Application of tartaric acid, long-acting nitrification inhibitor and preparation method

Abstract

The invention discloses application of tartaric acid as a protective agent of a nitrification inhibitor 3, 4-dimethylpyrazole phosphate, a long-acting nitrification inhibitor prepared from tartaric acid and 3, 4-dimethylpyrazole phosphate and a preparation method of the long-acting nitrification inhibitor. The invention finds that tartaric acid has inhibition and protection effects on decomposition of DMPP, and the nitration inhibition performance of DMPP can be effectively prolonged by combining tartaric acid and DMPP.

Description

Technical Field

[0001] The invention relates to the field of nitrogen fertilizer nitrification inhibitors, and in particular to use of tartaric acid as a protective agent for nitrification inhibitors, a long-acting nitrification inhibitor and a preparation method thereof. Background Art

[0002] Stable fertilizers are fertilizers that add urease inhibitors and (or) nitrification inhibitors during the production process to regulate the microbial and enzyme activities in the soil that affect the conversion of fertilizer nitrogen, thereby achieving high efficiency and long-term nitrogen. The application of stable fertilizers can effectively increase the retention of ammonium nitrogen in the soil, improve nitrogen utilization by 20%-38%, and reduce the emission of different forms of nitrogen such as ammonia and nitrate to the atmosphere and water environment by 25%-71%. Nitrification inhibitors are the core of stable fertilizers, which can greatly improve the utilization rate of nitrogen fertilizers, reduce nitrate leaching and gas emissions such as nitrous oxide. DMPP (3,4-dimethylpyrazole phosphate) is a nitrification inhibitor that is currently used more frequently. However, DMPP is easily disturbed by the soil environment, especially the pH. It is easy to decompose in an alkaline environment, causing inactivation and unable to play its role. There are various soil types, among which alkaline soils exist in large areas, mainly concentrated in the eastern coastal areas of the north, saline-alkali land in the Songnen Plain in the northeast, and semi-desert inland saline soils. Therefore, developing a protective agent for DMPP and improving its effect in alkaline soil has very high application value. Summary of the invention

[0003] One of the purposes of the present invention is to provide the use of tartaric acid as a protective agent for nitrification inhibitor DMPP. Tartaric acid, also known as 2,3-dihydroxysuccinic acid, dihydroxysuccinic acid, and gluconic acid, has a chemical formula of C4H6O6, a molecular weight of 150.09, a melting point of 200 to 206°C, a boiling point of 399.3°C, and a density of 1.886 g / cm3. CAS No.: 133-37-9 (DL), 147-71-7 (D), and 87-69-4 (L). The present invention finds that tartaric acid can effectively protect DMPP in alkaline soil, slow down the decomposition of DMPP, and fully exert its function as a nitrification inhibitor.

[0004] Another object of the present invention is to provide a long-acting nitrification inhibitor, which is made of the following components by weight: 8-9 parts of tartaric acid and 1-2 parts of 3,4-dimethylpyrazole phosphate.

[0005] The present invention also provides a method for preparing the above-mentioned long-acting nitrification inhibitor, comprising the following steps:

[0006] Step 1: dissolving 8-9 parts of tartaric acid and 1-2 parts of 3,4-dimethylpyrazole phosphate in water to obtain a mixed solution;

[0007] Step 2: heating and drying the mixed solution while stirring until the water content of the material is 3.0% w / w to obtain a dried material;

[0008] Step 3: The dried material is crushed by a mechanical crusher to obtain a long-acting nitrification inhibitor.

[0009] Preferably, in step 1, 8-9 parts of tartaric acid and 1-2 parts of 3,4-dimethylpyrazole phosphate are dissolved in 10-15 parts of water to obtain a mixed solution;

[0010] In the step 2, the mixed solution is heated to 90° C.-95° C., and is dried under normal pressure while being stirred until the moisture content of the material reaches 3.0% w / w, thereby obtaining a dried material;

[0011] In the step 3, the dried material is crushed by a mechanical crusher to a particle size of ≤1 mm, and then crushed by an air flow vortex micronizer to 0.05-0.075 mm to obtain a long-acting nitrification inhibitor.

[0012] The present invention has the following beneficial effects: according to the alkaline soil characteristics and the mechanism of DMPP decomposition under alkaline conditions, multiple materials that may have the ability to control the decomposition of DMPP are theoretically screened out, and then the effect and strength of these materials on the control of DMPP decomposition are studied through indoor simulation tests, and the toxicity, stability and current economic cost of each material are analyzed, and finally, through continuous plot and field tests, it is verified that tartaric acid is one of the relatively ideal nitrification inhibitor protective materials. The present invention finds that tartaric acid has an inhibitory and protective effect on the decomposition of DMPP, and the combination of tartaric acid and DMPP can effectively prolong the nitrification inhibition performance of DMPP. DETAILED DESCRIPTION

[0013] The present invention is further described below through specific implementation methods, and the following percentages are all by weight:

[0014] 1. Sample Preparation

[0015] At room temperature, 90 grams of tartaric acid and 10 grams of DMPP are dissolved in 100 grams of water, stirred for 5-8 minutes, and the temperature is raised to normal pressure, and the mixture is heated and dried while stirring, and the temperature is maintained at 90°C-95°C, and the moisture content of the material is dried to 3.0%; the material is crushed into particles ≤1 mm by a mechanical crusher, and then crushed into particles 0.05-0.075 mm by an air vortex micronizer to obtain a material A of tartaric acid and DMPP; at room temperature, 100 grams of DMPP are dissolved in 100 grams of water, stirred for 5-8 minutes, and the temperature is raised to normal pressure. The mixture is stirred and heat-dried while being maintained at 90°C-95°C, and dried to a moisture content of 3.0%; the material is crushed with a mechanical pulverizer to a particle size of ≤1 mm, and then crushed with an airflow vortex micronizer to 0.05-0.075 mm to obtain material B; 106 g of 85% phosphoric acid and 10 g of DMPP are dissolved in 84 g of water, stirred evenly, stirred for 5-8 minutes, and the temperature is increased to normal pressure while being stirred and heat-dried while being maintained at 90°C-95°C, and dried to a moisture content of 3.0% to obtain a viscous mixture C.

[0016] 2. Indoor simulation test

[0017] Soil from the tillage layer of 0-20cm was collected from the farmland in Fengshou Village, Bayi Township, Linhe District, Bayannur City, Inner Mongolia Autonomous Region, brought back to the laboratory, mixed evenly, and measured its pH to be 8.4 using a "Lemagnetic" acidometer pH meter S-25. The soil sample was air-dried to a moisture content of about 3.0%, and 18 portions of soil were taken, each weighing 500.0 grams, of which 9 portions: 9 portions of material B 0.050 grams were weighed, first mixed evenly with 5 grams of soil, then mixed evenly with the remaining 495 grams of soil, placed in a culture pot, and water was added to the content of 15.0%; the other 9 portions: 9 portions of material A 0.50 grams were weighed, first mixed evenly with 5 grams of soil, then mixed evenly with the remaining 495 grams of soil, placed in a culture pot, and water was added to the content of 15.0%. All 18 treated samples were placed in a constant temperature incubator, maintained at a temperature of 35.0℃, and water was regularly replenished according to weight loss every day. The content of DMPP in the soil was measured on the 3rd, 5th and 10th days. During the measurement, the soil sample in the culture pot was poured out and mixed, 5.0g of soil sample was taken into a shaking bottle, 50.0ml of deionized water was added, and the mixture was shaken at 180r / min for 2h, centrifuged at 1000r / min, and the clarified liquid was taken. The DMPP content was measured at a detection wavelength of 224nm using a liquid chromatograph, and the DMPP aqueous solution was used for detection and analysis to draw a standard curve. For each test, destructive sampling was used for DMPP and DMPP+tartaric acid treatments, and three soil samples from each culture pot were taken for testing, and the average was taken.

[0018] Table 1 Effect of tartaric acid on DMPP decomposition at different time points

[0019] Content (mg / kg) Day 3 Day 5 Day 10 DMPP 72.4 69.8 40.6 DMPP+Tartaric acid 79.2 75.3 68.1

[0020] It can be seen from Table 1 that at a culture temperature of 35°C, starting from the third day, tartaric acid showed a good inhibitory effect on the decomposition of DMPP, greatly prolonging the half-life of DMPP, so that DMPP was at a higher concentration and could maintain its stable effect state.

[0021] 3. Comparative test

[0022] Soil from the topsoil layer of 0-20 cm was collected from the farmland in Fengshou Village, Bayi Township, Linhe District, Bayannur City, Inner Mongolia Autonomous Region, brought back to the laboratory, mixed evenly, and the pH value was measured to be 8.4 using a "Leci" acidometer pH meter S-25. The soil sample was air-dried to a moisture content of about 3.0%. 18 portions of soil were taken, each portion was 500.0 g. Among them, 6 portions: 6 portions of material B were weighed, each portion was 0.050 g, first mixed with 5 g of soil, then mixed with the remaining 495 g of soil, put into a culture pot, and water was added to the content of 20.0%; 6 portions: 6 portions of material A were weighed, each portion was 0.50 g, first mixed with 5 g of soil, then mixed with the remaining 495 g of soil, put into a culture pot, and water was added to the content of 20.0%; 6 portions: 6 portions of viscous mixture C were weighed, each portion was 0.50 g, first mixed with 5 g of soil, then mixed with the remaining 495 g of soil, put into a culture pot, and water was added to the content of 20.0%. All 18 treated samples were placed in a constant temperature incubator, maintained at a temperature of 40.0°C, and water was regularly added according to weight loss every day. The content of DMPP in the soil was measured on the 2nd and 3rd days respectively. Pour out the soil sample in the culture pot and mix it evenly. Take 5.0g of soil sample in a shaking bottle, add 50.0ml of deionized water, shake at 180r / min for 2h, centrifuge at 1000r / min, take the clarified liquid, use liquid chromatography to determine the DMPP content at a detection wavelength of 224nm, and at the same time use DMPP aqueous solution for detection and analysis to draw a standard curve. For each test, all treatments use destructive sampling, take three soil samples from each culture pot for testing, and take the average.

[0023] Table 2 Effects of tartaric acid and phosphoric acid on the decomposition of DMPP at different time points

[0024] Content (mg / kg) Day 2 Day 3 DMPP 48.3 39.7 DMPP+Tartaric acid 57.2 48.4 DMPP+phosphoric acid 46.9 38.5

[0025] It can be seen from Table 2 that at a culture temperature of 40°C, tartaric acid showed a good protective effect, while phosphoric acid, which is more acidic than tartaric acid, did not show any effect. The reason may be that phosphoric acid dissolves much faster in the soil solution than tartaric acid, causing the separation of phosphoric acid and DMPP, and failing to provide a protective effect.

[0026] 4. Application in large-scale equipment production

[0027] The rotary drum granulation process is used to produce compound fertilizers with a nitrogen, phosphorus and potassium ratio of 22-18-10, and three kinds of fertilizers are produced respectively: (1) conventional compound fertilizer: the raw materials used per ton are 380.4 kg of urea (46%), 409.0 kg of monoammonium phosphate (11-44-0), 166.7 kg of potassium chloride (60%) and 43.9 kg of filler. All the materials are crushed through a 20-mesh sieve, mixed evenly, and put into a rotary drum for granulation, drying, cooling, screening and packaging to obtain conventional compound fertilizer C; (2) conventional compound fertilizer + DMPP: the raw materials used per ton are 380.4 kg of urea (46%), 409.0 kg of monoammonium phosphate (11-44-0), 166.7 kg of potassium chloride (60%), 1.0 kg of material B and 42.9 kg of filler. All the materials are crushed through a 20-mesh sieve. During operation, material B is firstly mixed with 20 times the weight of urea powder, then put into the urea feeding port, mixed evenly, then mixed evenly with monoammonium phosphate, potassium chloride, and filler, and then put into the drum for granulation, drying, cooling, sieving, and packaging to obtain compound fertilizer D containing DMPP; (3) Conventional compound fertilizer + DMPP + tartaric acid: the raw materials used per ton are urea (46%) 380.4kg, monoammonium phosphate (11-44-0) 409.0kg, potassium chloride (60%) 166.7kg, material A 10.0kg and filler 33.9kg, all of which are crushed through a 20-mesh sieve. During operation, material A is firstly mixed with 10 times the weight of urea powder, then put into the urea feeding port, mixed evenly, then mixed evenly with monoammonium phosphate, potassium chloride, and filler, and then put into the drum for granulation, drying, cooling, sieving, and packaging to obtain fertilizer E containing DMPP and tartaric acid.

[0028] 5. Cell experiment

[0029] The test site is located in Fengshou Village, Bayi Township, Linhe District, Bayannur City, Inner Mongolia Autonomous Region. The plot with uniform soil fertility was selected to plant corn. The soil pH was 8.4. The setting area was 25m 2There were 9 plots (5m*5m), and each treatment was repeated 3 times. (1) Conventional fertilizer: 0.71kg urea, 0.77kg monoammonium phosphate, and 0.31kg potassium chloride were applied to each plot. The three materials were crushed to a particle size of less than 0.1mm, and then the three materials were mixed evenly, and then mixed evenly with 10 times the weight of dry soil, and evenly spread on the surface, plowed, and sown; (2) Conventional fertilizer + DMPP: 0.71kg urea, 0.77kg monoammonium phosphate, 0.31kg potassium chloride, and 1.87g of the material B prepared above were applied to each plot. The three materials of urea, monoammonium phosphate, and potassium chloride were crushed to a particle size of less than 0.1m m, first mix material B with urea, then mix it with the other two materials, then mix it with 10 times the weight of dry soil, evenly spread it on the surface, plow and sow; (3) Conventional fertilizer + DMPP + tartaric acid: 0.71kg of urea, 0.77kg of monoammonium phosphate, 0.31kg of potassium chloride, and 18.7g of the above prepared material A were applied to each plot, and the three materials of urea, monoammonium phosphate and potassium chloride were crushed to a particle size of less than 0.1mm. Material A was first mixed with the three materials, then mixed with 10 times the weight of dry soil, evenly spread it on the surface, plow and sow. No topdressing was applied in the later stage of all treatments, and seeds, pesticides and other management were kept consistent. The amount of nitrate nitrogen and ammonium nitrogen in the soil was measured on the 20th, 80th and 100th days. During the measurement, soil samples of 0-20cm of the tillage layer were taken using a soil drill, and the five-point cross sampling method was adopted. 5 drills were taken from each plot, and about 300g of soil was taken. The soil samples were brought back to the laboratory, sieved, and mixed. 5.0 g of the soil samples were taken and the 2.00 mol·L -1 The corn was extracted with potassium chloride solution and measured with a 3-AA3 flow analyzer. The results are shown in Tables 2 and 3. The yield was measured at harvest time. From the 5th plant in each of the 4 middle ridges of each plot, 5 plants were taken continuously, for a total of 20 plants. The corn was broken off and brought back to the laboratory. It was threshed, air-dried, weighed, and the yield per mu was calculated. The results are shown in Table 5.

[0030] Table 3 Effect of tartaric acid combined with DMPP on reducing nitrate nitrogen

[0031] Nitrate nitrogen (mg / kg) Day 20 Day 80 Day 100 Conventional fertilization 45.7 27.5 17.3 Conventional fertilization + DMPP 39.5 28.2 22.1 Conventional fertilization + DMPP + tartaric acid 34.1 30.5 24.7

[0032] Table 4 Effect of tartaric acid combined with DMPP on increasing soil ammonium nitrogen

[0033] Ammonium nitrogen (mg / kg) Day 20 Day 80 Day 120 Conventional fertilization 29.3 19.2 15.4 Conventional fertilization + DMPP 37.0 27.8 23.4 Conventional fertilization + DMPP + tartaric acid 45.3 42.7 29.2

[0034] Table 5 Effect of tartaric acid combined with DMPP on increasing corn yield

[0035]

[0036] In summary, compared with the use of DMPP alone, DMPP protected by tartaric acid showed good effects in reducing soil nitrate nitrogen, increasing ammonium nitrogen and increasing corn yield.

[0037] 6. Field Experiment

[0038] The test site is located in Fengshou Village, Bayi Township, Linhe District, Bayannur City, Inner Mongolia Autonomous Region. The soil fertility is uniform and the terrain is flat. The pH of the soil plough layer was measured to be 8.4 before planting. Three treatments were set up: Treatment 1 conventional fertilization (using the conventional compound fertilizer C prepared above), Treatment 2 conventional compound fertilizer + DMPP (compound fertilizer D prepared above), Treatment 3 conventional compound fertilizer + DMPP + tartaric acid (compound fertilizer E prepared above), each treatment 3 replicates, each treatment area 1 mu. All three treatments applied the corresponding fertilizer products at 50 kg per mu of land, plowed, raked and then applied seed fertilizer with a seeder, sowing and fertilization were completed simultaneously. No more topdressing in the later period, weeding, spraying and other measures remained consistent. At the harvest time, a harvester was used, each replicate was harvested separately, and the weight was weighed after drying and dehydration to obtain the actual yield. The average yield of the three replicates was the final data.

[0039] Table 6 Effect of tartaric acid combined with DMPP on increasing corn yield

[0040]

[0041] 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 tartaric acid as a protective agent for nitrification inhibitor 3,4-dimethylpyrazole phosphate.

2. The use according to claim 1, characterized in that Tartaric acid is used to slow down the decomposition of the nitrification inhibitor 3,4-dimethylpyrazole phosphate in alkaline soils.

3. A long-acting nitrification inhibitor, characterized in that The invention is prepared from the following components by weight: 8-9 parts of tartaric acid and 1-2 parts of 3,4-dimethylpyrazole phosphate.

4. The method for preparing the long-acting nitrification inhibitor according to claim 3, characterized in that The steps include: Step 1: dissolving 8-9 parts of tartaric acid and 1-2 parts of 3,4-dimethylpyrazole phosphate in water to obtain a mixed solution; Step 2: heating and drying the mixed solution while stirring until the water content of the material is 3.0% w / w to obtain a dried material; Step 3: The dried material is crushed by a mechanical crusher to obtain a long-acting nitrification inhibitor.

5. The preparation method according to claim 4, characterized in that: In the step 1, 8-9 parts of tartaric acid and 1-2 parts of 3,4-dimethylpyrazole phosphate are dissolved in 10-15 parts of water to obtain a mixed solution; In the step 2, the mixed solution is heated to 90° C.-95° C., and is dried under normal pressure while being stirred until the moisture content of the material reaches 3.0% w / w, thereby obtaining a dried material; In the step 3, the dried material is crushed by a mechanical crusher to a particle size of ≤1 mm, and then crushed by an air flow vortex micronizer to 0.05-0.075 mm to obtain a long-acting nitrification inhibitor.

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