0065] Note: Different lowercase letters in the same row indicate significant differences between different treatments (P<0.05)

[0066] As can be seen from Table 1, after applying the fertilizer containing hydrogen-release capsules, the strawberry yield increased significantly compared to the fertilizer without hydrogen. This proves that the hydrogen donors carried by the hydrogen-release capsules can release hydrogen, enabling hydrogen to act on plants and increase the strawberry yield. Treatments 2, 3, and 4 are fertilizers applied with hydrogen-release capsules of different shell thicknesses. It can be seen that the fertilizer effect of Treatment 3, that is, the fertilizer obtained in Example 2, is the best. This may be caused by the shell thickness of the hydrogen-release capsules. When the shell thickness of the hydrogen-release capsules is small, after use, the shell of the hydrogen-release capsules is damaged in a short time, enabling the hydrides inside to react rapidly, generating a large amount of hydrogen, thus effectively promoting the growth and development of plants. For Treatment 4, that is, the hydrogen-release capsules used in Example 3 have a large shell thickness and cannot be damaged. However, due to its long action time, it can, to a certain extent, make up for the problem of less hydrogen release.

[0067] At the same time, relevant experiments were also carried out on liquid fertilizers. First, prepare the relevant liquid fertilizers:

[0068] Example 4:

[0069] Weigh 35 parts of urea, 20 parts of dipotassium hydrogen phosphate, 15 parts of potassium chloride, 0.5 part of trace elements (Zn, Mn); 15 parts of hydrogen-release capsules with a shell thickness of 0.75 mm; 5.5 parts of calcium alginate; 1 part of dispersant; 8 parts of fermentation broth. First, mix the hydrogen-release capsules with calcium alginate. After mixing evenly, add the dispersant, fermentation broth, and plant nutrient raw materials, and stir at a rate of 100 r / min under the condition of 20 °C, while controlling the density at 1.20 - 1.55 g / cm 3 , and after stirring evenly, carry out sealed bagging or sealed barreling.

[0070] Example 5:

[0071] Weigh 35 parts of urea, 20 parts of dipotassium hydrogen phosphate, 15 parts of potassium chloride, 0.5 part of trace elements (Zn, Mn); 20 parts of hydrogen-release capsules with a shell thickness of 0.75 mm; 5.5 parts of calcium alginate; 1 part of dispersant; 8 parts of fermentation broth. First, mix the hydrogen-release capsules with calcium alginate. After mixing evenly, add the dispersant, fermentation broth, and plant nutrient raw materials, and stir at a rate of 100 r / min under the condition of 20 °C, while controlling the density at 1.20 - 1.55 g / cm 3 , and after stirring evenly, carry out sealed bagging or sealed barreling.

[0072] Example 6:

[0073] Weigh 40 parts of urea, 20 parts of dipotassium hydrogen phosphate, 15 parts of potassium chloride, and 0.5 part of trace elements (Zn, Mn); 25 parts of hydrogen-release capsules with a shell thickness of 0.75 mm; 5.5 parts of calcium alginate; 1 part of dispersant; 8 parts of fermentation broth. First, mix the hydrogen-release capsules with calcium alginate. After mixing evenly, add the dispersant, fermentation broth, and plant nutrient raw materials, and stir at a rate of 100 r / min under the condition of 20 °C, while controlling the density at 1.20 - 1.55 g / cm 3 , and after stirring evenly, perform sealed bagging or sealed barreling.

[0074] Conduct relevant experiments on the fertilizers obtained from the above three examples:

[0075] Test crops: rice.

[0076] Test sites: moderately and slightly Cd-polluted farmlands in Guangdong and Guangxi.

[0077] Experimental design

[0078] This experiment has 4 treatments, and the area of each plot is 30 m 2 , and each treatment has 6 replicates. The plots are randomly arranged with isolation rows, and single irrigation and single drainage are adopted between plots to avoid cross-irrigation and cross-drainage. Except for the different test fertilizer products among treatments, the rest are all managed according to the local farmers' conventional cultivation methods. The specific experimental design is as follows:

[0079] Treatment 1: Conventional fertilization + fertilizer without hydrogen-release capsules (the difference from Example 4 is that hydrogen-release capsules are not added), 30 kg / mu;

[0080] Treatment 2: Conventional fertilization + fertilizer provided in Example 4, 30 kg / mu;

[0081] Treatment 3: Conventional fertilization + fertilizer provided in Example 5, 30 kg / mu;

[0082] Treatment 4: Conventional fertilization + fertilizer provided in Example 6, 30 kg / mu;

[0083] Among them, the conventional fertilization is to apply 50 kg of the same compound fertilizer as the base fertilizer per mu.

[0084] Fertilization method: Conventional fertilization before rice transplanting is used as the base fertilizer, 10 kg is applied per mu 5 - 7 days after rice transplanting, and 20 kg is applied from rice tillering to before filling.

[0085] Sampling method and determination items

[0086] Before rice planting, the soil pH value in Guangdong was 5.61, and the soil Cd content was 0.91 mg / kg; the soil pH value in Guangxi was 6.45, and the soil Cd content was 0.85 mg / kg. After rice harvest, soil samples of 0-20 cm were taken from each plot to measure the soil pH value; each plot was harvested separately and the yields were measured respectively, and the Cd content in the grains was measured. The yield results are shown in Table 2, and the Cd content in the grains is shown in Table 3.

[0087] Table 2 Rice yields under different treatments (kg / mu)

[0088]

[0089]

[0090] Table 3 Cd content in rice grains under different treatments (mg / kg)

[0091]

[0092] The effects of continuous application of the test product for 3 years on the soil pH value are shown in Table 4.

[0093] Table 4 Changes in soil pH values under different treatments

[0094]

[0095] Result analysis

[0096] From Tables 2, 3 and 4, it can be seen that after applying a certain amount of hydrogen-releasing fertilizer, the rice grain yield is significantly increased compared with that without hydrogen-releasing fertilizer, the Cd content in the rice grains is reduced, and the Cd content in the grains of Treatment 3 (Example 5) and Treatment 4 (Example 6) does not exceed the grain standard (≤0.2 mg / kg), and the soil pH value is increased. This shows that adding an appropriate amount of hydrogen donor can effectively improve the heavy metal stress resistance of rice, improve crop quality and soil properties. At the same time, regarding the yield of rice, it is found that there is no significant difference in the yields of Treatment 3 and Treatment 4, which may be due to the balance between the added amount of hydrogen-releasing material and the demand of rice. Therefore, the added amount of hydrogen-releasing capsule is not the more the better, but needs to be adjusted according to the growth characteristics of different plants to optimize the effect and economic benefits. At the same time, with the increase of the added amount of hydrogen-releasing capsule, the pH of the soil increases, which indicates that the hydride in the hydrogen-releasing material reduces the soil acidity through a series of changes, which provides certain technical support for the repair of slightly acidic heavy metal pollution with this fertilizer.

[0097] The above only discloses several specific embodiments of the present invention, but the present invention is not limited thereto, and any changes that can be thought of by those skilled in the art should fall within the protection scope of the present invention.

Claims

1. A controlled-release hydrogen capsule fertilizer, characterized in that, it is composed of a plant nutrient raw material and a hydrogen-release capsule. Calculated by mass percentage, the contents of each component are as follows: plant nutrient raw material: 70-90%; hydrogen-release capsule 10-30%; wherein, the plant nutrient raw material is prepared by mixing 20-50% of nitrogen fertilizer, 5-30% of phosphate fertilizer, 5-30% of potassium fertilizer and 0.2-2% of trace elements; wherein, the preparation process of the hydrogen-release capsule is as follows: Weigh 15 parts of olive oil, 20 parts of hydrogenated palm oil, 20 parts of modifier, 2 parts of calcium hydride, 1 part of antioxidant THBQ, and 2 parts of lipophilic dispersant sodium polyacrylate as the core material; Add olive oil, hydrogenated palm oil, modifier, THBQ, calcium hydride, and sodium polyacrylate in sequence, and stir at 30°C for 2 h at a rotation speed of 200 r / min to obtain material A; Then weigh 10 parts of glycerol, 20 parts of carrageenan, 10 parts of propylene glycol alginate, and 15 parts of deionized water as the outer shell; Among them, glycerol and deionized water are stirred at 50-60°C for 30 min at a rotation speed of 250 r / min, then carrageenan and gelatin are added and stirred for 30 min, and then kept warm and static to remove bubbles for 30 min to obtain material B; Under a film press, material B is pressed into an outer shell layer, and then material A is filled in, and the upper and lower films are pressed to form a primary capsule; Then enter a rolling dryer and quickly dry and form at a temperature of 60°C for 30 min, and ventilate and dry at a temperature of 40°C for 6 h; wherein, the modifier is obtained by reacting a potassium hydroxide-methanol solution with imidazole at a molar ratio of 1:1 at 25-30°C for 30-40 min, then adding the same molar amount of [Bmim]Br at 25-30°C and magnetically stirring and reacting at 180 r / min for 2-3 h, then adding an appropriate amount of anhydrous ether and reacting at 25-30°C for 15-20 h, filtering and evaporating 2-5 times, and finally drying in a vacuum drying oven at 50-60°C for 18-24 h.

2. A preparation method of a controlled-release hydrogen capsule fertilizer, characterized in that, used for preparing the controlled-release hydrogen capsule fertilizer described in claim 1, including the following steps: S1. Weigh each substance according to the required weight parts; S2. Put the weight parts of the hydrogen-release capsule and the plant nutrient raw material into a reaction kettle, stir at a rate of 100-300 r / min under the condition of 15°C - 40°C, and after stirring evenly, carry out sealed bagging or sealed barreling to obtain a solid controlled-release hydrogen capsule fertilizer.

3. A controlled-release hydrogen capsule fertilizer, characterized in that, including a plant nutrient raw material, a hydrogen-release capsule, and also including calcium alginate, a dispersant and a fermentation broth. According to the mass percentage, the proportions of each substance are: plant nutrient raw material: 50-70%; hydrogen-release capsule 10-30%; sodium alginate: 5-10%; 5% calcium salt solution: 0.5-2%; dispersant: 1-10%; fermentation broth: 5-20%; Among them, the preparation process of the hydrogen-release capsule is as follows: Weigh 15 parts of olive oil, 20 parts of hydrogenated palm oil, 20 parts of modifier, 2 parts of calcium hydride, 1 part of antioxidant THBQ, and 2 parts of lipophilic dispersant sodium polyacrylate as the core material; Add olive oil, hydrogenated palm oil, modifier, THBQ, calcium hydride, and sodium polyacrylate in sequence, stir at 30 °C for 2 h, with a rotation speed of 200 r / min to obtain Material A; Then weigh 10 parts of glycerol, 20 parts of carrageenan, 10 parts of propylene glycol alginate, and 15 parts of deionized water as the shell; Among them, glycerol and deionized water are stirred at 50-60 °C for 30 min, with a rotation speed of 250 r / min, then add carrageenan and gelatin and stir for 30 min, keep warm and stand still to remove bubbles for 30 min to obtain Material B. Under the film press, press Material B into the shell layer, then fill in Material A, and press the upper and lower films to form the initial capsule; Then enter the rolling dryer and quickly dry and form at a temperature of 60 °C for 30 min, and ventilate and dry at a temperature of 40 °C for 6 h. Among them, the modifier is prepared by reacting potassium hydroxide-methanol solution and imidazole at a molar ratio of 1:1 at 25-30 °C for 30-40 min, then adding the same molar amount of [Bmim]Br at 25-30 °C and magnetically stirring and reacting at 180 r / min for 2-3 h, then adding an appropriate amount of anhydrous ether and reacting at 25-30 °C for 15-20 h, filtering and evaporating 2-5 times in cycles, and finally drying in a vacuum drying oven at 50-60 °C for 18-24 h.

4. The controlled-release hydrogen capsule fertilizer according to claim 3, characterized in that the dispersant is one or a mixture of acrylate, rhamnolipid, sucrose ester or phosphatidylcholine, and the fermentation broth is industrial and agricultural waste organic resources such as alcohol molasses waste liquid, yeast waste liquid, and monosodium glutamate waste liquid.

5. A preparation method of a controlled-release hydrogen capsule fertilizer, characterized in that used for preparing the controlled-release hydrogen capsule fertilizer according to any one of claims 3-4, including the following steps: S1: Weigh each substance according to the required weight parts; S2: Put the hydrogen-release capsule and sodium alginate into the rolling disc, rotate the disc to wrap the sodium alginate on the surface of the hydrogen-release capsule, then roll and spray 5% calcium salt solution, transfer to the reaction kettle after standing for 10-20 min, and add plant nutrient raw materials, dispersant and fermentation broth and stir; S3: After stirring for 1-2 hours, seal and store to obtain the liquid controlled-release hydrogen capsule fertilizer.

6. The preparation method of the controlled-release hydrogen capsule fertilizer according to claim 5, characterized in that: The temperature of stirring is controlled at 15°C - 40°C; the stirring speed of the rolling disc is 10 - 100 r / min; when stirring, it is necessary to measure the density of the whole solution so that the density is controlled between 1.20 - 1.55 g / cm 3 3 7. The controlled-release hydrogen capsule fertilizer according to claim 1 or 3, characterized in that during the pressing and forming process of Material B, the thickness of the shell layer is controlled at 0.5-1.0 mm; during the drying and forming process in the rolling dryer, the particle size of the hydrogen-release capsule is controlled at 2-5 mm, and the particle weight is 0.05-0.15 g.

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