CN115141225A - Stable urease inhibitor and preparation method and application thereof - Google Patents
Stable urease inhibitor and preparation method and application thereof Download PDFInfo
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- 239000002601 urease inhibitor Substances 0.000 title claims abstract description 56
- 229940090496 Urease inhibitor Drugs 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000004202 carbamide Substances 0.000 claims abstract description 47
- 239000003337 fertilizer Substances 0.000 claims abstract description 38
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000002195 synergetic effect Effects 0.000 claims abstract description 6
- -1 benzylamine thiophosphoric triamide Chemical compound 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical group ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 claims description 5
- FNGLQNMQHOAIJQ-UHFFFAOYSA-N Cl[S](Cl)Cl Chemical compound Cl[S](Cl)Cl FNGLQNMQHOAIJQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 230000000813 microbial effect Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003516 soil conditioner Substances 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 229960001952 metrifonate Drugs 0.000 abstract 1
- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002689 soil Substances 0.000 description 12
- HEPPIYNOUFWEPP-UHFFFAOYSA-N n-diaminophosphinothioylbutan-1-amine Chemical compound CCCCNP(N)(N)=S HEPPIYNOUFWEPP-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000618 nitrogen fertilizer Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 101100406597 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) OST1 gene Proteins 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 108010046334 Urease Proteins 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007909 melt granulation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- PNNCWTXUWKENPE-UHFFFAOYSA-N [N].NC(N)=O Chemical compound [N].NC(N)=O PNNCWTXUWKENPE-UHFFFAOYSA-N 0.000 description 1
- BMDVPRGEZHHGLJ-UHFFFAOYSA-N [S](Cl)(Cl)Cl.[P] Chemical compound [S](Cl)(Cl)Cl.[P] BMDVPRGEZHHGLJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000008039 phosphoramides Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/224—Phosphorus triamides
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Soil Sciences (AREA)
- Fertilizers (AREA)
Abstract
The invention relates to a stable urease inhibitor and a preparation method and application thereof, belonging to the field of fertilizer synergists. The invention takes benzylamine and trichlorfon as starting raw materials to prepare stable urease inhibitor benzylamine thiophosphoric triamide (NLT). The urease inhibitor is stable to water and temperature, is not easy to decompose, has a good effect of inhibiting urea decomposition, is applied to the preparation of synergistic urea and synergistic fertilizers, and has the advantages of short processing flow, good stability, high utilization rate, convenience in use, low cost, easiness in popularization and the like.
Description
Technical Field
The invention discloses a stable urease inhibitor and preparation and application methods thereof, and belongs to the field of fertilizer synergists.
Background
In the 80 s of the 20 th century, the grain yield was generally improved along with the common use of chemical fertilizers. According to the estimation of the food and agriculture organization of the United nations, 55 percent of the grain yield increase of the developing countries comes from the effect of chemical fertilizers. At present, the annual nitrogen fertilizer yield of China is about 5000 ten thousand tons (converted into pure nitrogen), wherein the urea yield is over 3000 ten thousand tons (converted into pure nitrogen). Urea quiltAfter being applied to soil, the soil is rapidly decomposed into ammonium nitrogen and carbon dioxide under the action of urease in the soil, and if the soil adsorption capacity cannot be combined with released ammonium nitrogen, part of gaseous NH 3 The nitrogen is volatilized from soil, so that the loss of nitrogen is serious, the problems of reduction of the utilization rate of urea, environmental pollution and the like are caused, and the average utilization rate of the nitrogen fertilizer in China is about 35 percent at present.
Since urea is the nitrogen fertilizer with the highest nitrogen content to date, it is also the main nitrogen fertilizer source in the world. The addition of urease inhibitors to urea is one of the effective methods to reduce nitrogen loss caused by urease. At present, urease inhibitor products on the market comprise hydroquinone, phosphoramide compounds and the like. Hydroquinone has been restricted by the nation for its greater environmental hazard. Phosphoramide urease inhibitors are the most used urease inhibitors at present.
The n-butyl thiophosphoric triamide (NBPT) is a phosphoramide urease inhibitor with a wider application range at present, and has a remarkable effect of inhibiting urea decomposition. However, NBPT is sensitive to water and temperature, cannot be added directly to the urea production process, and is unstable when used directly in combination with urea-based fertilizers, and thus is generally prepared as a liquid formulation containing a stabilizer, coated on the surface of solid urea-containing fertilizer particles or added to urea-containing liquid fertilizers, but the liquid solvent used is costly and poses certain difficulties for scale-up.
In addition, chinese patent document CN109810126A discloses a urease inhibitor, a binuclear slow release urea fertilizer containing the same and a preparation method thereof, wherein the structural formula of the urease inhibitor is as follows:
however, the urease inhibitor is only disclosed to be applied to normal temperature spraying, and the stability of the urease inhibitor in use under high temperature conditions is difficult to predict, so that the application is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a stable urease inhibitor and a preparation method and application thereof. The urease inhibitor can be directly mixed with a urea-based fertilizer, shows better stability and urease inhibiting effect, greatly reduces the use cost, is beneficial to large-scale popularization, and has important significance for improving the utilization rate of a nitrogen fertilizer and developing green agriculture.
The technical scheme of the invention is as follows:
a stable urease inhibitor is used for improving the use efficiency of urea nitrogen in the agricultural field, and the chemical component of the urease inhibitor is benzylamino thiophosphoric triamide (NLT), and the structural formula is as follows:
according to the invention, the preparation method of the stable urease inhibitor comprises the following steps:
(1) Mixing trichloro-sulfur and benzylamine with solvent respectively, adding an acid-binding agent into the mixture of trichloro-sulfur and solvent, and adjusting the temperature to-5-0 ℃;
(2) Slowly dripping a mixture of benzylamine and a solvent into a trichlorothiophosphoryl solvent mixture, and keeping a certain temperature for continuous reaction after dripping;
(3) And then introducing ammonia gas into the reaction liquid for reaction, maintaining the temperature to be not higher than 10 ℃, adding water to separate an organic phase I after the HPLC detection reaction is finished, and removing the solvent to obtain the target product.
According to the invention, the molar ratio of benzylamine, trichloro sulfur phosphorus and acid-binding agent in the step (1) is preferably 0.5-1.5:0.5-1.5:0.5-1.5.
According to the present invention, preferably, the solvent in step (1) is dichloromethane or ethyl acetate.
According to the present invention, preferably, the acid-binding agent in step (1) is potassium carbonate or sodium hydroxide.
According to the invention, the time for dropping the mixed solution of benzylamine and the solvent in the step (2) is preferably 1 to 2 hours.
According to the present invention, it is preferable that the reaction temperature in the step (2) is maintained at-5 to 5 ℃ and the reaction time is 1 to 4 hours.
According to the present invention, it is preferable that the reaction temperature in the step (3) is 0 to 10 ℃.
According to the present invention, preferably, the step (3) further comprises extracting the aqueous phase with an organic solvent to obtain an organic phase ii, combining the organic phase ii with the organic phase i, and removing the solvent.
According to the present invention, preferably, the solvent in step (3) can be recovered by distillation and recycled.
According to the present invention, there is also provided a method of using the above stable urease inhibitor, the method comprises the following steps:
for granular fertilizers: directly adding the stable urease inhibitor into a production line of the urea-based fertilizer before granulation according to the required proportion for granulation, or preparing a solution and uniformly spraying the solution on the surfaces of solid urea-based fertilizer particles;
for powdered or liquid fertilizers: the stable urease inhibitor is directly added according to the required proportion and then is uniformly mixed with the urea-based fertilizer.
According to the invention, the addition amount of the stable urease inhibitor is preferably 0.01-5% of the mass of the fertilizer; further preferably, the addition amount of the stable urease inhibitor is 0.01-1% of the mass of the fertilizer.
According to the present invention, it is preferable that the urea-based fertilizer includes urea, and a compound fertilizer, a liquid fertilizer, a foliar fertilizer, a microbial fertilizer, or a soil conditioner containing urea.
According to the present invention, there is also provided a synergistic urea-based fertilizer comprising at least the above-described stable urease inhibitor and urea.
According to the present invention, the synergistic urea-based fertilizer may be present in the form of regular or irregular granules, in the form of powder, in the form of a solution, suspension, emulsion or the like.
According to the present invention there is also provided the use of benzylamino thiophosphoric triamide as a stable urease inhibitor.
The invention has the beneficial effects that:
1. the stable urease inhibitor has stable property, and the loss rate of the stable urease inhibitor NLT in urea for 2 months is less than 18 percent under the condition of not melting at high temperature; after high-temperature melting, the stable urease inhibitor shows good high-temperature decomposition resistance, and after melting granulation, the loss rate of the stable urease inhibitor in urea is less than 52% after 0.2 months. Can be directly mixed with urea-containing fertilizer for use, and can also be used as an additive to participate in the granulation process, and the use is convenient.
2. The preparation method of the stable urease inhibitor is simple, does not need a special reactor or an organic matter as an acid-binding agent, has low reaction temperature requirement and low energy consumption, and is easy to control the reaction process.
3. The stable urease inhibitor disclosed by the invention does not need an organic solvent, so that the use cost is reduced, and the cost of each raw material used in the preparation process is lower, so that the stable urease inhibitor is wider in production cost and lower in NBPT, and is more favorable for large-scale popularization.
Drawings
FIG. 1 is a graph showing the loss rate of different urease inhibitors according to the present invention in test example 1 as a function of time.
Detailed Description
The present invention will be further described with reference to the following detailed description of embodiments thereof, but not limited thereto, in conjunction with the accompanying drawings.
Example 1
In a 500mL three-necked flask, 200mL of methylene chloride was added, stirring was turned on (250-300 rpm), 34.30g of thiophosphoryl chloride was added, cooling was carried out to-5 ℃ and 13.82g of potassium carbonate was added in one portion and stirred for 10min. A solution of benzylamine in dichloromethane (22.47 g benzylamine, 50mL dichloromethane) was added dropwise over a period of about 1.5h, at a reaction temperature of 0-5 deg.C. After the dropwise addition, the reaction is continued for 2h at the temperature of 0-5 ℃.
Directly introducing ammonia gas into the reaction system, and maintaining the temperature of the reaction system at 0-10 ℃ until no ammonia gas is absorbed. Subsequently, 200g of deionized water was added to the reaction system, and stirred overnight. After the liquid separation, the organic phase was taken, the aqueous phase was extracted with dichloromethane (100 mL. Times.2), the organic phases were combined, and dichloromethane was recovered by atmospheric distillation to obtain 35.44g of a yellowish solid. Yield: 88.16% and HPLC purity 94.18%.
Example 2
In a 500mL three-necked flask, 200mL of ethyl acetate was added, stirring was started (250-300 rpm), 34.30g of thiophosphoryl chloride was added, the mixture was cooled to 0 ℃ and 13.82g of potassium carbonate was added in one portion, and the mixture was stirred for 10 minutes. A solution of benzylamine in ethyl acetate (22.47 g benzylamine, 50mL ethyl acetate) was added dropwise over a period of about 1.5h, at a reaction temperature of 0-5 deg.C. After the dropwise addition, the reaction is continued for 2h at the temperature of 0-5 ℃.
Directly introducing ammonia gas into the reaction system, and maintaining the temperature of the reaction system at 0-10 ℃ until no ammonia gas is absorbed. Subsequently, 200g of deionized water was added to the reaction system, and the mixture was stirred overnight. After the liquid separation, the organic phase was taken, the aqueous phase was extracted with ethyl acetate (100 mL × 2), the organic phases were combined, and ethyl acetate was recovered by atmospheric distillation to obtain 35.00g of a yellowish solid, yield 87.06%, and HPLC purity 93.83%.
Example 3
In a 500mL three-necked flask, 200mL of methylene chloride was added, stirring was started (250-300 rpm), 34.30g of thiophosphoryl chloride was added, the mixture was cooled to 0 ℃ and 8.00g of sodium hydroxide was added in one portion and stirred for 10min. A dichloromethane solution of benzylamine (22.47 g benzylamine, 50mL dichloromethane) was added dropwise over a period of about 1.5h, at a reaction temperature of 0-5 deg.C. After the dropwise addition, the reaction is continued for 2h at the temperature of 0-5 ℃.
Directly introducing ammonia gas into the reaction system, and maintaining the temperature of the reaction system at 0-10 ℃ until no ammonia gas is absorbed. Subsequently, 200g of deionized water was added to the reaction system, and stirred overnight. After the liquid separation, the organic phase was taken, the aqueous phase was extracted with dichloromethane (100 mL. Times.2), the organic phases were combined, dichloromethane was recovered by atmospheric distillation, and the mixture was cooled and allowed to stand to give 36.49g of a yellowish viscous substance, yield 90.77%, and HPLC purity 83.91%.
Test example 1 stability test
Test time: 16/8/2017-13/10/2017
The test method comprises the following steps: samples containing 0.06% urease inhibitor were prepared by different methods and NLT used the product of example 1. Standing and tracking and detecting the content of the urease inhibitor, wherein the preparation method of each sample is shown in the following table 1:
TABLE 1
| Raw materials | Preparation method |
| Urea powder and NBPT liquid | Spraying of paint |
| Urea powder + NLT solid | Blending |
| Urea powder + NBPT liquid (melt) | Melt granulation after spray coating |
| Urea powder + NLT solid (melt) | Melt granulation after blending |
Of the starting materials, NBPT liquid contains stabilizer, formulation 2g97% NBPT +2g polyethyleneimine +3.0g benzyl alcohol +2.3g DMF; NLT is a solid with a purity of 94%.
The results of the detection are shown in FIG. 1.
According to the data in figure 1, the stable urease inhibitor NLT has higher stability in urea without high-temperature melting, and the loss rate is only 17.27 percent after 2 months, while the loss rate of NBPT is as high as 73.5 percent. After high-temperature melting, the stable urease inhibitor shows good high-temperature decomposition resistance, the loss rate after melting and granulation is 0, and the loss rate of NLT in urea is 51.33% after about 2 months. By contrast, the loss rate of NBPT after high-temperature melt granulation reached 34.47%, and after approximately two months, the loss rate reached 82.17%. Thus, the urease inhibitor NLT of the invention shows better stability whether directly blended or melted at high temperature.
Test example 2 test for Effect of suppressing Urea decomposition
Test time: 1/8/2017-30/8/2017
Test materials: gas detecting tube (0-4.0 mg/m) 2 ) Neat and shang environmental testing, ltd, tin-free; NLT, example 1 product.
The test method comprises the following steps: weighing 50g of soil, placing the soil in a 100mL plastic bottle with a cover, wherein the cover is provided with a hole, a gas detection tube capable of being communicated in a closed manner is arranged, 4 treatments of blank (soil 50 g), CK (soil 50g and urea 0.008 g), NLT1 (soil 50g and urea 0.008g +0.04wt% NLT) and NLT2 (soil 50g and urea 0.008g +0.08wt% NLT) are respectively arranged, and the gas detection tube can measure the gas content passing through the tube, so that the ammonia volatilization amount in the soil is judged by continuously observing the data indicated by the upper end of a color change area of the gas detection tube.
The test results are shown in table 2.
TABLE 2
| |
1 day | 2 |
5 days | 8 days | 21 days | 28 |
| Blank space | ||||||
| 0 | 0 | 0 | 0 | 0 | 0 | |
| CK | 0.8 | 1.9 | 4.0 | -- | -- | -- |
| |
0 | 0 | 0.5 | 1.0 | 4.0 | -- |
| |
0 | 0 | 0 | 0.6 | 2.6 | 3.8 |
The results of the above test in Table 2 show that the amount of ammonia released from urea in the absence of urease inhibitor for 5 days exceeds the maximum value of the gas detector tube, whereas the NLT1 treatment at a concentration of 0.04% does not release any ammonia at all when the NLT2 treatment is at a concentration of 0.5 and 0.08%. Over time, the 0.04% content of NLT1 treatment reached a measurable maximum in the gas detection tube after 21 days, while the 0.08% content of NLT2 treatment did not reach a measurable maximum after 28 days. The stable urease inhibitor can effectively inhibit urea decomposition, and has a more obvious inhibiting effect along with the increase of the dosage within a certain range.
The above description is provided for the purpose of further elaboration of the technical solutions provided in connection with the preferred embodiments of the present invention, and it should not be understood that the embodiments of the present invention are limited to the above description, and it should be understood that various simple deductions or substitutions can be made by those skilled in the art without departing from the spirit of the present invention, and all such alternatives are included in the scope of the present invention.
Claims (10)
1. A stable urease inhibitor is characterized in that the chemical component of the urease inhibitor is benzylamino thiophosphoryl triamide, and the structural formula is as follows:
2. a method of preparing the stable urease inhibitor of claim 1 comprising the steps of:
(1) Mixing trichloro-sulfur and benzylamine with solvent respectively, adding an acid-binding agent into the mixture of trichloro-sulfur and solvent, and adjusting the temperature to-5-0 ℃;
(2) Slowly dripping a mixture of benzylamine and a solvent into a trichlorothiophosphoryl solvent mixture, and keeping a certain temperature for continuous reaction after dripping;
(3) And then introducing ammonia gas into the reaction liquid for reaction, maintaining the temperature to be not higher than 10 ℃, adding water to separate an organic phase I after the HPLC detection reaction is finished, and removing the solvent to obtain the target product.
3. The method for preparing a stable urease inhibitor according to claim 2, wherein the molar ratio of benzylamine, trichlorphos and the acid-binding agent in step (1) is 0.5-1.5:0.5-1.5:0.5-1.5;
preferably, the solvent in the step (1) is dichloromethane or ethyl acetate;
preferably, the acid-applying agent in step (1) is potassium carbonate or sodium hydroxide.
4. The method for preparing a stable urease inhibitor according to claim 2, wherein the time for dropping the mixed solution of benzylamine and the solvent in the step (2) is 1-2h;
preferably, the reaction temperature in the step (2) is maintained at-5 to 5 ℃, and the reaction time is 1 to 4 hours.
5. The method of preparing a stable urease inhibitor according to claim 2 wherein the step (3) reaction temperature is 0-10 ℃;
preferably, the step (3) further comprises extracting the aqueous phase with an organic solvent to obtain an organic phase II, combining the organic phase II with the organic phase I, and then removing the solvent;
preferably, the solvent in the step (3) is recovered by distillation and recycled.
6. A method of using the stable urease inhibitor of claim 1 comprising the steps of:
for granular fertilizers: directly adding the stable urease inhibitor into a production line of the urea-based fertilizer before granulation according to the required proportion for granulation, or preparing a solution and uniformly spraying the solution on the surfaces of solid urea-based fertilizer particles;
for powdered or liquid fertilizers: the stable urease inhibitor is directly added according to the required proportion and then is uniformly mixed with the urea-based fertilizer.
7. The method of using the stable urease inhibitor according to claim 6 wherein the amount of stable urease inhibitor added is 0.01-5% of the mass of the fertilizer.
8. The method of using a stable urease inhibitor according to claim 6 wherein the urea-based fertilizer includes urea, and a compound fertilizer, liquid fertilizer, foliar fertilizer, microbial fertilizer or soil conditioner containing urea.
9. A synergistic urea-based fertilizer, characterized in that it comprises at least the stable urease inhibitor of claim 1 and urea;
preferably, the synergistic urea-based fertilizer exists in the form of regular or irregular particles, or powder, or in the form of solution, suspension or emulsion.
10. An application of benzylamino thiophosphoric triamide as the stable urease inhibitor.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4530714A (en) * | 1983-03-16 | 1985-07-23 | Allied Corporation | N-aliphatic and N,N-aliphatic phosphoric triamide urease inhibitors and urease inhibited urea based fertilizer compositions |
| CN1872800A (en) * | 2006-06-09 | 2006-12-06 | 大连轻工业学院 | Long acting urea, method of preparation, and synthesizing N alkyl thiophosphoryl triamide of urease inhibitor |
| CN101412733A (en) * | 2008-11-20 | 2009-04-22 | 大连理工大学 | Preparation of N-alkyl thiophosphoryl triamide by one-pot method |
| CN105399767A (en) * | 2015-11-20 | 2016-03-16 | 江西吉翔医药化工有限公司 | Production method of N-alkyl substituted phosphoric triamide |
| CN107207375A (en) * | 2014-09-30 | 2017-09-26 | 罗地亚经营管理公司 | For D2EHDTPA triamide or the solvent and correlation technique of dicyandiamide solution |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4530714A (en) * | 1983-03-16 | 1985-07-23 | Allied Corporation | N-aliphatic and N,N-aliphatic phosphoric triamide urease inhibitors and urease inhibited urea based fertilizer compositions |
| CN1872800A (en) * | 2006-06-09 | 2006-12-06 | 大连轻工业学院 | Long acting urea, method of preparation, and synthesizing N alkyl thiophosphoryl triamide of urease inhibitor |
| CN101412733A (en) * | 2008-11-20 | 2009-04-22 | 大连理工大学 | Preparation of N-alkyl thiophosphoryl triamide by one-pot method |
| CN107207375A (en) * | 2014-09-30 | 2017-09-26 | 罗地亚经营管理公司 | For D2EHDTPA triamide or the solvent and correlation technique of dicyandiamide solution |
| CN105399767A (en) * | 2015-11-20 | 2016-03-16 | 江西吉翔医药化工有限公司 | Production method of N-alkyl substituted phosphoric triamide |
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