Application and use method of allicin, fertilizer preparation method and fertilizer

Abstract

The invention discloses application of allicin as a nitrification inhibitor, a use method of the allicin as the nitrification inhibitor, a preparation method of a fertilizer formed by the allicin and the fertilizer. According to indoor simulation and field plot and field experiments, the allicin shows a good inhibition effect on soil ammonia oxidizing bacteria when the dosage per mu is 5.0-15.0 g, conversion from ammonium nitrogen to nitrate nitrogen can be effectively delayed, and meanwhile, compared with a traditional nitrification inhibitor, the allicin has a soil cleaning effect and has a very good application prospect.

Description

Technical Field

[0001] The present invention relates to the field of fertilizers, and in particular to the use of allicin as a nitrification inhibitor, a use method, a fertilizer preparation method, and the fertilizer. Background Art

[0002] Fertilizers are the "food" of food and are crucial for ensuring national food security and ecological safety. Stable fertilizers containing nitrification inhibitors can delay the conversion of ammonium nitrogen (including ammonium nitrogen directly contained in nitrogen fertilizers or compound fertilizers, or ammonium nitrogen converted from amide nitrogen) to nitrate nitrogen, allowing nitrogen to exist in the soil in the form of ammonium nitrogen that is easily adsorbed by soil colloids. Their nutrient release pattern is synchronized with crop absorption patterns, significantly improving fertilizer utilization efficiency and providing an effective approach to addressing fertilizer resource waste and agricultural non-point source pollution. Existing chemically synthesized nitrification inhibitors suffer from shortcomings such as a single inhibitor source, a short effective life in soil, and easy decomposition. In recent years, BASF in Germany has launched new inhibitors, LIMUS and DMPSA, respectively. However, their core products are still derivatives of the existing urease inhibitor NBPT and nitrification inhibitor DMPP. Despite these innovations, a series of problems remain. The inhibitors are still primarily derived from chemical synthesis, are significantly affected by environmental factors, are easily decomposed by heat, and degrade rapidly in soil. This reduces the inhibitor's efficiency and increases its application cost. Therefore, the development of a new generation of plant-derived and microbial-derived inhibitors has broad prospects.

[0003] Allicin is an organic sulfur compound extracted from the bulb of garlic (Allium genus) of the Allium family. It has a melting point of 25°C, a boiling point of 248.6, and a density of 1.148 g / cm 3 , refractive index 1.561. It is soluble in ethanol, chloroform, or ether, and has a solubility of 24 g / L in water (10°C). Allicin has many applications in the fertilizer field. For example, invention patent application CN1319576A discloses a compound organic fertilizer and its production method. The compound organic fertilizer includes plant residues, animal feces, etc., as well as pesticides and fungicides such as nicotine and allicin. Invention patent application CN108440161A discloses a grape fertilizer with the effect of increasing yield and resisting disease, which contains organic fertilizer, salicylic acid, allicin, etc. Invention patent CN107459385A discloses a trace high-efficiency fertilizer additive containing sodium polyacrylate, humic acid, allicin, growth regulators, etc. However, in the prior art, allicin is mostly used as a general fungicide, and the nitrification inhibition function of allicin is not mentioned. Even more, allicin is not combined with nitrogen fertilizer or compound fertilizer to form a fertilizer with nitrification inhibition function. Summary of the Invention

[0004] One of the purposes of the present invention is to provide the use of allicin as a nitrification inhibitor, that is, allicin can effectively inhibit the conversion of ammonium nitrogen directly contained in nitrogen fertilizers or compound fertilizers or ammonium nitrogen converted from amide nitrogen such as urea to nitrate nitrogen, thereby effectively improving the performance of these fertilizers.

[0005] Another object of the present invention is to provide a method for preparing a fertilizer, comprising mixing urea or compound fertilizer with allicin, wherein the weight of the allicin is 0.01-0.10% of the weight of the urea or compound fertilizer.

[0006] Optionally, the urea or compound fertilizer and allicin are mixed in one of the following two ways: (a) the urea or compound fertilizer and solid allicin are crushed and then mechanically mixed evenly; (b) allicin is dissolved in ethanol to prepare a solution, and then the solution is evenly sprayed on the surface of urea or compound fertilizer particles and dried.

[0007] Optionally, when allicin is dissolved in ethanol to prepare a solution, the volume ratio of allicin to ethanol is 5-15 g: 200-300 mL.

[0008] The invention also provides a fertilizer, which consists of urea or compound fertilizer and allicin, wherein the weight of the allicin is 0.01-0.10% of the weight of the urea or compound fertilizer.

[0009] The invention also provides a method for using allicin, which comprises mixing the allicin with nitrogen fertilizer or compound fertilizer at a dosage of 5.0-15.0 g per mu and applying the mixture to crop fields.

[0010] Preferably, the nitrogen fertilizer is urea, the weight of allicin is 0.02-0.07% of the weight of urea, and the crop is corn, rice or wheat.

[0011] The present invention has the following beneficial effects: in the early stage of research and development, based on the structural and functional characteristics of ammonia-oxidizing bacteria, more than one hundred materials including allicin that may have an inhibitory effect were initially selected. After the first round of effectiveness screening tests, more than twenty materials with nitrification inhibitory effects were selected. Then, a second round of screening for chemical stability, environmental performance, and toxicity and economic cost analysis was carried out. The materials selected in the second round were subjected to a third round of plot and field tests. Allicin was one of the materials that passed the third round of screening and was suitable as a nitrification inhibitor. The present invention has concluded through indoor simulation, field plot and field tests that allicin exhibits a good inhibitory effect on soil ammonia-oxidizing bacteria at a dosage of 5.0-15.0 g per mu, can effectively delay the conversion of ammonium nitrogen to nitrate nitrogen, and can effectively increase per mu yield by mixing allicin with nitrogen fertilizer or compound fertilizer and applying it to farmland. DETAILED DESCRIPTION

[0012] The present invention will be further described below through specific embodiments:

[0013] 1. Indoor simulation test

[0014] Take the 0-20cm soil sample of cultivated layer at the experimental site of Jilin Academy of Agricultural Sciences, Gongzhuling City, Jilin Province, air-dry, grind the sieve of 2mm for subsequent use.The test group is 0.2% (percentage by weight, the same below) of urea amount according to allicin, and 0.5% of urea amount is an air-dried soil amount, first urea is pulverized through a 1mm sieve, then allicin (lower than 25 ℃ of operations) is pulverized through a 1mm sieve under the solid state, then urea and allicin are mixed, then mixed with the soil sample, culture basin is packed into, 200.0g of soil is filled in each culture basin; The control group is 0.5% of air-dried soil amount according to urea amount, first urea is pulverized through a 1mm sieve, then urea and soil sample are carried out both blending evenly, culture basin is packed into, 200.0g of soil is filled in each culture basin. The test group and the control group all add water to soak the soil, make soil moisture remain on 25%, be placed in equal constant temperature (30 ℃) environment, every day according to weight loss, replenish water. The nitrate nitrogen content in the soil was measured on the 10th, 30th, 50th and 70th day respectively. The results are shown in Table 1. Each time the soil in the culture pot was poured out and mixed evenly, 5.0 g of it was taken and placed in a conical flask, and 2.00 mol·L -1 100.0 mL of potassium chloride solution was placed in an oscillator and extracted for 1 hour. The solution was filtered and then measured using a 3-AA3 flow analyzer. The low nitrate nitrogen content indicates that allicin, as a nitrification inhibitor, can delay the conversion of ammonium nitrogen from the decomposition of urea in the soil to nitrate nitrogen.

[0015] Table 1 Monitoring results of nitrate nitrogen content in soil

[0016]

[0017] From the above results, it can be seen that allicin showed nitrification inhibition effect from the 10th day to the 70th day after application, effectively reducing the nitrate nitrogen content compared with the control group, making nitrogen fertilizer exist in the soil in the form of ammonium nitrogen, reducing the loss of nitrate nitrogen and improving its utilization rate.

[0018] 2. Comparative test

[0019] Soil samples from the topsoil layer (0-20 cm) were collected at the Jilin Academy of Agricultural Sciences experimental site in Gongzhuling City, Jilin Province, air-dried, and ground through a 2 mm sieve for later use. For the experimental group, allicin was mixed at a concentration of 0.2% w / w of urea and 0.5% w / w of urea relative to the air-dried soil (the allicin mixing procedure was the same as above). The samples were then placed in culture pots, with 200 g of soil per pot. A control group used DMPP (3,4-dimethylpyrazole phosphate), a commonly used chemically synthesized control. DMPP was mixed at a concentration of 0.2% w / w of urea and 0.5% w / w of urea relative to the air-dried soil. The mixture was ground through a 1 mm sieve, mixed, and placed in culture pots, with 200 g of soil per pot. Both the experimental and control groups were watered to a moisture content of 25% w / w. The soils were kept at a constant temperature (30°C) and watered daily based on weight loss. The nitrate nitrogen content in the soil was measured on the 10th, 30th, 50th and 70th day respectively. The results are shown in Table 2. Each time the soil in the culture pot was poured out and mixed evenly, 5.0 g of it was taken and placed in a conical flask, and 2.00 mol·L -1 100.0 mL of potassium chloride solution was placed in an oscillator, extracted for 1 hour, filtered, and measured using a 3-AA3 flow analyzer.

[0020] Table 2 Comparison results of allicin and DMPP

[0021]

[0022] As shown in the table above, when compared to DMPP at the same dosage of 0.2% of urea, allicin's nitrification inhibition ability was lower from day 10 to day 70. However, allicin still performed well in inhibiting nitrate nitrogen production, demonstrating its practical value. Furthermore, allicin can inhibit the activity of some harmful bacteria in the soil, thus cleaning the soil. Furthermore, the cost of large-scale production of allicin is lower than that of DMPP. In summary, allicin has a better application prospect than DMPP.

[0023] 3. Cell Trial

[0024] The plot experiment was conducted in the farmland of Shazhalan Village, Fuxin Town, Fumeng County, Fuxin City, Liaoning Province, with each plot covering an area of ​​25m 2The experimental treatments were as follows: 1. Conventional fertilization: 991.7 grams of urea, 398.0 grams of triple superphosphate, and 323.4 grams of potassium sulfate were applied to each plot. The three were crushed through a 1mm sieve and then mixed evenly. 2. Conventional fertilization plus allicin: the amounts and types of nitrogen, phosphorus, and potassium used were the same as for conventional fertilization. On this basis, 10.0 grams of allicin were applied per mu, and 0.37 grams were applied to each plot (the amount of allicin was 0.037% of urea). First, allicin (maintained at a solid state below 25°C), urea, triple superphosphate, and potassium sulfate were crushed through a 1mm sieve, and allicin was directly mixed with urea powder, and then mixed evenly with triple superphosphate and potassium sulfate powders. The plots where allicin was applied and the control plots where allicin was not applied maintained the same seeds, pesticides, and tillage and management methods. When applying fertilizer, 10 times the weight of dry farmland soil was mixed with fertilizer and evenly spread on the surface. The soil was plowed, raked, and corn was sown. Each plot had 8 ridges and 20 plants per ridge. The amount of nitrate nitrogen and ammonium nitrogen in the soil was measured on the 20th, 40th, 60th, 80th, and 120th days, respectively. The results are shown in Tables 3 and 4. Test method for nitrate nitrogen and ammonium nitrogen in soil: Soil samples of 0-20cm of the tillage layer were taken with a soil drill. The five-point cross sampling method was used. Five drills were taken from each plot, and about 300g of soil was taken. The soil samples were brought back to the laboratory, sieved, mixed, and 5.0g was taken. The 2.00mol·L -1 The solution was extracted with potassium chloride and measured with a 3-AA3 flow analyzer.

[0025] Table 3 Monitoring results of nitrate nitrogen in soil

[0026]

[0027] Table 4 Monitoring results of ammonium nitrogen in soil

[0028]

[0029] Yield was measured at harvest time. Starting from the fifth plant in each of the two central ridges of each plot, five plants were harvested consecutively, totaling 10 plants. The corn was broken off and brought back to the laboratory, threshed, air-dried, and weighed. The average yield for the experimental and control groups was 809.1 kg / mu (approximately 1.6 lb) and 723.1 kg / mu (approximately 1.6 lb). The average yield increase was 10.6%.

[0030] In summary, allicin showed a good nitrification inhibition effect in the plot experiment, effectively increasing the ammonium nitrogen content in the soil, reducing the nitrate nitrogen content, and effectively increasing corn yield.

[0031] 4. Field trials

[0032] Field trials were conducted in Liaoning for corn, Heilongjiang for rice, and Hebei for wheat.

[0033] 1. Liaoning Corn Trial: The trial was located in Shazalan Village, Fuxin Town, Fumeng County, Fuxin City, Liaoning Province. Two treatments were set up: conventional fertilization and conventional fertilization + allicin. Each treatment had three replicates, and each treatment area was 1 mu. Initial fertility levels were maintained consistent across plots. The allicin dosage was 15.0 g per mu, prepared by dissolving allicin in 250.0 mL of ethanol. A solution was then applied at a rate of 24.5 kg of urea (0.061% of the weight of the urea), 9.0 kg of potassium chloride (≥62% potassium oxide), and 11.0 kg of diammonium phosphate (18-46-0) per mu. The allicin ethanol solution was evenly sprayed onto the surface of urea granules, allowed to dry, and then evenly mixed with the potassium chloride and diammonium phosphate. Seed fertilizer was applied using a seed drill, with sowing and fertilization completed simultaneously. For conventionally fertilized plots, 24.5 kg of urea, 9.0 kg of potassium chloride (K2O ≥ 62%), and 11.0 kg of diammonium phosphate (18-46-0) were applied per mu. Urea, potassium chloride, and diammonium phosphate were directly mixed evenly, and seed fertilizer was applied using a seed drill, allowing simultaneous seeding and fertilization. No additional fertilizer was applied later, and weeding and pesticide application measures remained consistent. At harvest, each plot was harvested individually using a harvester, dried, dehydrated, and weighed to determine the actual yield. The final yield was the average of the three plots.

[0034] 2. Heilongjiang Rice Experiment: The experiment was conducted at the experimental field of the Rice Research Institute in Fangzheng County, Heilongjiang Province. Two treatments were set up: conventional fertilization and conventional fertilization + allicin. Each treatment had three replicates, and each treatment area was 1 mu. The initial fertility level of each plot was kept consistent. The allicin dosage was 5.0 g per mu. The allicin solution was dissolved in 250.0 mL of ethanol to prepare a solution. Urea (0.023% allicin dosage), potassium chloride (potassium oxide ≥ 62%), potassium chloride (potassium oxide ≥ 62%), and diammonium phosphate (18-46-0) were applied at a rate of 21.8 kg per mu. The allicin ethanol solution was evenly sprayed onto the surface of urea granules, allowed to dry, and then evenly mixed with potassium chloride and diammonium phosphate. The solution was then spread on the farmland, plowed, soaked, raked, and transplanted. Conventionally fertilized plots were applied at a rate of 21.8 kg of urea, 9.7 kg of potassium chloride (K2O ≥ 62%), and 10.8 kg of diammonium phosphate (18-46-0) per mu. The urea, potassium chloride, and diammonium phosphate were evenly mixed and spread over the fields. The fields were then plowed, soaked, raked, and rice seedlings were planted. During the greening period, all treatments were broadcast at a rate of 10.0 kg of urea per mu. All other later weeding and pesticide spraying measures remained the same. At harvest, each plot was harvested individually using a harvester, dried, dehydrated, and weighed to determine actual yield. The yield of the three plots was the average of the final data.

[0035] 3. Hebei wheat trial: The trial was located in Hetianfeng Modern Agricultural Park, Tongxia Village, Wangdu County, Baoding City, Hebei Province. Two treatments were set up: conventional fertilization and conventional fertilization + allicin. Each treatment had three replicates and each treatment area was 1 mu. The initial fertility level of each plot was kept consistent. The allicin dosage was 10.0 g per mu. Allicin was dissolved in 250.0 mL of ethanol to prepare a solution. Urea (0.067% of allicin dosage), potassium chloride (potassium oxide ≥ 62%), and diammonium phosphate (18-46-0) were applied at a rate of 15.0 kg per mu. The ethanol solution of allicin was evenly sprayed on the surface of urea granules, dried, and evenly mixed with potassium chloride and diammonium phosphate. The soil was then spread on the farmland, plowed, and sown. Conventionally fertilized plots were treated with 15.0 kg of urea, 10.0 kg of potassium chloride (K2O ≥ 62%), and 20.0 kg of diammonium phosphate (18-46-0) per mu. The urea, potassium chloride, and diammonium phosphate were evenly mixed and spread on the fields, plowed, and sown. All treatments broadcast 15.0 kg of urea before spring irrigation. Subsequent weed control and pesticide application procedures remained consistent. At harvest, each plot was harvested individually using a harvester, dried, and dehydrated, and weighed to determine actual yield. The yield of the three plots was averaged, as shown in Table 5.

[0036] Table 5 Yield measurement results at harvest time

[0037] Yield (kg / mu) Liaoning corn Heilongjiang rice Hebei wheat experimental group 951 637 663 control group 883 582 579 Yield increase rate (%) 7.7 8.6 14.5

[0038] In summary, allicin can be used as a nitrification inhibitor to effectively inhibit the conversion of ammonium nitrogen in fertilizers to nitrate nitrogen. The fertilizer made by mixing allicin with urea can effectively increase grain yield after application.

[0039] The above embodiments are intended to illustrate rather than limit the present invention. Under the concept of the present invention, technical solutions that have not been substantially changed are still protected by the present invention.

Claims

1. Use of allicin as a nitrification inhibitor.

2. The use according to claim 1, characterized in that Allicin is used to convert ammonium nitrogen contained or produced in nitrogen fertilizers or compound fertilizers into nitrate nitrogen.

3. A method for making a fertilizer, characterized in that Urea or compound fertilizer is mixed with allicin, and the weight of allicin is 0.01-0.10% of the weight of urea or compound fertilizer.

4. The method for making the fertilizer according to claim 3, characterized in that The urea or compound fertilizer is mixed with allicin in one of the following two ways: (a) the urea or compound fertilizer and the solid allicin are crushed and then directly mechanically mixed evenly; (b) the allicin is dissolved in ethanol to prepare a solution, and then the solution is evenly sprayed on the surface of the urea or compound fertilizer particles and dried.

5. The method for making the fertilizer according to claim 4, characterized in that When allicin is dissolved in ethanol to prepare a solution, the mass ratio of allicin to the volume of ethanol is 5-15g:200-300mL.

6. A fertilizer, characterized in that The invention is composed of urea or compound fertilizer and allicin, wherein the weight of the allicin is 0.01-0.10% of the weight of the urea or compound fertilizer.

7. The fertilizer according to claim 6, characterized in that It is manufactured by the manufacturing method according to any one of claims 3 to 5.

8. The method for using allicin is characterized in that Mix 5.0-15.0g of allicin per mu with nitrogen fertilizer or compound fertilizer and apply to crop fields.

9. The method of using allicin as claimed in claim 8, characterized in that The nitrogen fertilizer is urea, the weight of allicin is 0.02-0.07% of the weight of urea, and the crop is corn, rice or wheat.

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