Hydrogen-containing fertilizer and its preparation method and application

Abstract

The present invention provides a hydrogen-containing fertilizer and a preparation method and application thereof, and relates to the field of fertilizer technology. The hydrogen-containing fertilizer provided by the present invention is mainly composed of a hydrogen donor, a water-soluble plant nutrient raw material, oil, a hydrophilic emulsifier, an emulsifier and a dispersant in a specific ratio, and the pH is 7-8. The hydrogen-containing fertilizer can well solve the difficulties in the application of hydrogen donors, solve the problem that the hydrogen donors are easy to react with water, acid, oxides, etc. during storage and transportation, resulting in reduced functions; and also prevent the product packaging containers from swelling barrels or bags due to the generation of gas. The hydrogen-containing fertilizer is made by combining hydrogen donors, water-soluble plant nutrient raw materials, oils, and hydrophilic emulsifiers, and has the advantages of wide selection of fertilization methods, low cost, and high efficiency; at the same time, it can also be promoted safely, stably, and on a large scale, and can be better applied in fields, greenhouses, and intelligent agriculture.

Description

Technical Field

[0001] The invention relates to the technical field of fertilizers, and in particular to a hydrogen-containing fertilizer and a preparation method and application 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, the Chinese invention patent "Preparation method and application of slow-release hydrogen fertilizer or composite hydrogen fertilizer (CN201610747544.3)" is prepared by adding or not adding clay, fertilizer, pesticide and other substances in a certain proportion to one or more hydrogen production or storage materials, using a granulator to form compressed particles of a certain size, and then using inorganic or organic polymer waterproof materials for coating. On the one hand, the invention only performs coating once, and the coating effect is poor, and the stability of the hydrogen production / storage materials cannot be guaranteed; on the other hand, during the production process, the hydrogen production / storage materials are mixed with various substances, which are easily affected by water, temperature, pH, oxidants, etc., and are prone to a series of reactions and produce flatulence and reduce the functionality of the hydrogen production / storage materials. At the same time, the plant nutrient elements of this patent are not fully water-soluble products, and they need to be slowly released when applied to the soil, which cannot reflect the rapid effect of the product, especially when plants encounter salt damage, drought, frost damage and need timely remedial measures, or when fruits and vegetables grow and develop and improve nutritional quality. It is difficult to play a role in time.

[0006] Therefore, how to obtain hydrogen fertilizer and method with low cost, simple application method and good storage stability is a problem that needs to be solved urgently in this field.

[0007] In view of this, the present invention is proposed. Summary of the invention

[0008] The first purpose of the present invention is to provide a hydrogen-containing fertilizer, which is made by combining a hydrogen donor, a water-soluble plant nutrient raw material, oil, a hydrophilic emulsifier, an emulsifier aid, and a dispersant. The hydrogen-containing fertilizer is stable, not prone to reaction and flatulence, and is easy to produce, store, and operate, so as to solve at least one of the above-mentioned problems.

[0009] The second object of the present invention is to provide a method for preparing the above hydrogen-containing fertilizer.

[0010] The third object of the present invention is to provide application of the above hydrogen-containing fertilizer.

[0011] In a first aspect, the present invention provides a hydrogen-containing fertilizer, which is mainly composed of a hydrogen donor, a water-soluble plant nutrient raw material, a hydrophilic oil emulsifier, an emulsifier aid and a dispersant;

[0012] The mass ratio of the hydrogen donor to the water-soluble plant nutrient raw material is 1:90 to 1:10;

[0013] The mass ratio of the hydrogen donor to the oil is 1:15 to 1:1;

[0014] The mass ratio of the hydrogen donor to the hydrophilic emulsifier is 1:10 to 5:1;

[0015] The mass ratio of the hydrogen donor to the co-emulsifier is 1:5 to 5:1;

[0016] The mass ratio of the hydrogen donor to the dispersant is 1:2 to 25:1;

[0017] The pH of the hydrogen-containing fertilizer is 7-8.

[0018] As a further technical solution, the hydrogen-containing fertilizer includes, by weight: 1-5 parts of hydrogen donor, 60-90 parts of water-soluble plant nutrient raw materials, 5-15 parts of oil, 1-10 parts of hydrophilic emulsifier, 1-5 parts of auxiliary emulsifier, 0.2-2 parts of dispersant, 1-5 parts of antioxidant and 1-5 parts of desiccant.

[0019] As a further technical solution, the hydrogen donor includes: at least one of calcium hydride, magnesium hydride, potassium borohydride or sodium borohydride;

[0020] The water-soluble plant nutrient raw material includes: at least one of nitrogen fertilizer, phosphorus fertilizer, potassium fertilizer or trace element fertilizer;

[0021] The oil comprises: at least one of medium chain triglycerides, silicone oil, tea oil, olive oil, palm oil or grape seed oil;

[0022] The hydrophilic emulsifier includes at least one of sodium carboxymethyl cellulose, sodium alginate, xanthan gum or caprylic decanoate;

[0023] The auxiliary emulsifier includes at least one of vegetable glycerin, n-octanol or methanol.

[0024] As a further technical solution, the water-soluble plant nutrient raw materials include 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 element fertilizer by weight.

[0025] As a further technical solution, the antioxidant includes at least one of a free radical absorber or an oxygen absorber;

[0026] Preferably, the free radical absorber comprises at least one of THBQ, BHA, BHT, PG, benzylphenol, vitamin E, guaiac resin or astaxanthin;

[0027] Preferably, the oxygen absorbent comprises iron powder.

[0028] Preferably, the desiccant comprises at least one of shell powder, crab powder and shrimp shell powder or calcium chloride.

[0029] As a further technical solution, the dispersant includes at least one of sodium polyacrylate or rhamnolipid, sucrose ester or phosphatidylcholine;

[0030] Preferably, the dispersant has a fineness of 20-100 mesh and a viscosity of 300-1500 mPa·s.

[0031] In a second aspect, the present invention provides a method for preparing the above-mentioned hydrogen-containing fertilizer, comprising: mixing oil, antioxidant, desiccant, hydrophilic emulsifier and co-emulsifier to obtain a mixed liquid, mixing a hydrogen donor, a water-soluble plant nutrient raw material and a dispersant to obtain a mixture, and then mixing the obtained mixed liquid and the mixture to prepare the hydrogen-containing fertilizer.

[0032] As a further technical solution, the mixing method of the mixed liquid and the mixture includes stirring;

[0033] Preferably, the stirring speed is 100-1000 r / min, the time is 0.5-2 h, and the temperature is 15°C-45°C.

[0034] In a third aspect, the present invention provides an application of a hydrogen-containing fertilizer in plant cultivation, wherein the application method of the hydrogen-containing fertilizer includes flushing, hole application or spraying;

[0035] Preferably, the hydrogen-containing fertilizer is applied during the plant growth period.

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

[0037] 1) The present invention combines a hydrogen donor, a water-soluble plant nutrient raw material, oil, a hydrophilic emulsifier, an emulsifier aid and a dispersant to prepare a stable and uniform hydrogen-containing fertilizer, thereby solving the problem that hydrogen-containing products are prone to react with water, acid, oxidizing substances and the like during storage and transportation, resulting in reduced functionality; and also preventing problems such as bulging barrels or bags in product packaging containers due to the generation of gas.

[0038] 2) The hydrogen-containing fertilizer provided by the present invention has the advantages of wide selection of fertilization methods, low cost, high efficiency, etc. It can be promoted on a large scale safely, at low cost, stably and efficiently, and can be better applied in fields, greenhouses and intelligent agriculture.

[0039] 3) The plant nutrient raw materials selected for the hydrogen-containing fertilizer provided by the present invention are water-soluble, and can be replenished in time according to the needs of crops for nutrient elements, and the effect is quick.

[0040] 4) The hydrogen-containing fertilizer provided by the present invention is emulsified by adding a hydrophilic emulsifier and an emulsifier aid, and after application, the oil will be emulsified to form an oil-in-water state, and the oil will become small molecules, thereby reducing the side effects of plant oils on soil and plants.

[0041] 5) The hydrogen-containing fertilizer of the present invention can be applied by flushing (water-fertilizer integration), hole application (drip irrigation) or spraying (drone spraying), etc., with a wide range of application methods, low cost and high efficiency. DETAILED DESCRIPTION

[0042] The embodiments of the present invention will be described in detail below in conjunction with the embodiments and examples, but it will be appreciated by those skilled in the art that the following embodiments and examples are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. If specific conditions are not specified, proceed according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0043] In the first aspect, the present invention provides a hydrogen-containing fertilizer, which is mainly composed of a hydrogen donor, a water-soluble plant nutrient raw material, oil, a hydrophilic emulsifier, an emulsifier and a dispersant, and the pH is 7.0-8.0. Wherein, the hydrogen donor includes a hydride such as calcium hydride, magnesium hydride, potassium borohydride, sodium borohydride or a mixture thereof, and the hydrogen donor can generate hydrogen when it reacts with water. At the same time, since the pH is controlled at 7.0-8.0, on the one hand, the stability of the product can be guaranteed, and on the other hand, the hydrogen can be slowly released during use to maximize the functionality of hydrogen. Oil as a solvent for hydrogen-containing fertilizers can be medium-chain triglycerides, silicone oil, tea oil, olive oil, palm oil, grape seed oil or a mixture thereof, which are antioxidant / reducing, medium alkaline, hydrophobic liquids. Under the action of the solvent, the functionality of the hydrogen donor can be well guaranteed. At the same time, the oil is preferably dried at 45-55°C, which helps to solve the problem that the hydrogen donor is easy to react with water, acid, oxidizing substances, etc. during storage and transportation, resulting in reduced functionality. Water-soluble plant nutrition raw materials are dissolved in water, can be replenished in time according to the needs of crops for nutrient elements, and have quick effects. At the same time, water-soluble plant nutrition raw materials are selected with non-oxidizing, medium-alkaline raw materials, and hydrogen donors can stably coexist with water-soluble plant nutrition raw materials in solvents. Hydrophilic emulsifiers are sodium carboxymethyl cellulose, sodium alginate, caprylic acid glyceride or its mixture. Under the effect of hydrophilic emulsifiers, after the hydrogen-containing fertilizer of the present invention is used, grease can form water-in-oil substances, and grease becomes small molecules, reducing the side effects of grease on soil and plants. Co-emulsifiers can be adsorbed on the oil-water interface to further reduce interfacial tension, enhance the fluidity of the interfacial film, reduce the bending energy required when the emulsion is formed, so that the emulsion can be formed spontaneously, and the stability of the emulsified oil is enhanced. Dispersants can reduce the time and energy required to complete the dispersion process, and enhance the stability of the system.

[0044] In the present invention, the mass ratio of hydrogen donor to oil is 1:15 to 1:1, the mass ratio of hydrogen donor to water-soluble plant nutrition raw material is 1:90 to 1:10, the mass ratio of hydrogen donor to hydrophilic emulsifier is 1:10 to 5:1, the mass ratio of hydrogen donor to auxiliary emulsifier is 1:5 to 5:1, and the mass ratio of hydrogen donor to dispersant is 1:2 to 25:1. Hydrogen donors can be prepared into hydrogen-containing fertilizers by combining corresponding components of water-soluble plant nutrition raw materials, oils and fats, and hydrophilic emulsifiers. While providing nitrogen, phosphorus, potassium and other elements required for plant growth, hydrogen can also be provided to improve plant stress resistance, regulate plant hormones, and promote plant growth.

[0045] In some preferred embodiments, the hydrogen-containing fertilizer comprises: a hydrogen donor, a water-soluble plant nutrient raw material, oil, a hydrophilic emulsifier, an emulsifier aid, a dispersant, an antioxidant and a desiccant.

[0046] Among them, the mass fraction of hydrogen donor can be, for example, but not limited to 1 part, 2 parts, 3 parts, 4 parts or 5 parts; the mass fraction of water-soluble plant nutrition raw materials can be, for example, but not limited to 60 parts, 70 parts, 80 parts or 90 parts; the mass fraction of oil can be, for example, but not limited to 5 parts, 7 parts, 9 parts, 11 parts, 13 parts or 15 parts; the mass fraction of hydrophilic emulsifier can be, for example, but not limited to 1 part, 2 parts, 4 parts, 6 parts, 8 parts or 10 parts; the mass fraction of auxiliary emulsifier can be, for example, but not limited to 1 part, 2 parts, 3 parts, 4 parts or 5 parts; the mass fraction of dispersant can be, for example, but not limited to 0.2 parts, 0.5 parts, 1 part, 1.5 parts or 2 parts; the mass fraction of antioxidant can be, for example, but not limited to 1 part, 2 parts, 3 parts, 4 parts or 5 parts; the mass fraction of desiccant can be, for example, but not limited to 1 part, 2 parts, 3 parts, 4 parts or 5 parts. Under this ratio, plants can obtain comprehensive nutrition. Among them, the antioxidant prevents the hydrogen donor from being oxidized, thereby enhancing the stability of the system; the desiccant is used to absorb moisture in the oil and prevent the hydrogen donor from reacting with water, thereby ensuring the stability of the system.

[0047] In some preferred embodiments, water-soluble plant nutrient raw materials include but are not limited to nitrogen sources: such as urea, lime nitrogen, ammonium chloride, etc., phosphorus sources: such as dipotassium hydrogen phosphate, potassium polymetaphosphate, diammonium hydrogen phosphate, ammonium polyphosphate, etc., potassium sources: such as potassium chloride, dipotassium hydrogen phosphate, potassium polymetaphosphate, etc., and plant trace elements include but are not limited to at least one of iron, manganese, zinc, copper, molybdenum and boron. For the types and amounts of the above-mentioned nutrient elements, those skilled in the art can select as needed, 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; further preferably, the nitrogen source is urea, the phosphorus source is dipotassium hydrogen phosphate, and the potassium source is potassium chloride; wherein urea can undergo endothermic reaction, making the paste hydrogen fertilizer system more stable.

[0048] In some preferred embodiments, the antioxidant is a free radical absorber such as THBQ, BHA, BHT, PG, benzylphenol, vitamin E, guaiac resin or astaxanthin or an oxygen absorber such as iron powder. Since the hydrogen donor has a strong reducing property, the addition of an antioxidant can improve the stability of the hydrogen donor during storage.

[0049] In some preferred embodiments, the dispersant is a lipophilic dispersant, and the lipophilic dispersant is preferably at least one of sodium polyacrylate, rhamnolipid, sucrose ester or phosphatidylcholine. The fineness of the solid lipophilic dispersant is 20-100 mesh and the viscosity is 300-1500 mPa·s. Under the action of the dispersant, all the raw materials are evenly dispersed, making the system more stable and more conducive to exerting their respective effects and producing a synergistic effect.

[0050] In some preferred embodiments, the co-emulsifier is vegetable glycerin, n-octanol or methanol, which can make the emulsifier form smaller droplets, which is beneficial to the stability of the system and the emulsification of the oil after application. Particularly preferably, the co-emulsifier is methanol.

[0051] In some preferred embodiments, the desiccant is shell powder of shell crab and shrimp. Shell powder of shell crab and shrimp is a green and environmentally friendly material with a porous structure and strong adsorption capacity. Shell powder of shell crab and shrimp also contains astaxanthin, which can induce crops to produce a variety of resistance substances and effectively control a variety of pathogens. After contact with the plants, they are induced to produce antibodies and glucanases, and the growth of pathogens is inhibited. Astaxanthin can induce lignification of plants around the epidemic site, forming a physical barrier to prevent reinfection of the disease; astaxanthin can induce the accumulation of plant phenolic substances, enhance disease resistance, and improve the crops themselves, so it has excellent stress resistance and disease resistance, and can produce a good synergistic effect on hydrogen-containing fertilizers. In addition, the desiccant can prevent the hydrogen donor from being oxidized or reacting with water, improve the stability of the hydrogen donor during storage, and ensure the stability of the hydrogen-containing fertilizer.

[0052] In the present invention, active metals such as calcium and magnesium, and hydrides such as calcium hydride, magnesium hydride, potassium borohydride, and sodium borohydride can obtain activated hydrogen at room temperature and pressure, such as:

[0053] Ca+2H2O→Ca(OH)2+H2↑

[0054] MgH2+H2O→MgO+2H2↑

[0055] It can be seen from the above relationship that the occurrence of this reaction can be slowed down under alkaline conditions and the rapid overflow of hydrogen molecules can be reduced.

[0056] At the same time, after hydrogen-containing fertilizers are dissolved in water, the change in pH can accelerate the acquisition of hydrogen-rich water with different saturations. The hydrogen molecules in hydrogen-rich water are highly dense, which enhances the activity of hydrogen molecules. Under alkaline conditions, hydrogen molecules are further activated, thereby reducing heavy metal ions:

[0057] Cd 2+ +H2+2OH - =Cd+2H2O

[0058] Pb 2+ +H2+2OH - =Pb+2H2O

[0059] That is, activated hydrogen molecules are obtained under alkaline conditions to simply and efficiently reduce heavy metal ions.

[0060] Therefore, the present invention controls the pH value at 7.0-8.0, thereby solving the problem of reduced function of the product due to hydrogen donor reaction during storage, and preventing problems such as product bulging in barrels or bags due to gas generation.

[0061] In a second aspect, the present invention provides a method for preparing a hydrogen-containing fertilizer, comprising the following steps:

[0062] S1. Prepare materials according to weight;

[0063] S2, adding parts by weight of the oil to parts by weight of the antioxidant, desiccant, hydrophilic emulsifier, and co-emulsifier to mix evenly to obtain a mixed solution, and mixing parts by weight of the hydrogen donor, nitrogen fertilizer, phosphate fertilizer, potash fertilizer, trace elements, and lipophilic dispersant to obtain a mixture;

[0064] S3, mixing the mixed liquid and the mixture evenly to obtain a hydrogen-containing fertilizer;

[0065] In some preferred embodiments, the mixing method of the mixed liquid and the mixture includes stirring, and the stirring speed can be, for example, but not limited to 100r / min, 300r / min, 500r / min or 1000r / min, and the stirring time can be, for example, but not limited to 0.5h, 1h, 1.5h or 2h; during the stirring process, the temperature of the solution of the plant nutrient raw material can be, for example, but not limited to 15°C, 25°C, 35°C or 45°C.

[0066] Through the above method, a stable hydrogen-containing fertilizer can be prepared, and the preparation method is simple and easy to implement. The preparation process provided in this embodiment is as follows: 1) by combining the hydrogen donor with oil, water-soluble plant nutrient raw materials, hydrophilic emulsifier, co-emulsifier and dispersant; 2) by using a lipophilic dispersant to evenly disperse the various substances; 3) by using an antioxidant and a desiccant to stabilize the hydrogen donor; 4) by controlling the stirring speed to make the materials uniform; 5) by combining materials, especially by adding plant nutrients, a high-quality hydrogen fertilizer is obtained; 6) the product controls the temperature parameters during the production process, stirs the reaction evenly into a mixture until the finished product is packaged to ensure product stability; 7) by using a hydrophilic emulsifier and a co-emulsifier to reduce the side effects of oil on soil and plants after the application of hydrogen-containing fertilizers.

[0067] In a third aspect, the present invention provides an application of a hydrogen-containing fertilizer in plant cultivation.

[0068] The hydrogen-containing fertilizer provided by the present invention comprises plant nutrients and hydrogen donors, can provide plants with nutrients necessary for growth, improve plant stress resistance, promote plant growth, and can be used for plant planting.

[0069] In the present invention, the application method of the hydrogen-containing fertilizer is widely selected, including but not limited to flushing, hole application or spraying, or an application method well known to those skilled in the art.

[0070] In some preferred embodiments, hydrogen-containing fertilizers are applied during the plant growth period. Applying the hydrogen-containing fertilizers of the present invention during the growth period has the greatest effect on plants, can effectively improve plant stress resistance, and promote plant growth.

[0071] In addition, compared with CN201610747544.3, the present invention has the following differences and advantages: 1. The formula is different. The present invention contains various types of plant nutrients in addition to hydrogen donors with stable performance; 2. The manufacturing process is different. The present invention adopts oils, antioxidants, desiccants, etc. to maintain the functionality of the hydrogen donor, and can prepare functionally stable hydrogen-containing fertilizers without multi-layer granulation technology. The manufacturing process is simple, low-cost, and low-energy consumption; 3. The effect of the product is different. The technical product of the present invention is a water-soluble product, which can be replenished in time according to the needs of crops for large, medium, trace and other elements, and the effect is fast; 4. The agricultural application method and scope are different. The present invention can select fertilization methods such as water-fertilizer integration, drone spraying, and soilless cultivation drip irrigation; 5. The packaging and transportation of the products are different. The product of the present invention is transported safely and efficiently by barrels or bags with a sealed effect.

[0072] Compared with CN201210154005.0, the present invention has the following differences and advantages: 1. Different formulas, the present invention contains not only stable hydrogen donors but also various plant nutrients; 2. Different manufacturing processes, using oils, antioxidants, desiccants, etc. to prepare hydrogen-containing fertilizers; 3. Different packaging and transportation of products, the present invention's products are transported safely, efficiently and at low cost through barrels and bags with airtight effects. 4. It is convenient for farmers to apply, and can be connected to mechanized and automated fertilization systems.

[0073] The present invention is further described below by means of specific examples and comparative examples. However, it should be understood that these examples are only used for more detailed description and should not be construed as limiting the present invention in any form.

[0074] Example 1

[0075] A hydrogen-containing fertilizer has a pH value of 7.0-8.0. The plant nutrient raw materials include, by weight, 50 parts of urea, 20 parts of dipotassium hydrogen phosphate, 5 parts of potassium chloride, 0.25 parts of trace elements (EDTA-Zn); 1.25 parts of hydrogen donor potassium borohydride; 5 parts of oil and fat olive oil; 5 parts of antioxidant THBQ; 5 parts of desiccant shell powder; 5 parts of hydrophilic emulsifier sodium alginate; 1.5 parts of auxiliary emulsifier methanol; and 2 parts of lipophilic dispersant sodium polyacrylate.

[0076] Preparation method: firstly, the olive oil is dried at 55°C, and then THBQ, shell powder, sodium alginate and methanol are added to obtain a mixed solution; then potassium borohydride, urea, dipotassium hydrogen phosphate, potassium chloride trace elements and sodium polyacrylate are mixed to obtain a mixture; then the mixture and the mixed solution are mixed in a reactor, the speed is 800r / min, the temperature is maintained at 30°C, and after 1h of stirring reaction, a paste-like hydrogen-containing fertilizer is obtained, and the density is controlled at 1.05-1.55g / cm 3 , sealed bags or sealed barrels.

[0077] Example 2

[0078] A hydrogen-containing fertilizer with a pH of 7.0-8.0. The plant nutrient raw materials include, by weight: 40 parts of urea, 25 parts of dipotassium hydrogen phosphate, 7.5 parts of potassium chloride, trace elements (EDTA-Zn, MnCl2)

[0079] 0.25 parts; hydrogen donor potassium borohydride 2.5 parts; grease silicone oil 5 parts; antioxidant astaxanthin 3 parts; desiccant calcium chloride 2 parts; hydrophilic emulsifier sodium carboxymethyl cellulose 3 parts; auxiliary emulsifier methanol 2 parts;

[0080] 2 parts of lipophilic dispersant rhamnolipid.

[0081] Preparation method: First, the silicone oil is dried at 50°C, and then astaxanthin, calcium chloride, sodium carboxymethyl cellulose, and methanol are added to obtain a mixed solution; then potassium borohydride, urea, dipotassium hydrogen phosphate, chlorine

[0082] Potassium trace elements and rhamnolipid are mixed to obtain a mixture; the mixture and the mixed solution are mixed in a reaction kettle 0, the speed is 500r / min, the temperature is maintained at 25°C, and the reaction is stirred for 1.5h to obtain a paste

[0083] Hydrogen fertilizer, density controlled at 1.05-1.55g / cm 3 , sealed bags or sealed barrels.

[0084] Example 3

[0085] Same as Example 1, except that the hydrogen donor is calcium hydride.

[0086] Example 4

[0087] 5 Same as Example 1, except that the amount of potassium borohydride added is 5 parts.

[0088] Example 5

[0089] Same as Example 1, except that no antioxidant or desiccant is added.

[0090] Example 6

[0091] Same as Example 2, except that the hydrogen donor is magnesium hydride.

[0092] 0 Example 7

[0093] Same as Example 1, except that the raw material ratio is different. By mass, the plant nutrition raw materials include: 20 parts of urea, 20 parts of dipotassium hydrogen phosphate, 20 parts of potassium chloride, trace elements (EDTA-Zn)

[0094] 0.25 parts; hydrogen donor potassium borohydride 1 part; oil olive oil 15 parts; antioxidant THBQ 1 part;

[0095] 1 part of desiccant shell powder; 10 parts of hydrophilic emulsifier sodium alginate; 5 parts of auxiliary emulsifier methanol; 0.2 parts of lipophilic dispersant sodium polyacrylate.

[0096] Comparative Example 1

[0097] Same as Example 5, except that the grease is not dried.

[0098] Comparative Example 2

[0099] Same as Example 5, except that the amount of fat added is 0 parts and the amount of water added is 10 parts.

[0100] Test Example 1

[0101] Test fertilizer: hydrogen-containing fertilizer provided in Example 1 and Example 4.

[0102] Test crops: Chinese flowering cabbage.

[0103] Test location: Hunan, Guangdong.

[0104] Experimental design

[0105] This experiment has 4 treatments, each with an area of ​​10m 2 Each treatment was repeated 3 times. Each plot was randomly arranged with isolated rows, and flushing was adopted between each plot. Except for the different fertilizer products tested, the rest of the treatments were cultivated and managed according to the routine practices of local farmers. The specific experimental design is as follows:

[0106] Treatment 1: CK without fertilizer; equal amount of water was applied three times;

[0107] Treatment 2: 30 kg / mu of non-hydrogen-containing fertilizer (the difference from Example 1 is that no hydrogen donor is added); applied three times, 10 kg / mu in the seedling stage, 10 kg / mu in the growth stage and 10 kg / mu in the vigorous stage respectively;

[0108] Treatment 3: 30 kg / mu of hydrogen-containing fertilizer provided in Example 1; applied three times, 10 kg / mu in the seedling stage, 10 kg / mu in the growth stage and 10 kg / mu in the vigorous stage respectively;

[0109] Treatment 4: 30 kg / mu of hydrogen-containing fertilizer provided in Example 4; applied three times, 10 kg / mu in the seedling stage, 10 kg / mu in the growth stage and 10 kg / mu in the vigorous stage respectively;

[0110] Sampling methods and measurement items

[0111] After the amaranth was harvested, each plot was harvested individually and the yield was measured separately. The yield results are shown in Table 1.

[0112] Table 1 Fresh weight of Chinese cabbage after different treatments (kg / mu)

[0113]

[0114] Note: Different lowercase letters in the same row indicate significant differences among treatments (P<0.05).

[0115] Results Analysis

[0116] As shown in Table 1, the yield of Chinese cabbage increased significantly by more than 20% after applying hydrogen fertilizer containing 1.25% potassium borohydride compared with the non-hydrogen fertilizer, while the yield of Chinese cabbage did not increase significantly after applying hydrogen fertilizer containing 5% potassium borohydride. This shows that adding an appropriate amount of hydrogen donor can significantly increase the yield of Chinese cabbage.

[0117] Test Example 2

[0118] Fertilizers tested: hydrogen-containing fertilizers provided in Examples 2 and 6.

[0119] Test crops: Rice.

[0120] Test location: lightly and moderately Cd-polluted areas in Guangdong and Hunan.

[0121] Experimental design

[0122] This experiment has four treatments, each with an area of ​​30m 2 Each treatment was repeated 3 times. Each plot was randomly arranged with isolated rows, and each plot was irrigated and rowed separately to avoid cross-irrigation and cross-rowing. Except for the different fertilizer products, the rest of the treatments were cultivated and managed according to the routine practices of local farmers. The specific experimental design is as follows:

[0123] Treatment 1: CK without fertilizer;

[0124] Treatment 2: conventional fertilization + hydrogen-free fertilizer (the difference from Example 2 is that no hydrogen donor is added) 30 kg / mu;

[0125] Treatment 3: conventional fertilization + 30 kg / mu of hydrogen-containing fertilizer provided in Example 2;

[0126] Treatment 4: conventional fertilization + 30 kg / mu of hydrogen-containing fertilizer provided in Example 6;

[0127] The conventional fertilizer is 18-8-15 as base fertilizer, applied at 40 kg per mu.

[0128] Fertilization method: conventional fertilizer is applied as base fertilizer before rice transplanting, 10kg is applied per mu 5-7 days after rice transplanting, and 20kg is applied from rice tillering to before filling.

[0129] Sampling methods and measurement items

[0130] Before rice planting, the soil pH value in Guangdong was 5.4, and the soil Cd content was 0.72 mg / kg; the soil pH value in Guangdong was 5.8, and the soil Cd content was 0.66 mg / kg. After rice harvest, 0-20 cm soil samples were taken from each plot to measure the soil pH value; each plot was harvested separately, and the yield and grain Cd content were measured separately. The yield results are shown in Table 2, and the grain Cd content is shown in Table 3.

[0131] Table 2 Rice yield under different treatments (kg / mu)

[0132]

[0133] Table 3 Cd content in rice grains under different treatments (mg / kg)

[0134]

[0135] The effects of continuous application of the test products for 3 years on soil pH are shown in Table 4.

[0136] Table 4 Changes of soil pH value under different treatments

[0137]

[0138] Results Analysis

[0139] As shown in Table 2, after applying hydrogen fertilizer containing 2.5% potassium borohydride or magnesium hydride, the rice grain yield increased significantly by more than 15% compared with the fertilizer without hydrogen, the Cd in rice grains did not exceed the grain standard (≤0.2 mg / kg), and the soil pH value increased. This shows that adding an appropriate amount of hydrogen donors can effectively improve the heavy metal stress capacity of rice and improve the properties of crops and soil.

[0140] In order to fully illustrate the stability of the hydrogen donors in the examples and comparative examples of the present invention, the following experiments were conducted.

[0141] Test fertilizers: hydrogen-containing fertilizers provided in Example 1, Example 5, Comparative Example 1 and Comparative Example 2.

[0142] Effect: Compared with Example 1, the hydrogen-containing fertilizer without oil drying (Comparative Example 1) or without antioxidant and desiccant (Example 5) showed a small amount of bubbles and solids on the surface after long-term unsealed storage. The hydrogen-containing fertilizer without oil protection, Example 2, reacted violently and bubbled, and there was a problem of hydrogen donor function failure. Example 1 reacted slowly, and hydrogen could not escape under the action of oil.

[0143] Appearance inspection: Observe the color and shape of the sample with the naked eye, and confirm whether there is turbidity, floccules or precipitation, as shown in Table 5.

[0144] Table 5 Reaction status and appearance

[0145]

[0146] From the test examples, it can be seen that the hydrogen-containing and preparation method thereof of the present invention have achieved excellent stability.

[0147] Specifically, by comparing Comparative Example 2 with Example 1, it can be seen that when the solvent is water, the hydrogen donor reacts quickly. By comparing Comparative Example 1 and Example 5 with Example 1, Comparative Example 1 shows a small amount of bubbles after being placed for 3 months; Comparative Example 1 shows more bubbles after being placed for 6 months, while Example 5 shows a small amount of bubbles.

[0148] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A hydrogen-containing fertilizer, characterized in that It is mainly composed of hydrogen donor, water-soluble plant nutrient raw materials, oil, hydrophilic emulsifier, auxiliary emulsifier and dispersant; The mass ratio of the hydrogen donor to the water-soluble plant nutrient raw material is 1:90 to 1:10; The mass ratio of the hydrogen donor to the oil is 1:15 to 1:1; The mass ratio of the hydrogen donor to the hydrophilic emulsifier is 1:10 to 5:1; The mass ratio of the hydrogen donor to the co-emulsifier is 1:5 to 5:1; The mass ratio of the hydrogen donor to the dispersant is 1:2 to 25:1; The pH of the hydrogen-containing fertilizer is 7-8; The hydrogen donor includes: at least one of calcium hydride, magnesium hydride, potassium borohydride or sodium borohydride; the water-soluble plant nutrient raw material includes: at least one of nitrogen fertilizer, phosphorus fertilizer, potassium fertilizer or trace element fertilizer; the oil includes: at least one of medium-chain triglycerides, silicone oil, tea oil, olive oil, palm oil or grape seed oil; the hydrophilic emulsifier includes: at least one of sodium carboxymethyl cellulose, sodium alginate, xanthan gum or caprylic acid glyceride; the auxiliary emulsifier includes at least one of vegetable glycerin, n-octanol or methanol; the dispersant includes at least one of sodium polyacrylate or rhamnolipid, sucrose ester or phosphatidylcholine.

2. The hydrogen-containing fertilizer according to claim 1, characterized in that The hydrogen-containing fertilizer comprises, by weight, 1-5 parts of a hydrogen donor, 60-90 parts of a water-soluble plant nutrient raw material, 5-15 parts of oil, 1-10 parts of a hydrophilic emulsifier, 1-5 parts of an auxiliary emulsifier, 0.2-2 parts of a dispersant, 1-5 parts of an antioxidant and 1-5 parts of a desiccant.

3. The hydrogen-containing fertilizer according to claim 1, characterized in that Calculated by weight, the water-soluble plant nutrient raw materials include 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 element fertilizer.

4. The hydrogen-containing fertilizer according to claim 2, characterized in that The antioxidant includes at least one of a free radical absorber or an oxygen absorber.

5. The hydrogen-containing fertilizer according to claim 4, characterized in that The free radical absorber comprises at least one of THBQ, BHA, BHT, PG, benzylphenol, vitamin E, guaiac resin or astaxanthin.

6. The hydrogen-containing fertilizer according to claim 4, characterized in that The oxygen absorbent includes iron powder.

7. The hydrogen-containing fertilizer according to claim 2, characterized in that The desiccant comprises at least one of shell powder, crab powder and shrimp shell powder or calcium chloride.

8. The hydrogen-containing fertilizer according to claim 1, characterized in that The dispersant includes at least one of sodium polyacrylate, rhamnolipid, sucrose ester or phosphatidylcholine.

9. The hydrogen-containing fertilizer according to claim 8, characterized in that The fineness of the dispersant is 20-100 meshes and the viscosity is 300-1500 mPa·s.

10. The method for preparing the hydrogen-containing fertilizer according to any one of claims 1 to 9, characterized in that: include: The oil, antioxidant, desiccant, hydrophilic emulsifier and co-emulsifier are mixed to obtain a mixed liquid, the hydrogen donor, water-soluble plant nutrient raw material and dispersant are mixed to obtain a mixture, and then the obtained mixed liquid and the mixture are mixed to prepare a hydrogen-containing fertilizer.

11. The preparation method according to claim 10, characterized in that: The mixing method of the mixed liquid and the mixture includes stirring.

12. The preparation method according to claim 11, characterized in that: The stirring speed is 100-1000 r / min, the time is 0.5-2h, and the temperature is 15°C-45°C.

13. Use of the hydrogen-containing fertilizer according to any one of claims 1 to 9 or the hydrogen-containing fertilizer prepared by the preparation method according to any one of claims 10 to 12 in plant cultivation, characterized in that: The hydrogen-containing fertilizer can be applied by flushing, hole application or spraying.

14. The use according to claim 13, characterized in that The hydrogen-containing fertilizer is applied during the plant growth period.

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