CN104628493B - Nitrogen fertilizer potentiating agent and the nitrogenous fertilizer containing the nitrogen fertilizer potentiating agent - Google Patents
Nitrogen fertilizer potentiating agent and the nitrogenous fertilizer containing the nitrogen fertilizer potentiating agent Download PDFInfo
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- CN104628493B CN104628493B CN201310565474.6A CN201310565474A CN104628493B CN 104628493 B CN104628493 B CN 104628493B CN 201310565474 A CN201310565474 A CN 201310565474A CN 104628493 B CN104628493 B CN 104628493B
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- Prior art keywords
- potentiating agent
- polymer
- salt
- nitrogen fertilizer
- fertilizer
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Classifications
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- 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
- C05G5/20—Liquid fertilisers
- C05G5/23—Solutions
-
- 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
Abstract
The present invention relates to a kind of nitrogen fertilizer potentiating agent, the polymer or polymer salt of its nitrogenous fertilizer inhibitor for including 0.1%~50% mass percent and 50%~99.9% mass percent, the nitrogenous fertilizer inhibitor are combined with the polymer or polymer salt by Covalent bonding together or by ionic bond.The nitrogen fertilizer potentiating agent is by the way that nitrogenous fertilizer inhibitor is combined with polymer or polymer salt, the volatilization after directly nitrogenous fertilizer inhibitor is added in nitrogenous fertilizer and hydrolysis problem can effectively be prevented, significantly reduce degradation efficiency of the nitrogenous fertilizer inhibitor in soil after nitrogen application, extend its half-life period in soil, its efficiency for suppressing nitrogenous fertilizer nitrification is significantly played, so as to improve the environmental resistance of nitrogenous fertilizer.Moreover, it relates to a kind of nitrogenous fertilizer containing the nitrogen fertilizer potentiating agent.
Description
Technical field
The present invention relates to chemurgy field, the nitrogen more particularly, to a kind of nitrogen fertilizer potentiating agent and containing the nitrogen fertilizer potentiating agent
Fertilizer.
Background technology
It is typically to regard ammoniate as fertilizer to be applied fertilizer to plant.However, ammoniate in soil when shorter
In will be by microorganism conversion into the nitrification of nitrate, namely soil, the nitrate being consequently formed is by quickly from soil
Washed away in earth.Because the part being flushed away is no longer available for plant nutrient, therefore quick nitrification is the maximum of fertilizer loss
Reason.To better profit from nitrogen contained in fertilizer, research finds to add nitrification inhibitor can effectively suppress in fertilizer
Nitrification.But the nitrification inhibitor that tradition is used has higher volatility.By by nitrification inhibitor and other materials
With reference to can effectively suppress the volatility of nitrification inhibitor, but after being applied together with fertilizer, hydrolytic stability is not high in soil,
It is limited further to apply.
The content of the invention
Based on this, it is necessary to provide a kind of not volatile and not facile hydrolysis nitrogen fertilizer potentiating agent and containing the nitrogen fertilizer potentiating agent
Nitrogenous fertilizer.
A kind of nitrogen fertilizer potentiating agent, includes the nitrogenous fertilizer inhibitor and 50%~99.9% mass of 0.1%~50% mass percent
The polymer or polymer salt of percentage, the nitrogenous fertilizer inhibitor and the polymer or polymer salt by Covalent bonding together or
Person is combined by ionic bond.
In one of the embodiments, the nitrogenous fertilizer inhibitor is quinhydrones, normal-butyl thiophosphoryl triamine, diphenylphosphoryl two
At least one of the chloro- 6- trichloromethyls of amine, 2--pyridine, dicyandiamide and pyrazole compound.
In one of the embodiments, the polymer is poly- propylhomoserin or poly- propylhomoserin salt.
In one of the embodiments, the poly- propylhomoserin is that glutamic acid polymerize the poly- propylhomoserin to be formed with aspartic acid；It is described
Poly- propylhomoserin salt is that glutamic acid polymerize the poly- propylhomoserin salt to be formed with aspartic acid.
In one of the embodiments, the polymer is polyglutamic acid, poly-aspartate, humic acid, fulvic acid and sea
At least one of alginic acid.
In one of the embodiments, the polymer salt is polyglutamate, polyaspartic acid salts, humate, Huang
At least one of rotten hydrochlorate and alginate.
In one of the embodiments, the polymer salt is alkali metal salt, alkali salt or the ammonium salt of polymer.
In one of the embodiments, the formulation of the nitrogen fertilizer potentiating agent is the aqueous solution or solid powder.
A kind of nitrogenous fertilizer of the nitrogen fertilizer potentiating agent containing described in any of the above-described embodiment.
In one of the embodiments, mass percent of the nitrogen fertilizer potentiating agent in the nitrogenous fertilizer be 0.001~
30%。
Above-mentioned nitrogen fertilizer potentiating agent can be prevented effectively directly by the way that nitrogenous fertilizer inhibitor is combined with polymer or polymer salt
Volatilization and hydrolysis problem after nitrogenous fertilizer inhibitor is added in nitrogenous fertilizer, significantly reduce after nitrogen application nitrogenous fertilizer inhibitor in soil
In degradation efficiency, extend its half-life period in soil, significantly play its suppress nitrogenous fertilizer nitrification efficiency, so as to improve
The environmental resistance of nitrogenous fertilizer.
Brief description of the drawings
Fig. 1 is nitrogen fertilizer potentiating agent nuclear-magnetism figure prepared by embodiment 9；
Fig. 2 is nitrogen fertilizer potentiating agent mass spectrogram prepared by embodiment 9.
Embodiment
Below mainly in combination with specific embodiment to nitrogen fertilizer potentiating agent and the nitrogenous fertilizer containing the nitrogen fertilizer potentiating agent make further it is detailed
Thin explanation.
The nitrogen fertilizer potentiating agent of one embodiment, including the nitrogenous fertilizer inhibitor of 0.1%~50% mass percent and 50%~
The polymer or polymer salt of 99.9% mass percent.Nitrogenous fertilizer inhibitor passes through Covalent bonding together with polymer or polymer salt
Or combined by ionic bond.
Nitrogenous fertilizer inhibitor can be added in the nitrogen fertilizer potentiating agent preparation process in polymer or polymer monomer with gathering
Compound or the polymer direct combination of polymer monomer formation.Further, compound obtained compound can also be added to alkali
In the aqueous slkali or ammoniacal liquor of metal or alkaline-earth metal, the compound polymer salt of nitrogenous fertilizer inhibitor is obtained.
Wherein, in the present embodiment, nitrogenous fertilizer inhibitor can be quinhydrones, normal-butyl thiophosphoryl triamine, diphenylphosphoryl
The chloro- 6- trichloromethyls-pyridine of diamines, 2-（CP）, dicyandiamide（DCD）At least one of and pyrazole compound.
Polymer can be poly- propylhomoserin or poly- propylhomoserin salt, such as poly-aspartate, polyaspartic acid salts, polyglutamic acid, poly- paddy
Propylhomoserin salt or aspartic acid polymerize the poly- propylhomoserin or poly- propylhomoserin salt to be formed with glutamic acid.In addition, polymer can also for humic acid,
At least one of fulvic acid and alginic acid etc., accordingly, polymer salt can be in humic acid, fulvic acid and alginic acids
The salt of at least one polymer.Further, in the present embodiment, polymer salt is alkali metal salt, the alkaline-earth metal of polymer
Salt or ammonium salt.
The formulation of the nitrogen fertilizer potentiating agent of present embodiment is the aqueous solution or solid powder.After nitrogen fertilizer potentiating agent can be hydrolyzed
It is added in nitrogenous fertilizer or is directly appended in nitrogenous fertilizer.It is added to mass percent of the nitrogen fertilizer potentiating agent in nitrogenous fertilizer in nitrogenous fertilizer
For 0.001~30%.
The nitrogen fertilizer potentiating agent directly will can be prevented effectively by the way that nitrogenous fertilizer inhibitor is combined with polymer or polymer salt
Nitrogenous fertilizer inhibitor be added in nitrogenous fertilizer after volatilization and hydrolysis problem, significantly reduce after nitrogen application nitrogenous fertilizer inhibitor in soil
Degradation efficiency, extend its half-life period in soil, significantly play its suppress nitrogenous fertilizer nitrification efficiency, so as to improve nitrogen
The environmental resistance of fertilizer.
It is specific embodiment part below：
Embodiment 1：
In a round-bottomed flask equipped with magnetic stirring apparatus and reflux condensing tube, 42.1g sodium alginates are added
（0.1mol）, the chloro- 6- trichloromethyl pyridines of 2.3g2-（CP, 0.01mol）With 20mL water.Reactant mixture is slowly heated to 50
DEG C, until all undissolved part forms uniform solution.Then cool down, obtain the sea of N-serve modification
Alginates, the alginate that the N-serve is modified can be added in nitrogenous fertilizer directly as nitrification inhibitor
Use.
Embodiment 2：
In a round-bottomed flask equipped with magnetic stirring apparatus and reflux condensing tube, lower addition 100g fulvic acids are stirred vigorously
（About 0.1mol）, 0.97g3,5- dimethyl pyrazoles（0.01mol）, 200mL anhydrous tetrahydro furans and 20.6g dicyclohexyls carbon two
Imines（DCC, 0.1mol）, 2h is reacted at 10 DEG C, is then filtered, unreacted DCC is removed, then filtrate is evaporated and changed
The solid nitrogen fertilizer potentiating agent of property.
The above-mentioned solid nitrogen fertilizer potentiating agents of 10g are dissolved in 50mL water, the mixture is heated to 80 DEG C and in this temperature
The sodium hydroxide that lower addition mass concentration is 40%, until pH value is between 7-8, the modification nitrogen fertilizer potentiating agent for forming clarification is water-soluble
Liquid.The modification nitrogen fertilizer potentiating agent aqueous solution, which can be added in liquid nitrogen fertilizer or be applied directly in soil, plays effect.
Embodiment 3：
In a round-bottomed flask equipped with magnetic stirring apparatus and reflux condensing tube, it is stirred vigorously lower addition 200g corruption and plants
Acid, 9.7g3,5- dimethyl pyrazoles（0.1mol）, 200mL anhydrous tetrahydro furans and 20.6g dicyclohexylcarbodiimides（DCC,
0.1mol）, 2h is reacted at 10 DEG C, is then filtered, unreacted DCC is removed, then filtrate is evaporated and obtains modified solid
Nitrogen fertilizer potentiating agent.
The above-mentioned solid nitrogen fertilizer potentiating agents of 10g are dissolved in 50mL water, the mixture is heated to 80 DEG C and in this temperature
The sodium hydroxide that lower addition mass concentration is 40%, until pH value is between 7-8, the modification nitrogen fertilizer potentiating agent for forming clarification is water-soluble
Liquid.The modification nitrogen fertilizer potentiating agent aqueous solution, which can be added in liquid nitrogen fertilizer or be applied directly in soil, plays effect.
Embodiment 4：
In a round-bottomed flask equipped with magnetic stirring apparatus and reflux condensing tube, it is stirred vigorously lower addition 200g corruption and plants
Acid, 9.7g3,5- dimethyl pyrazoles（0.1mol）And 1000g water, 1h is stirred at 40 DEG C, quality is added at this temperature dense
The sodium hydroxide for 40% is spent, until pH value is between 7-8, the modification nitrogen fertilizer potentiating agent aqueous solution of clarification is formed.The modification nitrogenous fertilizer
The synergist aqueous solution, which can be added in liquid nitrogen fertilizer or be applied directly in soil, plays effect.
Embodiment 5
In a 1L glass reactor equipped with agitator and condenser pipe, lower mixing 73.5g polyglutamic acids are stirred vigorously
（0.5mol）, 48.5g poly-aspartates（0.5mol）And 131g thionyl chloride（1.1mol）, 5h is heated to reflux, is then distilled
Unnecessary thionyl chloride is removed, above-mentioned product is added in 100mL anhydrous tetrahydro furan, is progressively added dropwise at 20 DEG C and contains pyrrole
The tetrahydrofuran solution 40mL of azoles (9.6g, 0.1mol), reacts 4h, then boils off solvent, obtain polyglutamic acid and poly- asparagus fern ammonia
The modified pyrazoles nitrogen fertilizer potentiating agent of acid.
The pyrazoles nitrogen fertilizer potentiating agent that the above-mentioned polyglutamic acids of 10g and poly-aspartate are modified is dissolved in 50mL water, will be described
The sodium hydroxide that mixture is heated to 80 DEG C and addition mass concentration is 40% at this temperature, until pH value is between 8-9, shape
Into the modification nitrogen fertilizer potentiating agent aqueous solution of clarification.The modification nitrogen fertilizer potentiating agent aqueous solution can be added in liquid nitrogen fertilizer or direct
It is applied in soil and plays effect.
Embodiment 6
In a 1L glass reactor equipped with agitator and condenser pipe, lower mixing 147g polyglutamic acids are stirred vigorously
（1mol）, 100g fulvic acids（0.1mol）And 131g thionyl chloride（1.1mol）, 5h is heated to reflux, then distillation is gone unnecessary
Thionyl chloride, above-mentioned product is added in 100mL anhydrous tetrahydro furan, at 20 DEG C progressively be added dropwise containing (9.6g,
Tetrahydrofuran solution 40mL 0.1mol), reacts 4h, then boils off solvent, obtains the pyrazoles that polyglutamic acid and fulvic acid are modified
Nitrogen fertilizer potentiating agent.
The pyrazoles nitrogen fertilizer potentiating agent that the above-mentioned polyglutamic acids of 10g and fulvic acid are modified is dissolved in 50mL water, by the mixing
The sodium hydroxide that thing is heated to 80 DEG C and addition mass concentration is 40% at this temperature, until pH value is between 8-9, is formed clear
The clear modification nitrogen fertilizer potentiating agent aqueous solution.The modification nitrogen fertilizer potentiating agent aqueous solution can be added in liquid nitrogen fertilizer or directly apply
Effect is played into soil.
Embodiment 7
In a 1L glass reactor equipped with agitator and condenser pipe, lower mixing 73.5g Pidolidones are stirred vigorously
（0.5mol）, 48.5g aspartic acids（0.5mol）, 9.6g3,4- dimethyl pyrazoles（0.1mol）With 150mL water, and temperature is heated to
Spend for 140 DEG C, water is removed to distill.Remove after the water in solution, carry out condensation reaction at a temperature of 240 DEG C under high pressure.240 DEG C
At a temperature of reaction 10h after, terminate polycondensation reaction.Reactor is cooled down, the modified copolymerization propylhomoserin of khaki powder shape is obtained,
It can be used without further purification and directly.
The above-mentioned modified copolymerization propylhomoserins of 10g are dissolved in 100mL water, the mixture is heated to 80 DEG C and warm herein
The sodium hydroxide that the lower addition mass concentration of degree is 40%, until pH value is between 7-8, forms the aqueous solution of clarification, is obtained after being evaporated
The nitrogen fertilizer potentiating agent solid powder that copolymerization propylhomoserin is modified.The nitrogen fertilizer potentiating agent solid powder that the copolymerization propylhomoserin is modified can be added to liquid
In body nitrogenous fertilizer or it is applied directly in soil and plays effect.
Embodiment 8
In a 1L glass reactor equipped with agitator and condenser pipe, lower mixing 73.5g Pidolidones are stirred vigorously
（0.5mol）, 50g arbitrary amino acids（Such as alanine, leucine）, 9.6g3,4- dimethyl pyrazoles（0.1mol）And 150mL
Water, and temperature is heated to for 140 DEG C, remove water to distill.Remove after the water in solution, contracted under high pressure at a temperature of 240 DEG C
Close reaction.Reacted at a temperature of 240 DEG C after 10h, terminate polycondensation reaction.Reactor is cooled down, the warp of khaki powder shape is obtained
Modified copolymerization propylhomoserin, it can be used without further purification and directly.
The above-mentioned modified copolymerization propylhomoserins of 10g are dissolved in 100mL water, the mixture is heated to 80 DEG C and warm herein
The sodium hydroxide that the lower addition mass concentration of degree is 40%, until pH value is between 7-8, forms the aqueous solution of clarification, is obtained after being evaporated
The nitrogen fertilizer potentiating agent solid powder that copolymerization propylhomoserin is modified.The nitrogen fertilizer potentiating agent solid powder that the copolymerization propylhomoserin is modified can be added to liquid
In body nitrogenous fertilizer or it is applied directly in soil and plays effect.
Embodiment 9
In a 1L glass reactor equipped with agitator and condenser pipe, lower mixing 48.5g aspartic acids are stirred vigorously
（0.5mol）, 50g arbitrary amino acids（Such as alanine, leucine）, 19.2g3,4- dimethyl pyrazoles（0.1mol）And 150mL
Water, and temperature is heated to for 140 DEG C, remove water to distill.Remove after the water in solution, contracted under high pressure at a temperature of 240 DEG C
Close reaction.Reacted at a temperature of 240 DEG C after 10h, terminate polycondensation reaction.Reactor is cooled down, the warp of khaki powder shape is obtained
Modified copolymerization propylhomoserin, it can be used without further purification and directly.
The above-mentioned modified copolymerization propylhomoserins of 10g are dissolved in 100mL water, the mixture is heated to 80 DEG C and warm herein
The sodium hydroxide that the lower addition mass concentration of degree is 40%, until pH value is between 7-8.The aqueous solution of clarification is formed, is obtained after being evaporated
The nitrogen fertilizer potentiating agent solid powder that copolymerization propylhomoserin is modified.The nuclear magnetic resonance characterize data for forming the solid powder of nitrogen fertilizer potentiating agent is shown in
Accompanying drawing 1, mass spectral characteristi data are shown in accompanying drawing 2.The nitrogen fertilizer potentiating agent solid powder that the copolymerization propylhomoserin is modified can be added to liquid nitrogen fertilizer
In or be applied directly in soil and play effect.
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (9)
1. a kind of nitrogen fertilizer potentiating agent, it is characterised in that including the nitrogenous fertilizer inhibitor of 0.1%~50% mass percent and 50%
The polymer or polymer salt of~99.9% mass percent, the nitrogenous fertilizer inhibitor pass through with the polymer or polymer salt
Covalent bonding together；The polymer is poly- propylhomoserin；The polymer salt is poly- propylhomoserin salt；The nitrogenous fertilizer inhibitor polymerize with described
Thing or polymer salt are to add the monomer of at least one corresponding amino acid and nitrogenous fertilizer inhibitor to solvent by Covalent bonding together
Middle progress polycondensation reaction is obtained.
2. nitrogen fertilizer potentiating agent as claimed in claim 1, it is characterised in that the nitrogenous fertilizer inhibitor is quinhydrones, normal-butyl is thio
At least one of the chloro- 6- trichloromethyls of phosphoric triamide, diphenylphosphoryl diamines, 2--pyridine, dicyandiamide and pyrazole compound.
3. nitrogen fertilizer potentiating agent as claimed in claim 1, it is characterised in that the poly- propylhomoserin is that glutamic acid polymerize with aspartic acid
The poly- propylhomoserin formed；The poly- propylhomoserin salt is that glutamic acid polymerize the poly- propylhomoserin salt to be formed with aspartic acid.
4. nitrogen fertilizer potentiating agent as claimed in claim 1, it is characterised in that the polymer is polyglutamic acid and poly-aspartate
At least one of.
5. nitrogen fertilizer potentiating agent as claimed in claim 1, it is characterised in that the polymer salt is polyglutamate and poly- asparagus fern
At least one of propylhomoserin salt.
6. nitrogen fertilizer potentiating agent as claimed in claim 1, it is characterised in that the polymer salt for polymer alkali metal salt,
Alkali salt or ammonium salt.
7. nitrogen fertilizer potentiating agent as claimed in claim 1, it is characterised in that the formulation of the nitrogen fertilizer potentiating agent is the aqueous solution or solid
Body powder.
8. a kind of nitrogenous fertilizer of the nitrogen fertilizer potentiating agent containing as any one of claim 1-7.
9. nitrogenous fertilizer as claimed in claim 8, it is characterised in that mass percent of the nitrogen fertilizer potentiating agent in the nitrogenous fertilizer
For 0.001~30%.
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| CN106348915B (en) * | 2016-10-24 | 2020-04-28 | 重庆建峰工业集团有限公司 | Special fertilizer for hot pickled mustard tuber and preparation method thereof |
| CN106478299A (en) * | 2016-10-26 | 2017-03-08 | 秦皇岛五弦维爱科技开发有限公司 | A kind of carbamide enhanced fertilizer and preparation method thereof |
| CN107540442A (en) * | 2017-08-18 | 2018-01-05 | 山东远联化工有限公司 | A kind of pH stimulating responsives intelligence peptide synergist and its synthesis technique and the application in medicine fertilizer integration |
| CN109776154A (en) * | 2017-11-13 | 2019-05-21 | 深圳市芭田生态工程股份有限公司 | Fertilizer synergistic composition, its application and fertilizer |
| CN108440111A (en) * | 2018-05-02 | 2018-08-24 | 济南航晨生物科技有限公司 | A kind of environmentally protective curdlan slow-release fertilizer and preparation method thereof |
| CN109912339B (en) * | 2019-02-15 | 2021-10-22 | 金正大诺泰尔化学有限公司 | Stable nitrogen fertilizer synergist and preparation method and application thereof |
| CN112279726A (en) * | 2020-10-29 | 2021-01-29 | 河海大学 | Soil nitrification inhibitor slow-release body containing sodium carboxymethylcellulose and preparation method thereof |
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| CN101434503A (en) * | 2007-11-16 | 2009-05-20 | 中国科学院沈阳应用生态研究所 | Synergistic slow release urea fertilizer and preparation thereof |
| CN102584385B (en) * | 2012-01-11 | 2015-10-28 | 中航化肥有限公司 | A kind of preparation method of anti-aging long acting multifunction phosphate fertilizer |
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