Coated hydrogen donor, fertilizer containing coated hydrogen donor, preparation method and application thereof

Abstract

The present invention provides a coated hydrogen donor, a fertilizer containing the coated hydrogen donor, and a preparation method and application thereof, relating to the technical field of agriculture. The coated hydrogen donor provided by the present invention comprises 40-60 parts of a hydrogen storage material; 5-10 parts of an oil; 5-10 parts of a stabilizer; 5-10 parts of a dry powder; 15-20 parts of a modified β-cyclodextrin; 5-15 parts of sodium alginate; and 1-5 parts of a 5% calcium chloride solution. Using this coated hydrogen donor to prepare a fertilizer containing the coated hydrogen donor can provide hydrogen while providing elements such as nitrogen, phosphorus, and potassium required for plant growth. This fertilizer can well solve the difficulties in the application of hydrogen donors, solve the problem that hydrogen-containing products are prone to react with water, acids, oxidizing substances, etc. during storage and transportation, resulting in a reduction in their functions; and also prevent problems such as swelling of product packaging containers caused by the generation of gas. At the same time, this fertilizer can be safely, stably, and widely promoted, and can be better applied in fields, greenhouse greenhouses, fruit orchards, and intelligent agriculture.

Description

Technical Field

[0001] The present invention relates to the technical field of agriculture, and in particular to a coated hydrogen donor, a fertilizer containing the coated hydrogen donor, and a preparation method and application thereof. Background Art

[0002] Hydrogen is one of the 17 essential nutrient elements for plants, and only extremely scarce free hydrogen exists on the earth and in the earth's atmosphere. In the past 20-odd years, the research on the role of hydrogen has mainly been carried out in the fields of medicine, energy, etc., and certain achievements have been made. In the past 10-odd years, some agricultural science and technology workers in scientific research institutes have also been studying the role and application of hydrogen in agriculture, and found that hydrogen can improve plant stress resistance, regulate the action of plant hormones, and promote plant growth, and is also considered a potential substitute for pesticides and chemical fertilizers. However, since most scientific and technological workers in scientific research institutes only conduct research in the laboratory and do not fully consider the complexity of the production process of hydrogen-containing fertilizers, production costs, the difficulty of storage and transportation, the promotion applicability, the safety and convenience of farmers' use, and the combination with modern water and fertilizer application facilities, etc., the application and promotion of hydrogen fertilizers are still blocked.

[0003] At present, the experimental research basically involves introducing hydrogen gas in aluminum cans or alloy steel cylinders into water to form hydrogen-rich water with different saturations for irrigating crops, so as to induce plants to produce antioxidant enzymes, reduce oxidative stress damage and the level of reactive oxygen species, so as to enhance plant stress resistance and promote growth. However, at present, these technologies still have restrictive factors such as high costs, complex application methods, and easy escape of gas resulting in a significant reduction in utilization rate. At the same time, it is also unrealistic to irrigate by relying on the method of manufacturing hydrogen-rich water, which requires a large amount of water resources and is difficult to be widely applied in field production activities.

[0004] For example, in the Chinese invention patent "A Hydrogen-rich Liquid Plant Growth Regulator and Its Preparation Method and Application" (CN201210154005.0), this method discloses introducing hydrogen gas 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 dissolving hydrogen in liquid solves the problem that hydrogen can be directly used in paddy field production, but not all plants need to be watered in large amounts; at the same time, the hydrogen in the hydrogen-rich plant growth regulator prepared by this method is difficult to preserve and is easy to escape; therefore, this method has certain limitations.

[0005] For example, in the Chinese invention patent "Preparation Method and Application of Sustained-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, making them into compressed particles of a certain size by a granulator, and then coating them with inorganic or organic polymer waterproof materials. On the one hand, only one coating is carried out in this invention, and the coating effect is poor, unable to ensure the stability of the hydrogen production / storage materials; on the other hand, 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., and are prone to a series of reactions, resulting in problems such as gas swelling and reduction of the functionality of the hydrogen production / storage materials.

[0006] In view of this, the present invention is specifically proposed. Summary of the Invention

[0007] The first object of the present invention is to provide a coated hydrogen donor, which can avoid the reaction of the hydrogen storage material with water absorption and ensure the stability of the hydrogen donor.

[0008] The second object of the present invention is to provide a fertilizer containing a coated hydrogen donor. The coated hydrogen donor is combined with a water-soluble plant nutrient raw material to make a fertilizer containing a coated hydrogen donor. The prepared hydrogen-containing fertilizer is stable, does not react and cause gas swelling, etc., and is convenient for production, storage, and operation, so as to solve at least one of the above-mentioned problems in the prior art.

[0009] The third object of the present invention is to provide a preparation method of a hydrogen fertilizer, with a simple preparation process, low production cost, and strong promotion adaptability.

[0010] The fourth object of the present invention is to provide an application of a hydrogen-containing fertilizer in plant cultivation, which can be applied by methods such as furrow application, hole application, or broadcasting, and is applied during the growth period of plants.

[0011] In the first aspect, the present invention provides a coated hydrogen donor. By weight, the coated hydrogen donor includes 40-60 parts of a hydrogen storage material; 5-10 parts of an oil; 5-10 parts of a stabilizer; 5-10 parts of a dry powder; 15-20 parts of modified β-cyclodextrin; 5-15 parts of sodium alginate; 1-5 parts of a 5% calcium chloride aqueous solution; and the hydrogen storage material is a hydride, including calcium hydride, magnesium hydride, potassium borohydride, sodium borohydride, or a mixture thereof; the oil is medium-chain triglyceride, camellia oil, olive oil, grape seed oil, or a mixture thereof; the stabilizer is calcium chloride, magnesium chloride, calcium hydroxide, magnesium hydroxide, or graphene; the dry powder is shellfish and shrimp shell powder.

[0012] Preferably, the preparation method of the coated hydrogen donor includes the following steps:

[0013] (1) Mix the hydrogen storage material, the grease, and the dry powder for 10 - 15 minutes, and perform dry extrusion granulation to obtain primary coated particles; then screen the primary coated particles through a 20 - 30 mesh sieve;

[0014] (2) Place the primary coated particles in a disk granulator, then add the modified β - cyclodextrin powder into the disk granulator, and rotate the disk to make the modified β - cyclodextrin wrap around the outer layer of the primary coated particles to obtain secondary coated particles;

[0015] (3) Place the secondary coated particles in a disk granulator, then add the sodium alginate powder into the disk granulator, rotate the disk to make the sodium alginate wrap around the outer layer of the secondary coated particles, and spray a 5% calcium chloride aqueous solution to cross - link the sodium alginate. The cross - linked sodium alginate serves as the outer coating of the secondary coated particles to obtain the coated hydrogen donor, and then screen the coated hydrogen donor through a 10 - 20 mesh sieve.

[0016] Preferably, the modified β - cyclodextrin is a composite material formed by coating hydroxy - iron oxide with cyclodextrin, wherein the mass ratio of cyclodextrin to hydroxy - iron oxide is 20 - 30:100.

[0017] In a second aspect, the present invention provides a fertilizer containing a coated hydrogen donor, which mainly consists of 80 - 90 parts of water - soluble plant nutrient raw materials and 10 - 20 parts of the aforementioned coated hydrogen donor.

[0018] Preferably, the fully water - soluble plant nutrient raw materials include 20 - 50 parts of nitrogen fertilizer, 5 - 30 parts of phosphate fertilizer, 5 - 30 parts of potassium fertilizer, and 0.2 - 2 parts of trace elements.

[0019] As a further technical solution, the nitrogen fertilizer is urea, ammonium chloride, or ammonium nitrate; the phosphate fertilizer is potassium hydrogen phosphate, potassium dihydrogen phosphate, monoammonium phosphate, potassium polyphosphate, diammonium hydrogen phosphate, diammonium dihydrogen phosphate, or ammonium polyphosphate; the potassium fertilizer is potassium chloride, potassium sulfate, potassium nitrate, potassium hydrogen phosphate, or potassium polyphosphate; the trace elements include at least one of iron, manganese, zinc, copper, molybdenum, and boron.

[0020] In a third aspect, the present invention provides a preparation method of a hydrogen - containing fertilizer, which includes the following steps: S1. Prepare materials according to the aforementioned weight parts;

[0021] S2. Mix the coated hydrogen donor, nitrogen fertilizer, phosphate fertilizer, potassium fertilizer, and trace elements in the corresponding weight parts evenly to obtain a mixture;

[0022] The mixing is carried out by stirring, the rotation speed of the stirring is 100 - 200 r / min, the time is 1 - 2 h, and the temperature is maintained at 15℃ - 40℃.

[0023] In a fourth aspect, the present invention provides an application of the hydrogen - containing fertilizer in plant cultivation.

[0024] As a further technical solution, the application method of the hydrogen-containing fertilizer includes ditch application, hole application or broadcast application.

[0025] As a further technical solution, the application is the application of the hydrogen-containing fertilizer during the growth period of plants.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] 1) The present invention uses modified β-cyclodextrin and crosslinked sodium alginate as the coating material, and a hydrogen storage material as the core material, and obtains a coated hydrogen donor through a multi-step granulation and coating technology. This coated hydrogen donor solves the problem that hydrogen-containing products are prone to react with water, acids, oxidizing substances, etc. during storage and transportation, resulting in a reduction in their functions, ensures the stability of the hydrogen storage material, and has a slow-release effect, greatly improving the utilization rate of the hydrogen storage material.

[0028] 2) At room temperature, a process combining extrusion granulation and disk granulation is adopted to prepare coated hydrogen donors with uniform size. The process is simple and suitable for industrial production.

[0029] 3) The coated hydrogen donor of the present invention is combined with the nutrients required by crops to prepare a fertilizer containing a coated hydrogen donor, which can be safely, low-cost, stably and efficiently promoted on a large scale, and can be better applied in fields, greenhouse greenhouses, fruit orchards and intelligent agriculture.

[0030] 4) The selected plant nutrient raw materials of the hydrogen-containing fertilizer provided by the present invention are fully water-soluble, can be replenished in a timely manner according to the needs of crops for nutrient elements, and have a quick effect.

[0031] 5) The hydrogen-containing fertilizer of the present invention can be applied by ditch application, hole application or broadcast application, etc. The application methods have a wide selection, low cost and high efficiency. Specific embodiments

[0032] 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. Those not specified in specific conditions are carried out according to conventional conditions or conditions recommended by the manufacturer. Those reagents or instruments not specified in the manufacturer are all conventional products that can be obtained through commercial purchase. The raw materials used in the present invention are all obtained through conventional market purchases unless otherwise specified.

[0033] First aspect, the present invention provides a coated hydrogen donor. By weight, it mainly consists of 40 - 60 parts of hydrogen storage material, 5 - 10 parts of oil, 5 - 10 parts of stabilizer, 5 - 10 parts of dry powder, 15 - 20 parts of modified β - cyclodextrin, 5 - 15 parts of sodium alginate, and 1 - 5 parts of calcium chloride aqueous solution with a concentration of 5%. Among them, the hydrogen donor includes hydrides such as calcium hydride, magnesium hydride, potassium borohydride, sodium borohydride or their mixtures. The hydrogen storage material reacts with water to generate hydrogen. At the same time, due to multiple coating treatments, on the one hand, it can ensure the stability of the product, and on the other hand, it can make hydrogen slowly release during use, maximizing the utilization of the functionality of hydrogen. The oil is medium - chain triglyceride, tea oil, olive oil, grape seed oil or their mixtures. In this embodiment, the oil is used as the first coating layer to obtain primary coated particles. The present invention selects oil as the coating material, which has the following properties: 1. The coating material has antioxidant / reducing properties, medium alkalinity, and hydrophobicity, and is relatively stable; 2. The coating material has a certain viscosity; 3. The coating material has a coating effect, improves the appearance and fluidity of the hydrogen storage material; 4. The inner layer is a small amount of oil, which improves the dispersibility and stability of the particles and extends the shelf life. The stabilizer is calcium chloride, magnesium chloride, calcium hydroxide, magnesium hydroxide or graphene. The stabilizer can prevent the coated hydrogen donor from disintegrating during hydrolysis, thus ensuring a steady hydrogen release during hydrolysis. The dry powder is shell powder of shellfish, crab and shrimp. The shell powder of shellfish, crab and shrimp is a green environmental protection material, has a porous structure, strong adsorption force, and contains astaxanthin. Astaxanthin can induce crops to produce a variety of resistance substances and can effectively control a variety of pathogenic bacteria, so it has excellent stress resistance and disease resistance and can have a good synergistic effect on the fertilizer of the present invention.

[0034] In this embodiment, the modified β - cyclodextrin is used as the second coating layer. The modified β - cyclodextrin has a hydrophobic cavity inside, which can play a slow - release role in the penetration of water. In this embodiment, the cross - linked sodium alginate is used as the outermost coating layer, which solves the problem that the hydrogen donor is prone to react with water, acid, oxidation substances, etc. during storage and transportation, resulting in a reduction in its function. With the cooperation of the barrier of the cross - linked sodium alginate and the slow - release effect of the modified β - cyclodextrin, the hydrogen storage material will not be rapidly released after encountering water, the slow - release rate is more stable, and the slow - release is more persistent.

[0035] As a further implementation method, the preparation method of the coated hydrogen donor is as follows:

[0036] (1) Mix the hydrogen storage material, oil, stabilizer, and dry powder for 10 - 15 minutes. For example, the specific time can be 10 minutes, 12 minutes, or 15 minutes, but it is not limited to the listed values. Other unlisted values within the numerical range are also applicable. Then, perform dry extrusion granulation to obtain primary coated particles. After polishing the primary coated particles, sieve them through a 20 - 30 mesh sieve. For example, the specific mesh sieve can be 20 mesh, 25 mesh, or 30 mesh, but it is not limited to the listed values. Other unlisted values within the numerical range are also applicable. Through this step, a hydrogen donor of the target size can be obtained, and the polished particles are flat, facilitating the subsequent coating process. At the same time, the oil, stabilizer, and dry powder ensure the stability of the hydrogen storage material. Since it is dry extrusion granulation, the hydrogen storage material will not react with water during the process.

[0037] (2) Place the primary coated particles in a disk granulator, then add the modified β - cyclodextrin powder into the disk granulator. Rotate the disk to make the modified β - cyclodextrin wrap around the outer layer of the primary coated particles, obtaining secondary coated particles. By wrapping the modified β - cyclodextrin on the surface of the primary coated particles, the stability of the system is further improved.

[0038] (3) Place the secondary coated particles in a disk granulator, then add the sodium alginate powder into the disk granulator. Rotate the disk to make the sodium alginate wrap around the outer layer of the secondary coated particles, and spray a 5% calcium chloride aqueous solution to cross - link the sodium alginate. The cross - linked sodium alginate serves as the outer coating of the secondary coated particles, obtaining a coated hydrogen donor. Then, sieve the coated hydrogen donor through a 10 - 20 mesh sieve. For example, the specific mesh sieve can be 10 mesh, 16 mesh, or 20 mesh, but it is not limited to the listed values. Other unlisted values within the numerical range are also applicable, obtaining a coated hydrogen donor with the target particle size.

[0039] As a further embodiment, the modified β - cyclodextrin is a composite material formed by cyclodextrin coating hydroxy - iron oxide, wherein the mass ratio of cyclodextrin to hydroxy - iron oxide is 20 - 30:100. The modified β - cyclodextrin of the present invention has hydroxyl functional groups on its exterior, is hydrophilic, has a cyclic structural framework cavity inside, can adsorb hydrophobic substances, can further enhance the slow - release effect. At the same time, under the action of van der Waals forces, hydrophobic interactions, and the matching of host - guest molecules, a stable chemical compound is formed, thereby ensuring the stability of the hydrogen storage material during storage and transportation.

[0040] The present invention uses multi - layer coating to improve the controlled - release effect of hydrogen, and at the same time, the proportion of the coating material can be changed to adjust the film - forming effect, such as particle size, hardness, etc. During use, hydrogen can be slowly released, maximizing the functionality of hydrogen and having long - term effectiveness.

[0041] The coating technology can provide a physical barrier for hydrogen storage materials, separating them from the surrounding environment. Its advantages are as follows: (1) It can improve physical properties; (2) Control and regulate the release ability; (3) Improve the stability of the core material; (4) Shield flavors and odors; (5) Facilitate combined use. The purpose of coating is to make the hydrogen donor inside the coated hydrogen donor react slowly with the water in the soil after being applied to the soil and release slowly. Through coating, slow release of hydrogen can be achieved, coordinated with plant nutrient absorption, improving the utilization rate of hydrogen. At the same time, hydrogen fertilizer is also equivalent to a new type of fertilizer, which can reduce the dosage and frequency of topdressing and the increased labor cost, and reduce environmental pollution caused by fertilizer waste, realizing the sustainable development of agriculture and the environment.

[0042] In the embodiments of the present invention, the coated hydrogen donor fertilizer is composed of 80 - 90 parts of water-soluble plant nutrient raw materials and 10 - 20 parts of the aforementioned coated hydrogen donor. While providing elements such as nitrogen, phosphorus, and potassium required for plant growth, it can also provide hydrogen, improve plant stress resistance, regulate plant hormones, and promote plant growth; the plant nutrient raw materials are water-soluble plant nutrient raw materials, which dissolve in water and can supply nutrients in a timely manner according to the needs of crops for nutrient elements, with quick effects; under this ratio, plants can obtain comprehensive nutrition.

[0043] In some preferred embodiments, the water-soluble plant nutrient raw materials include but are not limited to nitrogen sources: such as urea, ammonium chloride, ammonium nitrate, etc.; phosphorus sources: such as potassium hydrogen phosphate, potassium dihydrogen phosphate, monoammonium phosphate, potassium metaphosphate, diammonium hydrogen phosphate, diammonium dihydrogen phosphate, ammonium polyphosphate, etc.; potassium sources: such as potassium chloride, potassium sulfate, potassium nitrate, potassium hydrogen phosphate or potassium metaphosphate, etc.; plant trace elements include but are not limited to at least one of iron, manganese, zinc, copper, molybdenum, and boron. For the types and dosages of the above nutrient elements, those skilled in the art can select according to needs, such as 20 - 50 parts of nitrogen fertilizer, 5 - 30 parts of phosphorus fertilizer, 5 - 30 parts of potassium fertilizer, and 0.2 - 2 parts of trace elements.

[0044] In the embodiments of the present invention, hydrides such as calcium hydride, magnesium hydride, potassium borohydride, and sodium borohydride can obtain activated hydrogen under normal temperature and pressure, such as:

[0045] CaH 2 +H 2 O=Ca(OH) 2 +H 2 ↑

[0046] MgH 2 +2H 2 O=Mg(OH) 2 +2H 2 ↑

[0047] KBH 4 +2H2 O = KBO 2 + 4H 2 ↑

[0048] NaBH 4 + 2H 2 O = NaBO 2 + 4H 2 ↑

[0049] In addition to hydrogen, the reaction products of these hydrogen storage materials with water also include borate radicals (BO 2 - ), Ca 2+ , Mg 2+ , K + , Na + ions. Except for Na + , all of them are elements required for plant growth. Among them, K + is the well-known potassium fertilizer. Sodium borohydride (NaBH 4 ) contains sodium ions that can easily cause salt damage. Therefore, potassium borohydride is preferred to replace sodium borohydride. However, since hydrogen can make plants tolerant to salinity and alkalinity, and sodium borohydride can release a large amount of hydrogen when it meets water, the actual application amount is very small, and a small amount of use will not cause salt damage. Therefore, sodium borohydride can also be applied under normal circumstances.

[0050] In addition, under alkaline conditions, it can help the following reactions to proceed, accelerate the reduction of heavy metal ions, and reduce heavy metal toxicity.

[0051] Cd 2+ + H 2 = Cd + 2H +

[0052] Pb 2+ + H 2 = Pb + 2H +

[0053] At the same time, after the hydrogen-containing fertilizer is dissolved in water, due to the change of pH, it can accelerate the acquisition of hydrogen-rich water with different saturations. The hydrogen molecules in the hydrogen-rich water are highly concentrated, enhancing the activity of hydrogen molecules. Under alkaline conditions, the hydrogen molecules are further activated, thereby reducing heavy metal ions:

[0054] Cd 2+ + H 2 + 2OH - = Cd + 2H 2 O

[0055] Pb 2+ + H 2 + 2OH - = Pb + 2H 2 O

[0056] That is, activated hydrogen molecules are obtained under alkaline conditions to simply and efficiently reduce heavy metal ions.

[0057] In a second aspect, the present invention provides a method for preparing a hydrogen-containing fertilizer, comprising the following steps:

[0058] S1. Prepare materials according to the stated parts by weight;

[0059] S2. Mix the stated parts by weight of the coated hydrogen donor, nitrogen fertilizer, phosphate fertilizer, potassium fertilizer, and trace elements evenly to obtain a mixture;

[0060] In some preferred embodiments, the substances are made uniform by stirring. The rotation speed of stirring can be, for example, but not limited to, 100 r / min, 150 r / min, or 200 r / min, and the stirring time can be, for example, but not limited to, 1 h, 1.5 h, or 2 h; during the stirring process, the temperature of the solution of the plant nutrient raw materials can be, for example, but not limited to, 15 °C, 25 °C, 35 °C, or 40 °C.

[0061] By the above method, a stable fertilizer containing a coated hydrogen donor can be prepared. The preparation method is simple and convenient, and the prepared fertilizer containing a coated hydrogen donor has good stability.

[0062] Due to the strict requirements of the hydrogen donor for environmental temperature and humidity, this poses a great challenge to its addition as a solid fertilizer. Even for conventional granulation temperature of solid granular fertilizers, it is not lower than 60 degrees. 2-6% of water needs to be added during this granulation process, and due to the particularity of the material addition during granulation (such as acid prohibition and oxidation prohibition), the raw materials cannot be evenly mixed. There are also problems in the production, packaging, and storage of solid fertilizer products where the temperature and humidity cannot be controlled. The preparation process provided in this embodiment: 1) Obtain a coated hydrogen donor by coating the hydrogen storage material with oil, stabilizer, dry powder, modified β-cyclodextrin, and cross-linked sodium alginate multiple times; 2) Make the materials uniform by controlling the stirring speed; 3) Obtain a high-quality hydrogen fertilizer through the combination of materials, especially the addition of plant nutrients; 4) Control the temperature parameters during the production process, stir and react evenly into a mixture until the packaged finished product to ensure product stability.

[0063] In a third aspect, the present invention provides an application of a hydrogen-containing fertilizer in plant cultivation.

[0064] The hydrogen-containing fertilizer provided by the present invention includes plant nutrients and a hydrogen donor, can provide the necessary nutrients for plant growth, improve the stress resistance of plants, promote plant growth, and can be used for plant cultivation.

[0065] In some preferred embodiments, the application methods of the hydrogen-containing fertilizer are diverse, including but not limited to furrow application, hole application, or broadcasting, or other application methods well-known to those skilled in the art.

[0066] In some preferred embodiments, the hydrogen-containing fertilizer is applied during the growth period of plants. Applying the hydrogen-containing fertilizer of the present invention during the growth period can maximize the effect on plants, effectively improve the stress resistance of plants, and promote plant growth.

[0067] In addition, when comparing the present invention with CN201610747544.3, the present invention has the following differences and advantages: 1. Different formulations. The present invention contains a hydrogen donor with stable properties and various water-soluble plant nutrients; 2. Different manufacturing processes. The present invention uses dry extrusion granulation and disk granulation technologies to obtain a multi-layer coated hydrogen donor, with simple processes, low costs, and low energy consumption; 3. Different effects of the products. The technical product of the present invention is a water-soluble product, which can supply nutrients in a timely manner according to the needs of crops for macro, meso, and micro elements, etc., with quick effects; 4. Different aspects of product packaging and transportation. The products of the present invention are packaged in barrels or bags with a sealing effect, ensuring safe and efficient transportation.

[0068] When comparing the present invention with CN201210154005.0, the present invention has the following differences and advantages: 1. Different formulations. The present invention contains a hydrogen donor with stable properties and various plant nutrients; 2. Different manufacturing processes. Using a multi-layer coating technology to prepare a fertilizer containing a coated hydrogen donor, with slow and controlled release of hydrogen, long-lasting effects, better results, and greatly improving the utilization rate of hydrogen, avoiding waste. Direct irrigation with hydrogen-rich water is costly, and at the same time, due to the easy volatilization of hydrogen, a large amount of waste is caused; 3. Different aspects of product packaging and transportation. The products of the present invention are packaged in barrels and bags with a sealing effect, ensuring safe, efficient, and low-cost transportation. 4. Convenient for farmers to apply, and can be connected to mechanized and automated fertilization systems.

[0069] The present invention will be further illustrated below through specific examples and comparative examples. However, it should be understood that these examples are only for more detailed illustration and should not be construed as limiting the present invention in any form.

[0070] Example 1

[0071] A coated hydrogen donor includes a hydrogen storage material, an oil, a dry powder, and a stabilizer. Among them, by weight, 60 parts of calcium hydride as the hydrogen storage material, 10 parts of olive oil as the oil, 10 parts of shellfish and shrimp shell powder as the dry powder, 8 parts of graphene as the stabilizer; 15 parts of modified β-cyclodextrin; 5 parts of sodium alginate; and 2 parts of a 5% calcium chloride aqueous solution.

[0072] Preparation method: (1) Add calcium hydride, olive oil, shell powder of shellfish and crab, and graphene into a mixer and mix for 15 min. Put the above mixture into a dry double-roll extrusion granulator with a power of 75 kW and a pore size of 1.0 mm for extrusion granulation. After cooling, sieve through a 30-mesh sieve to obtain primary coated granules; (2) Put the primary coated granules into a disk granulator, add the modified β-cyclodextrin powder in parts by weight into the disk for rolling coating, so that the modified β-cyclodextrin powder in parts by weight is wrapped on the primary coated granules to obtain secondary coated granules; (3) Put the secondary coated granules into a disk granulator, add the sodium alginate powder in parts by weight into the disk granulator for rolling coating, so that sodium alginate is wrapped on the outer layer of the secondary coated granules, and spray a 5% calcium chloride aqueous solution to crosslink sodium alginate. The crosslinked sodium alginate serves as the outer coating of the secondary coated granules to obtain a coated hydrogen donor, and then sieve through a 20-mesh sieve and air-dry at room temperature to obtain the finished product of the coated hydrogen donor.

[0073] Example 2

[0074] A coated hydrogen donor, comprising a hydrogen storage material, an oil, a dry powder, and a stabilizer. Among them, by weight, 60 parts of magnesium hydride as the hydrogen storage material, 10 parts of camellia oil as the oil, 10 parts of shell powder of shellfish and crab as the dry powder, 8 parts of magnesium hydroxide as the stabilizer; 15 parts of modified β-cyclodextrin; 5 parts of sodium alginate; 2 parts of a 5% calcium chloride aqueous solution.

[0075] Preparation method: (1) Add magnesium hydride, camellia oil, shell powder of shellfish and crab, and magnesium hydroxide into a mixer and mix for 15 min. Put the above mixture into a dry double-roll extrusion granulator with a power of 75 kW and a pore size of 1.0 mm for extrusion granulation. After cooling, sieve through a 30-mesh sieve to obtain primary coated granules; (2) Put the primary coated granules into a disk granulator, add the modified β-cyclodextrin powder in parts by weight into the disk for rolling coating, so that the modified β-cyclodextrin powder in parts by weight is wrapped on the primary coated granules to obtain secondary coated granules; (3) Put the secondary coated granules into a disk granulator, add the sodium alginate powder in parts by weight into the disk granulator for rolling coating, so that sodium alginate is wrapped on the outer layer of the secondary coated granules, and spray a 5% calcium chloride aqueous solution to crosslink sodium alginate. The crosslinked sodium alginate serves as the outer coating of the secondary coated granules to obtain a coated hydrogen donor, and then sieve through a 20-mesh sieve and air-dry at room temperature to obtain the finished product of the coated hydrogen donor.

[0076] Example 3

[0077] A coated hydrogen donor, comprising a hydrogen storage material, an oil, a dry powder, and a stabilizer. Among them, by weight, 40 parts of calcium hydride as the hydrogen storage material, 10 parts of olive oil as the oil, 10 parts of shell powder of shellfish and crab as the dry powder, 8 parts of graphene as the stabilizer; 15 parts of modified β-cyclodextrin; 5 parts of sodium alginate; 2 parts of a 5% calcium chloride aqueous solution.

[0078] Preparation method: (1) Add calcium hydride, olive oil, shell powder of shellfish and crab, and graphene into a mixer and mix for 15 minutes. Put the above mixture into a dry double-roll extrusion granulator with a power of 75 kW and a pore size of 1.0 mm for extrusion granulation. After cooling, sieve through a 30-mesh sieve to obtain primary coated granules; (2) Put the primary coated granules into a disk granulator, add the modified β-cyclodextrin powder in parts by weight into the disk for rolling coating, so that the modified β-cyclodextrin powder in parts by weight is wrapped on the primary coated granules to obtain secondary coated granules; (3) Put the secondary coated granules into a disk granulator, add the sodium alginate powder in parts by weight into the disk granulator for rolling coating, so that sodium alginate is wrapped on the outer layer of the secondary coated granules, and spray a 5% calcium chloride aqueous solution to crosslink sodium alginate. The crosslinked sodium alginate serves as the outer coating of the secondary coated granules to obtain a coated hydrogen donor, and then sieve through a 20-mesh sieve and air-dry at room temperature to obtain the finished product of the coated hydrogen donor.

[0079] Example 4

[0080] A coated hydrogen donor, comprising a hydrogen storage material, an oil, a dry powder, and a stabilizer. Among them, by weight, 40 parts of potassium borohydride as the hydrogen storage material, 10 parts of medium-chain triglyceride as the oil, 10 parts of shell powder of shellfish and crab as the dry powder, 10 parts of calcium chloride as the stabilizer; 20 parts of modified β-cyclodextrin; 10 parts of sodium alginate; 3 parts of a 5% calcium chloride aqueous solution.

[0081] Preparation method: (1) Add potassium borohydride, medium-chain triglyceride, shell powder of shellfish and crab, and calcium chloride into a mixer and mix for 10 minutes. Put the above mixture into a dry double-roll extrusion granulator with a power of 75 kW and a pore size of 1.0 mm for extrusion granulation. After cooling, sieve through a 25-mesh sieve to obtain primary coated granules; (2) Put the primary coated granules into a disk granulator, add the modified β-cyclodextrin powder in parts by weight into the disk for rolling coating, so that the modified β-cyclodextrin powder in parts by weight is wrapped on the primary coated granules to obtain secondary coated granules; (3) Put the secondary coated granules into a disk granulator, add the sodium alginate powder in parts by weight into the disk granulator for rolling coating, so that sodium alginate is wrapped on the outer layer of the secondary coated granules, and spray a 5% calcium chloride aqueous solution to crosslink sodium alginate. The crosslinked sodium alginate serves as the outer coating of the secondary coated granules to obtain a coated hydrogen donor, and then sieve through a 16-mesh sieve and air-dry at room temperature to obtain the finished product of the coated hydrogen donor.

[0082] Comparative Example 1

[0083] A coated hydrogen donor, comprising a hydrogen storage material, an oil, a dry powder, and a stabilizer. Among them, by weight, 60 parts of calcium hydride as the hydrogen storage material, 10 parts of olive oil as the oil, 10 parts of shell powder of shellfish and crab as the dry powder, and 8 parts of graphene as the stabilizer.

[0084] Preparation method: Add calcium hydride, olive oil, shell powder of shellfish and crab, and graphene into a mixer and mix for 15 minutes. Put the above mixture into a dry double-roll extrusion granulator with a power of 75 kW and a pore diameter of 1.0 mm for extrusion granulation. After cooling, sieve through a 30-mesh sieve to obtain the finished product of the first-stage coated hydrogen donor.

[0085] Comparative Example 2

[0086] A coated hydrogen donor, comprising a hydrogen storage material, an oil, a dry powder, and a stabilizer. Among them, by weight, 60 parts of calcium hydride as the hydrogen storage material, 10 parts of olive oil as the oil, 10 parts of shell powder of shellfish and crab as the dry powder, 8 parts of graphene as the stabilizer; 5 parts of sodium alginate; 2 parts of a 5% calcium chloride aqueous solution.

[0087] Preparation method: (1) Add calcium hydride, olive oil, shell powder of shellfish and crab, and graphene into a mixer and mix for 15 minutes. Put the above mixture into a dry double-roll extrusion granulator with a power of 75 kW and a pore diameter of 1.0 mm for extrusion granulation. After cooling, sieve through a 30-mesh sieve to obtain the first-stage coated particles; (2) Put the first-stage coated particles into a disk granulator, add the sodium alginate powder in parts by weight into the disk granulator for rolling coating, so that the sodium alginate is wrapped on the outer layer of the first-stage coated particles, and spray a 5% calcium chloride aqueous solution to crosslink the sodium alginate. The crosslinked sodium alginate serves as the outer coating of the second-stage coated particles to obtain the coated hydrogen donor, and then sieve through a 20-mesh sieve and air-dry at room temperature to obtain the finished product of the coated hydrogen donor.

[0088] Perform stability tests and simulated soil tests on the above comparative examples and four examples, and detect whether there is a situation of bag swelling and the time to start releasing hydrogen for the coated hydrogen donor. The results are shown in Table 1 below:

[0089] Table 1 Stability and hydrogen release time of different coated hydrogen donors

[0090]

[0091] Result analysis: As can be seen from the above table, the products of the coated hydrogen donors in Examples 1-4 are still stable after one month, and there are no phenomena such as bag swelling. In Comparative Example 1, without modified β-cyclodextrin coating, the crosslinking of sodium alginate occurs quickly and the hydrogen release is relatively intense; in Comparative Example 2, which is only crosslinked with sodium alginate, bag swelling also occurs and the hydrogen release is relatively fast; from the above two comparative examples, it can be obtained that by performing a second-stage coating of modified β-cyclodextrin powder on the first-stage coated particles and crosslinking sodium alginate on the outer layer of the second-stage coating, the hydrogen donor can be made stable and release hydrogen gently.

[0092] Example 5

[0093] A coated hydrogen donor fertilizer, comprising a plant nutrient raw material and the coated hydrogen donor of Example 1. Among them, by weight, the plant nutrient raw material includes: 40 parts of urea, 25 parts of dipotassium hydrogen phosphate, 14 parts of potassium chloride, 1 part of trace elements (Zn, B, Mn); 20 parts of the coated hydrogen donor of Example 1.

[0094] Preparation method: Mix the coated hydrogen donor, urea, dipotassium hydrogen phosphate, potassium chloride, and trace elements of Example 1 in parts by weight to obtain a mixture, stir in a reaction kettle to form a mixture, keep the temperature at 15°C, the stirring speed of the reaction kettle is 150 r / min, and after 2 h of stirring reaction, a solid hydrogen-containing fertilizer is obtained, which is packed in sealed bags or sealed barrels.

[0095] Example 6

[0096] A coated hydrogen donor fertilizer, comprising a plant nutrient raw material and the coated hydrogen donor of Example 2. Among them, by weight, the plant nutrient raw material includes: 40 parts of urea, 25 parts of dipotassium hydrogen phosphate, 19.8 parts of potassium sulfate, 0.2 part of trace elements (Fe, Mo); 15 parts of the coated hydrogen donor of Example 2.

[0097] Preparation method: Mix the coated hydrogen donor, urea, dipotassium hydrogen phosphate, potassium sulfate, and trace elements of Example 2 in parts by weight to obtain a mixture, stir in a reaction kettle to form a mixture, keep the temperature at 30°C, the stirring speed of the reaction kettle is 100 r / min, and after 2 h of stirring reaction, a solid hydrogen-containing fertilizer is obtained, which is packed in sealed bags or sealed barrels.

[0098] Comparative Example 3

[0099] A hydrogen-containing fertilizer, comprising a plant nutrient raw material and the hydrogen donor of Comparative Example 1. Among them, by weight, the plant nutrient raw material includes: 40 parts of urea, 25 parts of dipotassium hydrogen phosphate, 14 parts of potassium chloride, 1 part of trace elements (Zn, B, Mn); 20 parts of the hydrogen donor of the comparative example.

[0100] Preparation method: Mix the coated hydrogen donor, urea, dipotassium hydrogen phosphate, potassium chloride, and trace elements of Comparative Example 1 in parts by weight to obtain a mixture, stir in a reaction kettle to form a mixture; keep the temperature at 15°C, the stirring speed of the reaction kettle is 150 r / min, and after 2 h of stirring reaction, a solid hydrogen-containing fertilizer is obtained, which is packed in sealed bags or sealed barrels.

[0101] Test Example 1

[0102] Test crop: Rice.

[0103] Test sites: Mild to moderate Cd-polluted farmlands in Guangdong and Hunan.

[0104] Test design

[0105] This experiment had 4 treatments, with each plot having an area of 30 m 2 , and each treatment had 6 replicates. The plots were randomly arranged with isolation rows, and single irrigation and single drainage were adopted between plots to avoid cross-irrigation and cross-drainage. Except for the different test fertilizer products among the treatments, the rest were all managed according to the local farmers' conventional cultivation methods. The specific experimental design is as follows:

[0106] Treatment 1: Conventional fertilization + fertilizer without coated hydrogen donor (the difference from Example 5 is that the coated hydrogen donor is not added), 30 kg / mu;

[0107] Treatment 2: Conventional fertilization + fertilizer provided in Example 5, 30 kg / mu;

[0108] Treatment 3: Conventional fertilization + fertilizer provided in Comparative Example 3, 30 kg / mu;

[0109] Among them, the conventional fertilization was to apply 50 kg of the same compound fertilizer per mu as the base fertilizer.

[0110] Fertilization method: The conventional fertilization before rice transplanting was used as the base fertilizer, 10 kg was applied per mu 5 - 7 days after rice transplanting, and 20 kg was applied from rice tillering to before filling.

[0111] Sampling method and measurement items

[0112] Before rice planting, the pH value of the soil in Guangdong was 5.75, and the soil Cd content was 0.86 mg / kg; the pH value of the soil in Hunan was 5.98, and the soil Cd content was 0.95 mg / kg. After rice harvest, for each plot, 0 - 20 cm soil samples were taken to measure the soil pH value; each plot was harvested separately and measured for yield, 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.

[0113] Table 2 Rice yields of different treatments (kg / mu)

[0114]

[0115] Table 3 Cd contents in rice grains of different treatments (mg / kg)

[0116]

[0117] The influence of continuous application of the test products for 3 years on the soil pH value is shown in Table 4.

[0118] Table 4 Changes in soil pH values of different treatments

[0119]

[0120] Result analysis: As can be seen from Tables 2, 3, and 4, after applying the fertilizer containing the coated hydrogen donor with a certain amount, the grain yield of rice increased significantly compared to the fertilizer without the coated hydrogen donor, and the Cd content in rice grains decreased. The Cd content in Treatments 2 and 3 did not exceed the grain standard (≤0.2 mg / kg), and the soil pH value increased. This indicates that adding an appropriate amount of the coated hydrogen donor can effectively improve the heavy metal stress resistance of rice, and improve crop quality and soil properties. The effect of Treatment 2 is better than that of Treatment 3, which further verifies the effect of the coated hydrogen donor, providing certain technical support for the remediation of acidic and moderately heavy metal pollution with this fertilizer.

[0121] Test Example 2

[0122] Test fertilizers: The fertilizer containing the coated hydrogen donor provided in Example 6.

[0123] Test crops: Potatoes.

[0124] Test site: Guangdong.

[0125] This test was set with 3 treatments, 30 m per plot 2 , and each treatment had 6 replicates. A: Blank treatment without fertilization; B: The fertilizer of Example 6 without adding the coated hydrogen donor; C: The fertilizer containing the coated hydrogen donor provided in Example 6. During the flowering stage and tuber swelling stage of potatoes, apply by strip application at 30 kg per mu. Except for the different test fertilizer products among the treatments, the rest were all managed according to the local farmers' conventional cultivation methods. The results are shown in Table 5.

[0126] Table 5 Commercial rate and yield of potatoes after different treatments

[0127]

[0128] Result analysis: As can be seen from Table 5, after applying the fertilizer containing the coated hydrogen donor with a certain amount, the commercial rate and yield of potatoes can be effectively improved. This may be because the hydrogen generated in the coated hydrogen donor plays a certain positive role in the disease resistance of potatoes, and also plays a growth-promoting role in the growth of potatoes.

[0129] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A coated hydrogen donor, characterized in that, by weight, the coated hydrogen donor comprises: 40 - 60 parts of hydrogen storage material; 5 - 10 parts of oil; 5 - 10 parts of stabilizer; 5 - 10 parts of dry powder; 15 - 20 parts of modified β - cyclodextrin; 5 - 15 parts of sodium alginate; 1 - 5 parts of 5% calcium chloride solution; and the hydrogen storage material is a hydride, including calcium hydride, magnesium hydride, potassium borohydride, sodium borohydride or a mixture thereof; the oil is medium - chain triglyceride, camellia oil, olive oil, grape seed oil or a mixture thereof; the stabilizer is one of calcium chloride, magnesium chloride, calcium hydroxide, magnesium hydroxide or graphene; the dry powder is shell powder of shellfish, crab and shrimp.

2. The coated hydrogen donor according to claim 1, characterized in that, the preparation method of the coated hydrogen donor comprises the following steps: S1. Mix the hydrogen storage material, oil, stabilizer and dry powder for 10 - 15 min, and then perform dry extrusion granulation after obtaining the mixture to obtain primary coated granules; then polish the primary coated granules and screen them through a 20 - 30 - mesh sieve; S2. Put the primary coated granules into a disk granulator, and then add the modified β - cyclodextrin powder into the disk granulator, rotate the disk to make the modified β - cyclodextrin wrap around the outer layer of the primary coated granules to obtain secondary coated granules; S3. Put the secondary coated granules into a disk granulator, add the sodium alginate powder into the disk granulator, rotate the disk to make the sodium alginate wrap around the outer layer of the secondary coated granules, and spray 5% calcium chloride aqueous solution to cross - link the sodium alginate. The cross - linked sodium alginate serves as the outer coating of the secondary coated granules to obtain the coated hydrogen donor, and then screen the coated hydrogen donor through a 10 - 20 - mesh sieve.

3. The coated hydrogen donor according to claim 2, characterized in that, the modified β - cyclodextrin is a composite material formed by coating hydroxyl iron oxide with cyclodextrin, wherein the mass ratio of cyclodextrin to hydroxyl iron oxide is 20 - 30:

100.

4. A fertilizer containing a coated hydrogen donor, characterized in that, it mainly consists of 80 - 90 parts of water - soluble plant nutrient raw materials and 10 - 20 parts of the coated hydrogen donor according to any one of claims 1 - 3; the water - soluble plant nutrient raw materials include 20 - 50 parts of nitrogen fertilizer, 5 - 30 parts of phosphate fertilizer, 5 - 30 parts of potassium fertilizer and 0.2 - 2 parts of trace elements.

5. The fertilizer containing a coated hydrogen donor according to claim 4, characterized in that, the nitrogen fertilizer is urea, ammonium chloride or ammonium nitrate; the phosphate fertilizer is potassium hydrogen phosphate, potassium dihydrogen phosphate, monoammonium phosphate, potassium polyphosphate, diammonium hydrogen phosphate, diammonium dihydrogen phosphate or ammonium polyphosphate; the potassium fertilizer is potassium chloride, potassium sulfate, potassium nitrate, potassium hydrogen phosphate or potassium polyphosphate; the trace elements include at least one of iron, manganese, zinc, copper, molybdenum and boron.

6. A preparation method of a fertilizer containing a coated hydrogen donor based on claim 1, characterized in that, it comprises the following steps: S1. Prepare materials according to the stated weight parts; S2. Mix the coated hydrogen donor, nitrogen fertilizer, phosphate fertilizer, potassium fertilizer and trace elements evenly to obtain a mixture; ​ The mixing is carried out by stirring. The rotation speed of the stirring is 100 - 200 r / min, the time is 1 - 2 h, and the temperature is maintained at 15°C - 40°C.

7. Application of the coated hydrogen donor fertilizer according to claim 1 in plant cultivation, characterized in that, the application methods of the hydrogen-containing fertilizer include furrow application, hole application or broadcasting.

8. The application according to claim 7, characterized in that, the application is the application of the hydrogen-containing fertilizer during the growth period of plants.

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