A powder comprising n-butyl thiophosphoric triamide and its use

Abstract

The application relates to a powder containing n-butyl thiophosphoric triamide and application thereof. The powder containing n-butyl thiophosphoric triamide provided by the application can effectively reduce the decomposition rate of n-butyl thiophosphoric triamide after being added into a fertilizer, effectively prolong the action time of n-butyl thiophosphoric triamide, and improve the urease inhibition effect.

Description

Technical Field

[0001] This application belongs to the field of fertilizer enhancement technology, specifically relating to a powder containing n-butylthiophosphoric triamine, its preparation method, and its application in fertilizer production. Background Technology

[0002] my country is the world's largest consumer of fertilizers, with nitrogen fertilizer being the most widely used type in agricultural production. However, its nitrogen fertilizer utilization rate (30-35%) is far lower than that of developed countries in Europe and America (50-70%). A small portion of the nitrogen not utilized by crops remains in the soil, while the majority is lost to water and the atmosphere as ammonium and nitrate nitrogen, resulting not only in fertilizer waste but also environmental pollution. Therefore, improving nitrogen fertilizer utilization is a key and challenging issue for researchers in the fertilizer industry.

[0003] Studies have found that urease inhibitors are compounds that can inhibit the catalytic activity of urease in soil on urea. When mixed with urea-containing fertilizers and applied to the soil, they can effectively inhibit soil urease activity, achieve slow and controlled release of nitrogen, improve nitrogen fertilizer utilization, reduce nitrogen fertilizer application, and increase crop yield.

[0004] Butylthiophosphoric triamine (NBPT) is one of the most effective soil urease inhibitors. However, NBPT also has many drawbacks in practical applications, including: ① NBPT has poor physicochemical stability and is prone to clumping and decomposition during long-term storage; ② NBPT has many limitations in fertilizer application, for example, its decomposition is accelerated in compound fertilizers, especially phosphorus-containing compound fertilizers; ③ NBPT is relatively sensitive to temperature and decomposes more easily at higher temperatures.

[0005] Currently, the main marketed formulations of n-butylthiophosphoric triamine are liquid formulations, including BASF's Lemos and Solvay's Ambosty. However, the application of liquid formulations is mainly limited to their combination with mineral fertilizers, which presents certain limitations. Therefore, it is necessary to further expand the development of n-butylthiophosphoric triamine formulations and find more widely applicable and stable combinations. Summary of the Invention

[0006] On one hand, this application provides a powder containing n-butylthiophosphoric triamine, characterized in that the powder further contains:

[0007] 1) Cyclodextrin,

[0008] 2) The polymer is selected from one or a mixture of two of polyethyleneimine or polyacrylamide.

[0009] In some embodiments of this application, the powder may further comprise a pigment. In some embodiments of this application, the pigment is selected from water-soluble or alcohol-soluble pigments. In some embodiments of this application, the pigment may be lemon yellow, brilliant blue, carmine, chocolate brown, grape purple, or fruit green.

[0010] In some embodiments of this application, the cyclodextrin is selected from β-cyclodextrin or its derivatives. In some embodiments of this application, the β-cyclodextrin derivative is selected from methyl-β-cyclodextrin, dimethyl-β-cyclodextrin, trimethyl-β-cyclodextrin, hydroxyethyl-β-cyclodextrin, or hydroxypropyl-β-cyclodextrin. In some embodiments of this application, the hydroxypropyl-β-cyclodextrin is selected from 2-hydroxypropyl-β-cyclodextrin or 3-hydroxypropyl-β-cyclodextrin.

[0011] In some embodiments of this application, the polymer is selected from polyethyleneimine. In some embodiments of this application, the polymer is selected from polyacrylamide.

[0012] In some embodiments of this application, the polymer is selected from a mixture of polyethyleneimine and polyacrylamide. In some embodiments of this application, the polymer is selected from a mixture of polyethyleneimine and polyacrylamide, wherein the mass ratio of polyethyleneimine to polyacrylamide is 0.5-2, preferably 1:1, 1:2, or 2:1.

[0013] In some embodiments of this application, by weight, this application provides a powder containing 4 parts n-butylthiophosphoric triamine, 25-45 parts cyclodextrin, and 0.5-2 parts polymer. In some embodiments of this application, by weight, this application provides a powder containing 4 parts n-butylthiophosphoric triamine, 25-45 parts cyclodextrin, 0.5-2 parts polymer, and 0.05-0.15 parts pigment.

[0014] In some embodiments of this application, by weight, this application provides a powder containing 4 parts n-butylthiophosphoric triamine, 30-40 parts cyclodextrin, and 0.8-1.2 parts polymer. In some embodiments of this application, by weight, this application provides a powder containing 4 parts n-butylthiophosphoric triamine, 30-40 parts cyclodextrin, 0.8-1.2 parts polymer, and 0.08-0.12 parts pigment.

[0015] In some embodiments of this application, by weight, this application provides a powder containing 4 parts n-butylthiophosphoric triamine, 33-36 parts cyclodextrin, and 0.9-1.1 parts polymer. In some embodiments of this application, by weight, this application provides a powder containing 4 parts n-butylthiophosphoric triamine, 33-36 parts cyclodextrin, 0.9-1.1 parts polymer, and 0.09-0.11 parts pigment.

[0016] In some embodiments of this application, by weight, this application provides a powder containing 4 parts n-butylthiophosphoric triamine, 35 parts cyclodextrin, and 1 part polymer. In some embodiments of this application, by weight, this application provides a powder containing 4 parts n-butylthiophosphoric triamine, 35 parts cyclodextrin, 1 part polymer, and 0.1 parts pigment.

[0017] In some embodiments of this application, this application provides a powder composed of n-butylthiophosphoric triamine, cyclodextrin, and a polymer.

[0018] In some embodiments of this application, this application provides a powder composed of n-butylthiophosphoric triamine, cyclodextrin, polymer and pigment.

[0019] In some embodiments of this application, by weight, this application provides a powder composed of 4 parts n-butylthiophosphoric triamine, 25-45 parts cyclodextrin, and 0.5-2 parts polymer. In some embodiments of this application, by weight, this application provides a powder composed of 4 parts n-butylthiophosphoric triamine, 25-45 parts cyclodextrin, 0.5-2 parts polymer, and 0.05-0.15 parts pigment.

[0020] In some embodiments of this application, by weight, this application provides a powder composed of 4 parts n-butylthiophosphoric triamine, 30-40 parts cyclodextrin, and 0.8-1.2 parts polymer. In some embodiments of this application, by weight, this application provides a powder composed of 4 parts n-butylthiophosphoric triamine, 30-40 parts cyclodextrin, 0.8-1.2 parts polymer, and 0.08-0.12 parts pigment.

[0021] In some embodiments of this application, by weight, this application provides a powder composed of 4 parts n-butylthiophosphoric triamine, 33-36 parts cyclodextrin, and 0.9-1.1 parts polymer. In some embodiments of this application, by weight, this application provides a powder composed of 4 parts n-butylthiophosphoric triamine, 33-36 parts cyclodextrin, 0.9-1.1 parts polymer, and 0.09-0.11 parts pigment.

[0022] In some embodiments of this application, by weight, this application provides a powder composed of 4 parts n-butylthiophosphoric triamine, 35 parts cyclodextrin, and 1 part polymer. In some embodiments of this application, by weight, this application provides a powder composed of 4 parts n-butylthiophosphoric triamine, 35 parts cyclodextrin, 1 part polymer, and 0.1 parts pigment.

[0023] In some embodiments of this application, the particle size distribution of the powder satisfies X10≤50μm, X50≤200μm; preferably satisfies X10≤50μm, X50≤100μm; most preferably satisfies X10≤50μm, X50≤80μm.

[0024] On the other hand, this application provides a method for preparing a powder containing n-butylthiophosphoric triamine, comprising: NBPT and cyclodextrin in a solvent, stirring at a certain temperature for a period of time, adding a polymer, selectively adding a pigment, stirring evenly, and then spray drying.

[0025] This application provides a method for preparing a powder containing n-butylthiophosphoric triamine, comprising: dissolving NBPT in a solvent, adding cyclodextrin, stirring at a certain temperature, adding a polymer, selectively adding a pigment, stirring evenly, and then spray drying.

[0026] In some embodiments of this application, the solvent in the preparation method is selected from one or more of water, methanol, or ethanol. In some embodiments of this application, the solvent in the preparation method is selected from a mixture of methanol and ethanol, a mixture of water and ethanol, or a mixture of water and methanol. In some embodiments of this application, the volume ratio of the mixture is 1:0.5-2, preferably 1:1.

[0027] In some embodiments of this application, the stirring temperature in the preparation method is 20-90℃, preferably 40-80℃, and most preferably 40-60℃.

[0028] In some embodiments of this application, the stirring time in the preparation method is 3-15 h, preferably 4-12 h, and most preferably 4-8 h.

[0029] In some embodiments of this application, the spray drying conditions in the preparation method are: inlet temperature 180°C and outlet temperature 80°C.

[0030] On the other hand, this application provides the use of n-butylthiophosphoric triamine powder as a fertilizer additive.

[0031] This application provides a fertilizer, which includes a water-soluble fertilizer and fertilizer additives.

[0032] In some embodiments of this application, the fertilizer additive is the powder containing n-butylthiophosphoric triamine mentioned above.

[0033] In some embodiments of this application, the water-soluble fertilizer is selected from balanced, high-phosphorus, or high-potassium fertilizers. In some embodiments of this application, the water-soluble fertilizer is selected from balanced 20-20-20, high-phosphorus 15-30-15, or high-potassium 12-8-40.

[0034] In some embodiments of this application, the fertilizer contains 0.4%-0.8% by weight of n-butylthiophosphoric triamine. In some embodiments of this application, the fertilizer contains 0.5% by weight of n-butylthiophosphoric triamine.

[0035] The n-butylthiophosphoric triamine (NBPT) powder provided in this application has the following advantages: 1. It can effectively improve the physical properties of NBPT and enhance its chemical stability; 2. The powder can be stored for a long time and is not prone to clumping; 3. It is easy to use, expanding the application range of NBPT, and can be applied to various fertilizers, especially powdered water-soluble fertilizers; 4. When the powder is added to fertilizer, it can effectively reduce the decomposition rate of NBPT, effectively prolong the action time of NBPT, and improve the urease inhibition effect. Detailed Implementation

[0036] The technical solutions of this application are illustrated below with specific embodiments, but the scope of protection of this application is not limited to the scope of the described embodiments. All reagents used are commercially available products.

[0037] Detection method: High performance liquid chromatography; Column: AQUASIL C18 250*4.6; Mobile phase: Acetonitrile:water = 78:22; Flow rate: 0.8 mL / min; Column temperature: 30℃; Detector: UV; Detection wavelength: 224 nm.

[0038] Example 1:

[0039] Formula (by weight):

[0040] NBPT 4 copies 2-Hydroxypropyl-β-cyclodextrin 35 copies Polyethyleneimine 1 copy Pigment (Brilliant Blue) 0.1 copies

[0041] Preparation: Add 4g of NBPT to 100g of water, heat to 40℃ and stir to dissolve. Then add 35g of 2-hydroxypropyl-β-cyclodextrin and stir for 4h. Then add 1g of polyethyleneimine and 0.1g of pigment, stir evenly and spray dry to obtain a powdery solid containing NBPT with a particle size distribution that satisfies X10≤50μm and X50≤100μm.

[0042] Example 2:

[0043] Formula (by weight):

[0044] NBPT 4 copies 2-Hydroxypropyl-β-cyclodextrin 35 copies Polyacrylamide 1 copy Pigment (Brilliant Blue) 0.1 copies

[0045] Preparation: Add 4g of NBPT to 100g of water, heat to 40℃ and stir to dissolve. Then add 35g of 2-hydroxypropyl-β-cyclodextrin and stir to react for 4h. Then add 1g of polyacrylamide and 0.1g of pigment, stir evenly and spray dry to obtain a powdery solid containing NBPT with a particle size distribution that satisfies X10≤50μm and X50≤100μm.

[0046] Example 3:

[0047] Formula (by weight):

[0048] NBPT 4 copies 2-Hydroxypropyl-β-cyclodextrin 35 copies Polyethyleneimine and polyacrylamide (mass ratio 1:1) 1 copy Pigment (Brilliant Blue) 0.1 copies

[0049] Preparation: Add 4g of NBPT to 100g of water / ethanol (volume ratio 1:1), heat to 40℃ and stir to dissolve. Then add 35g of 2-hydroxypropyl-β-cyclodextrin and stir for 4h. Then add 1g of polyethyleneimine, polyacrylamide and 0.1g of pigment, stir evenly and spray dry to obtain a powdery solid containing NBPT with a particle size distribution that satisfies X10≤50μm and X50≤80μm.

[0050] Example 4:

[0051] Formula (by weight):

[0052] NBPT 4 copies 2-Hydroxypropyl-β-cyclodextrin 35 copies Polyethyleneimine 1 copy Pigment (Brilliant Blue) 0.1 copies

[0053] Preparation: Add 4g of NBPT to 100g of ethanol / methanol (volume ratio 1:1), heat to 40℃ and stir to dissolve. Then add 35g of 2-hydroxypropyl-β-cyclodextrin and stir for 12h. Then add 1g of polyethyleneimine and 0.1g of pigment, stir evenly and spray dry to obtain a powdery solid containing NBPT with a particle size distribution that satisfies X10≤50μm and X50≤100μm.

[0054] Example 5:

[0055] Formula (by weight):

[0056] NBPT 4 copies β-Cyclodextrin 35 copies Polyethyleneimine 1 copy Pigment (Brilliant Blue) 0.1 copies

[0057] Preparation: Add 4g of NBPT to 100g of water, heat to 40℃ and stir to dissolve. Then add 35g of β-cyclodextrin, heat to 80℃ and stir to react for 12h. Then add 1g of polyethyleneimine and 0.1g of pigment, stir evenly and spray dry to obtain a powdery solid containing NBPT with a particle size distribution that satisfies X10≤50μm and X50≤100μm.

[0058] Comparative Example 1:

[0059] formula:

[0060] NBPT 4 copies 2-Hydroxypropyl-β-cyclodextrin 35 copies Pigment (Brilliant Blue) 0.1 copies

[0061] Preparation: Add 4g of NBPT to 100g of water, heat to 40℃ and stir to dissolve, then add 35g of 2-hydroxypropyl-β-cyclodextrin, stir and react for 4h, then add 0.1g of pigment, stir evenly and spray dry to obtain a powdery solid containing NBPT.

[0062] Comparative Example 2

[0063] formula:

[0064] NBPT 2 copies DMSO 7 copies Polyethyleneimine 1 copy Pigment (Brilliant Blue) 0.1 copies

[0065] Preparation: Add 20g of NBPT to 70g of DMSO and stir to dissolve. Then add 10g of polyethyleneimine and 0.1g of pigment and stir until homogeneous to obtain the NBPT liquid preparation.

[0066] Comparative Example 3

[0067] formula:

[0068] NBPT 4 copies Pigment (Brilliant Blue) 0.1 copies

[0069] Preparation: Add 4g of NBPT to 50g of water, heat to 40℃ and stir to dissolve, then add 0.1g of pigment, stir evenly and spray dry to obtain NBPT powder solid.

[0070] Experimental results

[0071] Applications: Three types of fertilizers: Balanced 20-20-20, High Phosphorus 15-30-15, High Potassium 12-8-40

[0072] Examples 1-5: Add the powder prepared in Examples 1-5 (finally containing 0.5% NBPT) to the fertilizer and stir until homogeneous. Comparative Examples 1-3: Add the formulation prepared in Comparative Examples 1-3 (finally containing 0.5% NBPT) to the fertilizer and stir until homogeneous.

[0073] experiment 1 day % 10 days % 20 days % 30 days % 30-day loss rate % Example 1 (20-20-20) 0.0492 0.0480 0.0472 0.0467 5.1 Example 1 (15-30-15) 0.0504 0.0489 0.0476 0.0465 7.7 Example 1 (12-8-40) 0.0498 0.0486 0.0480 0.0475 4.6 Example 2 (20-20-20) 0.0496 0.0486 0.0478 0.0470 5.2 Example 2 (15-30-15) 0.0510 0.0499 0.0484 0.0477 6.4 Example 2 (12-8-40) 0.0507 0.0498 0.0487 0.0480 5.3 Example 3 (20-20-20) 0.0495 0.0489 0.0483 0.0475 3.9 Example 3 (15-30-15) 0.0497 0.0492 0.0488 0.0484 2.6 Example 3 (12-8-40) 0.0499 0.0493 0.0487 0.0482 3.4 Example 4 (20-20-20) 0.0497 0.0490 0.0482 0.0475 4.4 Example 4 (15-30-15) 0.0496 0.0484 0.0473 0.0464 6.5 Example 4 (12-8-40) 0.0505 0.0496 0.0489 0.0481 4.7 Example 5 (20-20-20) 0.0501 0.0479 0.0468 0.0458 8.6 Example 5 (15-30-15) 0.0504 0.0483 0.0469 0.0457 9.3 Example 5 (12-8-40) 0.0499 0.0486 0.0478 0.0465 6.8 Comparative Example 1 (20-20-20) 0.0503 0.0460 0.0425 0.0396 21.2 Comparative Example 1 (15-30-15) 0.0495 0.0459 0.0408 0.0353 28.7 Comparative Example 1 (12-8-40) 0.0498 0.0476 0.0450 0.0421 15.5 Comparative Example 2 (20-20-20) 0.0497 0.0453 0.0417 0.0376 24.4 Comparative Example 2 (15-30-15) 0.0504 0.0456 0.0401 0.0342 32.1 Comparative Example 2 (12-8-40) 0.0501 0.0474 0.0449 0.0413 17.6 Comparative Example 3 (20-20-20) 0.0510 0.0424 0.0309 0.0182 64.3 Comparative Example 3 (15-30-15) 0.0494 0.0361 0.0215 0.0104 78.9 Comparative Example 3 (12-8-40) 0.0492 0.0450 0.0346 0.0237 51.8 .

Claims

1. A powder composed of n-butylthiophosphoric triamine, cyclodextrin, and a polymer, wherein the polymer is selected from a mixture of polyethyleneimine and polyacrylamide, wherein, The mass ratio of polyethyleneimine to polyacrylamide is 1:1; by weight, the powder contains 4 parts of n-butylthiophosphoric triamine, 25-45 parts of cyclodextrin, and 0.5-2 parts of polymer; the preparation method of the powder includes: n-butylthiophosphoric triamine and cyclodextrin in a solvent, stirring, adding polymer, stirring evenly, and then spray drying, wherein the solvent is selected from a mixture of water and ethanol with a volume ratio of 1:

1.

2. A powder composed of n-butylthiophosphoric triamine, cyclodextrin, a polymer, and a pigment, wherein the polymer is selected from a mixture of polyethyleneimine and polyacrylamide, wherein... The mass ratio of polyethyleneimine to polyacrylamide is 1:1; by weight, the powder contains 4 parts of n-butylthiophosphoric triamine, 25-45 parts of cyclodextrin, and 0.5-2 parts of polymer; the preparation method of the powder includes: n-butylthiophosphoric triamine and cyclodextrin in a solvent, stirring, adding polymer and pigment, stirring evenly, and then spray drying, wherein the solvent is selected from a mixture of water and ethanol with a volume ratio of 1:

1.

3. The powder according to claim 2, wherein the pigment is selected from water-soluble or alcohol-based pigments.

4. The powder according to claim 2, wherein the pigment is selected from lemon yellow, brilliant blue, carmine, chocolate brown, grape purple, or fruit green.

5. The powder according to claim 1 or 2, wherein the cyclodextrin is selected from β-cyclodextrin or its derivatives.

6. The powder according to claim 1 or 2, wherein the cyclodextrin is selected from methyl-β-cyclodextrin, dimethyl-β-cyclodextrin, trimethyl-β-cyclodextrin, hydroxyethyl-β-cyclodextrin, or hydroxypropyl-β-cyclodextrin.

7. The powder according to claim 1 or 2, wherein the cyclodextrin is selected from 2-hydroxypropyl-β-cyclodextrin or 3-hydroxypropyl-β-cyclodextrin.

8. The powder according to claim 2, wherein, by weight, the powder contains 4 parts n-butylthiophosphoric triamine, 25-45 parts cyclodextrin, 0.5-2 parts polymer, and 0.05-0.15 parts pigment.

9. The powder according to claim 1 or 2, wherein, by weight, the powder contains 4 parts n-butylthiophosphoric triamine, 30-40 parts cyclodextrin, and 0.8-1.2 parts polymer.

10. The powder of claim 2, wherein, by weight, the powder contains 4 parts n-butylthiophosphoric triamine, 30-40 parts cyclodextrin, 0.8-1.2 parts polymer, and 0.08-0.12 parts pigment.

11. The powder according to claim 1 or 2, wherein, by weight, the powder contains 4 parts of n-butylthiophosphoric triamine, 33-36 parts of cyclodextrin, and 0.9-1.1 parts of polymer.

12. The powder of claim 2, wherein, by weight, the powder contains 4 parts of n-butylthiophosphoric triamine, 33-36 parts of cyclodextrin, 0.9-1.1 parts of polymer, and 0.09-0.11 parts of pigment.

13. The powder of claim 1 or 2, wherein, by weight, the powder contains 4 parts n-butylthiophosphoric triamine, 35 parts cyclodextrin, and 1 part polymer.

14. The powder of claim 2, wherein, by weight, the powder contains 4 parts n-butylthiophosphoric triamine, 35 parts cyclodextrin, 1 part polymer, and 0.1 part pigment.

15. The powder of claim 1, wherein the powder is composed of 4 parts by weight of n-butylthiophosphoric triamine, 35 parts by weight of cyclodextrin, and 1 part by weight of polymer.

16. The powder of claim 2, wherein, by weight, the powder comprises 4 parts n-butylthiophosphoric triamine, 35 parts cyclodextrin, 1 part polymer, and 0.1 parts pigment.

17. The powder as described in claim 1 or 2, wherein the particle size distribution of the powder satisfies X10≤50μm and X50≤200μm.

18. Use of the n-butylthiophosphoric triamine powder as described in claim 1 or 2 as a fertilizer additive.

19. A fertilizer comprising a water-soluble fertilizer and a fertilizer additive, wherein the fertilizer additive is the powder according to claim 1 or 2, and the fertilizer contains 0.4% - 0.8% by weight of n-butylthiophosphoric triamine.

20. The fertilizer of claim 19, wherein the fertilizer is selected from balanced, high-phosphorus, or high-potassium fertilizers.

21. The fertilizer as described in claim 19, wherein the fertilizer is selected from balanced type 20-20-20, high phosphorus type 15-30-15, or high potassium type fertilizer 12-8-40.