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

Abstract

The invention discloses an application of carvacrol as a nitrification inhibitor, a use method of carvacrol as the nitrification inhibitor, a preparation method of a fertilizer formed by carvacrol and the fertilizer. According to indoor simulation and field plot and field experiments, the carvacrol 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 compared with a traditional nitrification inhibitor, the carvacrol has the advantage in the later stage of nitrification inhibition.

Description

Technical Field

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

[0002] Fertilizer is the "food" of food, and it is of great importance to ensure national food security and ecological security. Due to the defects of traditional chemical fertilizers themselves and their unscientific and unreasonable application, a series of problems have been caused, such as low nutrient utilization rate, serious waste of fertilizer resources, and increased non-point source pollution. 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, so that nitrogen exists in the soil in the form of ammonium nitrogen that is easily adsorbed by soil colloids. At the same time, it has the characteristics of nutrient release mode being synchronized with crop absorption law, which can significantly improve fertilizer utilization rate and provide an effective way to solve problems such as fertilizer resource waste and agricultural non-point source pollution. Existing chemically synthesized nitrification inhibitors have the disadvantages of single inhibitor source, short effective period in soil, and easy decomposition. In recent years, Germany's BASF has launched new inhibitors LIMUS and DMPSA, but their core is still the derivatives of the original urease inhibitor NBPT and nitrification inhibitor DMPP, and there are still a series of problems. The source of inhibitors is still relatively single, mainly chemical synthesis, and there are still problems such as being greatly affected by environmental factors, easy to decompose under heat, and fast degradation in the soil, which reduces the efficiency of inhibitor use and increases the application cost. Therefore, the development of a new generation of plant-based and microbial-based inhibitors has broad prospects.

[0003] Carvacrol is an organic compound extracted from plants such as oregano and thyme. Its chemical formula is C 10 H 14O, easily soluble in alcohol and ether, almost insoluble in water. Melting point is about 0°C, boiling point 237-238°C, relative density 0.976 (20 / 4°C), flash point 105°C. Carvacrol has been used in the field of fertilizers. For example, invention patent application CN115152546A discloses a high-yield and high-quality cultivation method for corn, a southern crop. During the seedling management, the plant in the seedling stage is sprayed with foliar fertilizer, which includes 60-120 parts of water-soluble silicon fertilizer, 50-70 parts of potassium dihydrogen phosphate, 20-50 parts of 3-8% carvacrol, etc. Invention patent application CN117567194A discloses a multifunctional fertilizer for increasing yield and quality of crops and its preparation method. The functional fertilizer contains 85-87 parts of fertilizer ingredients, 2-4 parts of plant-derived antibacterial agents, 5-10 parts of antifreeze agents, etc. The plant-derived antibacterial agents include at least one of acrylic acid·carvacrol, citral·ene and thuja palm extract. Invention patent application CN117481003A discloses a method for planting organic spring wheat in the north. The method controls pests and diseases during the heading period, spraying 150ml of seaweed organic liquid fertilizer, 50ml of 1.5% osthole, and 50ml of carvacrol diluted with 500 times water per mu. Invention patent application CN118388302A discloses a functional water-soluble fertilizer containing glutathione and its preparation method. The fertilizer contains carvacrol to inhibit the growth of mold. It can be seen that the carvacrol currently used in the fertilizer field mainly utilizes its traditional insecticidal and antibacterial functions, does not involve nitrification inhibition function, and is not specially formulated with nitrogen fertilizers or compound fertilizers to form special fertilizers. Summary of the invention

[0004] One of the purposes of the present invention is to provide the use of carvacrol as a nitrification inhibitor, that is, carvacrol can inhibit the conversion of ammonium nitrogen contained in nitrogen fertilizers or compound fertilizers or ammonium nitrogen produced by the contained amide nitrogen into nitrate nitrogen. This new property of carvacrol has not been known before, let alone been specifically utilized.

[0005] Another object of the present invention is to provide a method for preparing fertilizer, wherein urea or compound fertilizer is mixed with carvacrol, and the weight of carvacrol is 0.01-0.1% of the weight of urea or compound fertilizer.

[0006] Preferably, the weight of carvacrol is 0.03-0.07% of the weight of urea or compound fertilizer.

[0007] Optionally, the urea or compound fertilizer is mixed with carvacrol in the following manner: carvacrol 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.

[0008] Optionally, when carvacrol is dissolved in ethanol to prepare a solution, the weight ratio of carvacrol to the volume of ethanol is 5.0-15.0 g: 250-300 mL.

[0009] Another object of the present invention is to provide a fertilizer consisting of urea or compound fertilizer and carvacrol, wherein the weight of carvacrol is 0.03-0.07% of the weight of the urea or compound fertilizer.

[0010] The invention also provides a method for using carvacrol, wherein 5.0-10.0 g of carvacrol is mixed with urea or compound fertilizer per mu and then applied to crop fields. The weight of carvacrol is 0.03-0.07% of the weight of urea or compound fertilizer, and the crop is corn, wheat or rice.

[0011] The present invention has the following beneficial effects: first, the use of carvacrol in the field of fertilizers for nitrification inhibition is discovered, and the use is discovered in multiple rounds of screening for nitrification inhibition performance of multiple materials. According to the screening results, it is judged that carvacrol has an inhibitory function on ammonia oxidizing bacteria, and has good chemical stability and environmental protection, and low toxicity. The present invention uses indoor simulation, field plots and field tests to conclude that carvacrol can inhibit soil ammonia oxidizing bacteria when the per-acre dosage is 5.0-15.0 g to effectively delay the conversion of ammonium nitrogen to nitrate nitrogen, can increase the content of ammonium nitrogen in the soil, reduce the content of nitrate nitrogen, and improve the utilization rate of nitrogen fertilizer. DETAILED DESCRIPTION

[0012] The present invention is further described below through specific implementation modes:

[0013] 1. Indoor simulation test

[0014] Soil samples of 0-20 cm of the tillage layer were collected at the experimental site of the National Field Scientific Observation and Research Station of Agricultural Ecosystem of the Chinese Academy of Sciences in Shenyang, Sujiatun District, Shenyang City, air-dried, ground and sieved through a 2 mm sieve for later use. In the experimental group, carvacrol was first dissolved in ethanol and sprayed on urea particles. After the ethanol volatilized, the urea particles were crushed and sieved through a 1 mm sieve, and then mixed evenly with the air-dried soil, and then placed in culture pots, each culture pot was filled with 200.0 g of soil, and the weight ratio was 0.1% (weight percentage, the same below) of carvacrol weight to urea weight, and the amount of urea was 0.5% of the amount of air-dried soil. In the control group, the urea amount was 0.5% of the amount of air-dried soil, and the two were mixed evenly and placed in culture pots, each culture pot was filled with 200.0 g of soil. Water was added to soak the soil in both the experimental group and the control group, so that the soil was kept at a moisture content of 25%. Placed in the same constant temperature (30° C.) environment, water was replenished every day according to weight loss. The nitrate nitrogen content in the soil was measured on the 10th, 30th, 50th and 70th days 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 -1100.0 mL of potassium chloride solution was placed in an oscillator, extracted for 1 hour, filtered, and measured using a 3-AA3 flow analyzer. The low nitrate nitrogen content indicates that carvacrol, as a nitrification inhibitor, delays the conversion of ammonium nitrogen from the decomposition of urea in the soil to nitrate nitrogen. The test results show that carvacrol exhibited a good nitrification inhibition effect from the 10th day to the 70th day, effectively reducing the nitrate nitrogen content, making the nitrogen fertilizer exist in the soil in the form of ammonium nitrogen, reducing the loss of nitrate nitrogen, and improving the utilization rate.

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

[0016] Nitrate nitrogen (mg / kg) Day 10 Day 30 Day 50 Day 70 Experimental Group 146.2 195.4 437.3 601.6 Control group 185.9 482.7 693.8 894.2

[0017] 2. Comparative test

[0018] Soil samples of 0-20cm of the tillage layer were collected at the experimental site of the National Field Scientific Observation and Research Station of Agricultural Ecosystem of the Chinese Academy of Sciences in Shenyang, Sujiatun District, Shenyang City, air-dried, and ground through a 2mm sieve for use. In the experimental group, carvacrol was dissolved in ethanol and sprayed on the surface of urea particles according to the weight of carvacrol being 0.1% of the weight of urea and the amount of urea being 0.5% of the air-dried soil. After the ethanol volatilized, the urea particles were crushed through a 1mm sieve, and then mixed with the soil evenly, and placed in a culture pot, with 200.0g of soil in each culture pot; the control group used DMPP (3,4-dimethylpyrazole phosphate) which is currently commonly chemically synthesized as a control, and DMPP was 0.1% of the urea amount and 0.5% of the air-dried soil amount. The two were mixed evenly and placed in a culture pot, with 200g of soil in each culture pot. Water was added to soak the soil in both the experimental group and the control group to keep the soil moisture content at 25%. Placed in the same constant temperature (30°C) environment, water was supplemented every day according to weight loss. The nitrate nitrogen content in the soil was measured on the 10th, 30th, 50th and 70th days, and 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.

[0019] Table 2 Comparison results of carvacrol and DMPP

[0020] Nitrate nitrogen (mg / kg) Day 10 Day 30 Day 50 Day 70 Test group - carvacrol 146.2 195.4 437.3 601.6 Control group-DMPP 169.4 186.3 467.2 636.9

[0021] It can be seen from the table above that, under the same dosage of carvacrol and DMPP, the nitrate nitrogen content of the carvacrol test group on the 10th, 50th and 70th days was lower than that of the DMPP control group. The DMPP control group was lower than the carvacrol test group in the 30th day measurement result. Combined with the analysis of the other three groups of data, the measurement result on the 30th day may have a large error. In addition, carvacrol is safer than DMPP and less toxic. Carvacrol has a good application prospect as a nitrification inhibitor.

[0022] 3. Cell experiment

[0023] A corn experiment was conducted in a plot in the corn field of Shuguang Farm in Jiamusi City, Heilongjiang Province. Each plot was 25m 2 (5m×5m). The experimental treatments were as follows: conventional fertilization (N), conventional fertilization + carvacrol, where the amount of carvacrol was 25.0 g per mu.

[0024] Conventional fertilization: 944.5g of urea, 450.6g of heavy superphosphate, and 370.4g of potassium sulfate were applied to each plot. The three were crushed and passed through a 1mm sieve respectively, and then mixed evenly. Conventional fertilization + carvacrol: carvacrol was dissolved in ethanol and sprayed on urea granules. After the ethanol evaporated, the urea granules were crushed and passed through a 1mm sieve. The amount and type of nitrogen, phosphorus and potassium used were the same as conventional fertilization. 25.0g of carvacrol was applied per mu, and 0.94g was applied to each plot (the weight of carvacrol was 0.099% of the weight of urea). The seeds, pesticides, and tillage and management methods of the plots where carvacrol was applied were consistent with those of the control plots where carvacrol was not applied. When applying fertilizer, the conventional fertilization plot uses 10 times the weight of farmland dry soil and fertilizer to mix evenly, evenly spread on the surface, and plow and sow corn. Each plot has 8 ridges, and 20 plants per ridge; in the conventional fertilization + carvacrol plot, carvacrol and fertilizer are mixed evenly, and then 10 times the weight of farmland dry soil and fertilizer are mixed evenly, spread on the surface, plowed and harrowed, and sown. 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: Use a soil drill to take soil samples from the 0-20cm tillage layer, use the five-point cross sampling method, take 5 drills in each plot, and take about 300.0g of soil. Take the soil sample back to the laboratory, sieve it, mix it, take 5.0g of it, and use 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] The yield was measured at the harvest time. In the 4th and 5th ridges in the middle of each plot, 5 plants were taken from the 7th plant in each ridge, for a total of 10 plants. The corn was broken off and brought back to the laboratory, threshed, air-dried, and weighed. The weight measurement results were: the average yield of the experimental group was 995.7 kg / mu; the average yield of the control group was 903.4 kg / mu. The average yield increase rate was 10.2%. It can be seen that carvacrol showed a good nitrification inhibition effect in the corn plot test, effectively increased the ammonium nitrogen content in the soil, reduced the nitrate nitrogen content, and effectively increased the corn yield.

[0030] 4. Field trials

[0031] Field trials were conducted to further test the effect of carvacrol combined with urea.

[0032] (1) Liaoning corn field experiment: The experimental site is located in Shilihe Town, Sujiatun District, Shenyang City. Settings: Conventional fertilization and conventional fertilization + carvacrol treatments, 3 replicates for each treatment, 1 mu for each treatment area, and the initial fertility level of each plot is consistent. The amount of carvacrol is 15.0 g per mu. First, carvacrol is dissolved in 300 mL of ethanol to prepare a solution. Then, 22.5 kg of urea (carvacrol is 0.067% w / w of urea), 9.0 kg of potassium chloride (potassium oxide ≥ 62%), and 10.5 kg of diammonium phosphate (18-46-0) are applied per mu. The ethanol solution of carvacrol is evenly sprayed on the surface of urea particles, dried, and evenly mixed with potassium chloride and diammonium phosphate. Seed fertilizer is applied with a seeder, and sowing and fertilization are completed simultaneously. For conventionally fertilized plots, 22.5 kg of urea, 9.0 kg of potassium chloride (potassium oxide ≥ 62%), and 10.5 kg of diammonium phosphate (18-46-0) are applied per mu. Urea, potassium chloride, and diammonium phosphate are directly mixed evenly, and the seed fertilizer is applied with the seeder, so that sowing and fertilization are completed simultaneously. No more topdressing is done in the later stage, and weeding, spraying and other measures remain the same. At the harvest time, a harvester is used, and each plot is harvested separately. After drying and dehydration, the harvest is weighed to obtain the actual yield. The average yield of the three plots is the final data.

[0033] (2) Field experiment of rice in Heilongjiang: The experiment was conducted at Shuguang Farm in Jiamusi City, Heilongjiang Province. Two treatments were set up: conventional fertilization and conventional fertilization + carvacrol. Each treatment was repeated three times and the area of ​​each treatment was 1 mu. The initial fertility level of each plot was kept consistent. The dosage of carvacrol was 10.0 g per mu. Carvacrol was first dissolved in 250.0 mL of ethanol to prepare a solution. According to the application of 21.5 kg of urea (carvacrol was 0.046% w / w of urea), 10.2 kg of potassium chloride (potassium oxide ≥ 62%), and 11.7 kg of diammonium phosphate (18-46-0) per mu, the ethanol solution of carvacrol was evenly sprayed on the surface of urea particles, dried, mixed evenly with potassium chloride and diammonium phosphate, and spread on the farmland. The field was plowed, soaked, raked, and transplanted. For the conventionally fertilized plots, 21.5 kg of urea, 10.2 kg of potassium chloride (potassium oxide ≥ 62%), and 11.7 kg of diammonium phosphate (18-46-0) were applied per mu. Urea, potassium chloride, and diammonium phosphate were directly mixed evenly and spread into the farmland, plowed, soaked, raked, and transplanted. Urea was applied at 10 kg / mu for all treatments during the green period, and the rest of the weeding and spraying measures were kept consistent. During the harvest period, a harvester was used to harvest each plot separately, and the actual yield was obtained after drying and dehydration. The average yield of the three plots was the final data.

[0034] (3) Hebei wheat field experiment: The experimental site is located in Shijing Village, Shijing Township, Mancheng District, Baoding City, Hebei Province. Settings: Two treatments: conventional fertilization and conventional fertilization + carvacrol, 3 replicates for each treatment, and 1 mu for each treatment. The dosage of carvacrol is 5 g per mu. Carvacrol is dissolved in 300 mL of ethanol to prepare a solution; 13.5 kg of urea (carvacrol is 0.037% w / w of urea), 11.0 kg of potassium chloride (potassium oxide ≥ 62%), and 21.5 kg of diammonium phosphate (18-46-0) are applied per mu. The ethanol solution of carvacrol is evenly sprayed on the surface of urea particles, dried, and evenly mixed with potassium chloride and diammonium phosphate. Seed fertilizer is applied with a seeder, and sowing and fertilization are completed simultaneously. For the conventionally fertilized plots, 13.5 kg of urea, 11.0 kg of potassium chloride (potassium oxide ≥ 62%), and 21.5 kg of diammonium phosphate (18-46-0) were applied per mu. Urea, potassium chloride, and diammonium phosphate were directly mixed evenly, and the seed fertilizer was applied with the seeder, so that sowing and fertilization were completed simultaneously. All treatments spread 15 kg of urea before spring irrigation, and the weeding and spraying measures were kept consistent. At the harvest time, a harvester was used to harvest each plot separately, and the actual yield was obtained by weighing after drying and dehydration. The average yield of the three plots was the final data.

[0035] Table 5 Yield measurement results at harvest time

[0036] Yield (kg / mu) Liaoning Corn Heilongjiang Rice Hebei wheat Experimental Group 946 629 648 Control group 883 582 579 Yield increase rate (%) 7.1 8.1 11.9

[0037] In summary, carvacrol can be used as a nitrification inhibitor to effectively inhibit the conversion of ammonium nitrogen in fertilizers to nitrate nitrogen. Mixing carvacrol with urea, compound fertilizer, etc. can effectively increase grain yields.

[0038] The above embodiments are intended to illustrate the present invention rather than to limit it. 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 carvacrol as a nitrification inhibitor.

2. The use according to claim 1, characterized in that Carvacrol is used to inhibit the conversion of ammonium nitrogen contained in or produced by urea or compound fertilizers into nitrate nitrogen.

3. A method for making a fertilizer, characterized in that The urea or compound fertilizer is mixed with carvacrol, and the weight of the carvacrol is 0.01-0.1% of the weight of the urea or compound fertilizer.

4. The method for making the fertilizer according to claim 3, characterized in that The weight of the carvacrol is 0.03-0.07% of the weight of the urea or compound fertilizer.

5. The method for making the fertilizer according to claim 3, characterized in that The urea or compound fertilizer is mixed with carvacrol in the following manner: carvacrol 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.

6. The method for making the fertilizer according to claim 5, characterized in that When carvacrol is dissolved in ethanol to prepare a solution, the weight ratio of carvacrol to the volume ratio of ethanol is 5.0-15.0 g: 250-300 mL.

7. A fertilizer, characterized in that The invention consists of urea or compound fertilizer and carvacrol, wherein the weight of the carvacrol is 0.03-0.07% of the weight of the urea or compound fertilizer.

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

9. A method for using carvacrol, characterized in that Mix 5.0-10.0 g of carvacrol per mu with urea or compound fertilizer and apply to crop fields.

10. The method for using carvacrol according to claim 9, characterized in that The weight of carvacrol is 0.03-0.07% of the weight of urea or compound fertilizer, and the crop is corn, wheat or rice.

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