CN103044137B - Nitrogen fertilizer stabilizer composition and preparation method thereof - Google Patents
Nitrogen fertilizer stabilizer composition and preparation method thereof Download PDFInfo
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- CN103044137B CN103044137B CN201210574164.6A CN201210574164A CN103044137B CN 103044137 B CN103044137 B CN 103044137B CN 201210574164 A CN201210574164 A CN 201210574164A CN 103044137 B CN103044137 B CN 103044137B
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Abstract
The invention discloses a nitrogen fertilizer stabilizer composition. The nitrogen fertilizer stabilizer composition comprises the following components in part by weight: 1-60 parts of nitrapyrin, 1-15 parts of wall material, 2-10 parts of emulsifier, 0.05-0.3 parts of viscosity regulator, 2-10 parts of dispersing agent and 0.1-100 parts of water. The invention further provides a preparation method of the nitrogen fertilizer stabilizer composition. The preparation method of the nitrogen fertilizer stabilizer composition comprises the following steps of: heating and melting active components, adding the macromolecular wall material, and stirring uniformly; adding a mother liquid containing the active components and the wall material into an emulsifier-containing water solution under a shearing condition, and emulsifying into an oil-in-water state; and controlling grain size as required, wherein the nitrogen fertilizer stabilizer composition can be in a liquid or solid state; and liquid drops containing the active components react with water molecules to form the macromolecular wall material. Through addition of a nitrapyrin product, the nitrogen fertilizer stabilizer composition can improve the using efficiency of an ordinary nitrogen fertilizer by decreasing nitrogen leaching and denitrification, is good in compatibility with a variety of fertilizers, pesticides, weedicides and bactericides, and can be mixed therewith for application.
Description
Technical field
The present invention relates to the manufacture field of fertilizer synergist aspect, be specifically related to a kind of nitrogenous fertilizer stablizer and preparation method thereof.
Background technology
Fertilizer nitrogen stablizer in the present invention refers to that N-serve (Nitrapyrin) is a kind of nitrogenous fertilizer nitrogen oxidation retarder.Physico-chemical property: molecular formula:
This product is white crystals shape solid, fusing point: 62-63 ℃, and the vapour pressure in the time of 23 ℃ is 370mpt, is insoluble in water, solubleness 40mg/kg water in water in the time of 22 ℃.Be soluble in acetone, methylene dichloride, dimethylbenzene.Toxicity: to rat acute LD50 of passing through mouth: 1072-1231mg/kg.Application: because the selection to vinelandii is active, can be used as nitrogen oxidation retarder and soil nitrogenous fertilizer protective material; When using with urea element and one, nitrogenous fertilizer, can postpone the oxygenizement of ammonium ion in soil.
China's recent two decades comes, and cannot change utilization rate of nitrogen fertilizer low (30%) always, waste serious situation, has produced serious surface water and atmosphere polluting problem.Nitrogenous fertilizer is a kind of very active fertilizer variety, it is after being manured into soil, under the effect of nitrobacteria, from the ammonium nitrogen form of positive charge, transform into very soon the nitre nitrogen form of negative charge, and soil itself is with negative charge, therefore ammonium nitrogen can mutually adsorb with soil and be difficult for running off, and nitric nitrogen repels each other with soil electricity, is just easy to cause leaching to run off under irrigation water and rainwash; Meanwhile, nitric nitrogen, under the effect of denitrifying bacterium, forms oxynitride, is mainly wherein greenhouse gases N
2o, 1 ton of N
2o is equivalent to 300 tons of CO
2greenhouse effect.
In fertilizer, add nitrogen stablizer and have the effect aspect three: 1. reduce the leaching of nitrogenous fertilizer (with NO
3 -form) and denitrification loss, improve the utilization ratio of nitrogenous fertilizer; 2. adjust supply, supply form and the supply time of nitrogenous fertilizer.For example increase nitrogenous fertilizer with NH
4 +form and reduce it with NO
3 -form supply with plant; 3. from the angle of plant pathology, consider, nitrogen oxidation retarder can reduce NO
3 -to planting the murder by poisoning of Seedling Stage, and then the ability of enhancing plant disease and pest resistance.Hence one can see that, and application nitrogen oxidation retarder not only can improve the utilization ratio of nitrogenous fertilizer but also can reduce the pollution of nitrogenous fertilizer to environment.How to filter out more effectively nitrogen oxidation retarder product and become the hot issue that over nearly, 20 year, scientist pays close attention to both at home and abroad.
From Goring in 1962, propose first after the nitrogen absorption stablizer of nitrogen pyridine as nitrogen element absorption; so far the mankind have been found that likens to, pyrimidine, pyridine, thiazole, thiocarbamide and amides etc. are that main nitrogen absorbs stablizer and just has hundreds of kind; but mainly only have at present two kinds of nitrogen to absorb stablizer, can in agriculture production, large-scale promotion apply, they be Dyhard RU 100 (DCD), the chloro-6-(trichloromethyl of 2-) pyridine.But Dyhard RU 100 DCD exists obvious defect, DCD is only just effective when the large 15～30kg/hm2 of amount of application, causes its use cost higher; In addition also have a kind of stablizer as 3,4-dimethyl pyrazole phosphoric acid salt (DMPP) because of its lasting period shorter, be only 4 to 10 weeks the action time in soil, and DMPP expensive be difficult at present promote come.
Nitrapyrin has obvious restraining effect to the nitrobacteria in soil, extended the transformation time of ammonium nitrogen to nitric nitrogen, the nitrated time of nitrogenous fertilizer of 7-14 under conventional situation days is risen to more than 30 days, and the leaching that has suppressed 16% nitrogenous fertilizer runs off, and has also indirectly reduced denitrification and has produced 51% N
2o, thus crop utilization rate of nitrogen fertilizer improved more than 50%, and significantly improve inorganic 28% nitrogen content in farmland, effectively strengthen soil fertility.
The current chloro-6-(trichloromethyl of 2-) the general using method of pyridine (Nitrapyfin) is according to certain ratio, Nitrapyrin to be added and entered in fertilizer, then fertilizer is sowed in soil.So Nitrapyrin also exists following shortcomings: 1.Nitrapyrin under the absorption of soil colloid at present as additive product, can be hydrolyzed to 6-chloropicolinic acid, serve loss to the utilization band of Nitrapyrin; 2.Nitrapyrin is easy to photodissociation, thus it be not suitable for ground top dressing, need to, by deep application of fertilizer, improve user's labour intensity; 3. different crops is different to the sensitivity of nitrogen oxidation retarder, when the amount of application of Nitrapyrin surpasses 1215mg/kg, the growth of seedling such as tomato, oat, Radix Dauci Sativae, onion and lettuce are just poisoned, so effectively control Nitrapyrin release concentration, reduce its side effect to seedling growth stage and become product advantage; 4.Nitrapyrin is added directly into the situation that still has volatilization after Fertilizer application, and the utilization of Nitrapyrin is reduced.5. visible Nitrapyrin liquid preparation forms liquid emulsion after also needing to add organic solvent dissolution, waste petroleum resources and the poisonous and harmful effect of generation solvent to environment and organism.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is for existing nitrapyrin (Nitrapyrin) product weak point in use, provide a kind of can permanently effective raising utilization rate of nitrogen fertilizer, the nitrogenous fertilizer stabiliser composition of applicable various crop, the preparation method of this nitrogenous fertilizer stabiliser composition is provided simultaneously.
Technical scheme of the present invention is, a kind of nitrogenous fertilizer stabiliser composition, and described composition comprises:
According to nitrogenous fertilizer stabiliser composition of the present invention, preferably, described cyst material is a kind of of polystyrene resin, styrene-propene acid resin; Described polystyrene-acrylic resin is made by polyreaction by vinylbenzene and redundant organism thereof.
Further, the granularity of described nitrogenous fertilizer stabiliser composition is controlled 0.1um ~ 20um.
According to nitrogenous fertilizer stabiliser composition of the present invention, preferably, described emulsifying agent is selected a kind of in aliphatic alcohol polyethenoxy series and derivative phosphoric acid ester, castor oil polyoxyethylene ether, oxyethane and propylene oxide segmented copolymer, sorbitan monolaurate, polyoxyethylene sorbitol acid anhydride monopalmitate or more than one.
According to nitrogenous fertilizer stabiliser composition of the present invention, preferably, described dispersion agent is selected a kind of in naphthalenesulfonic acid-formaldehyde condensate, styrene-maleic anhydride copolymer sodium salt, sulfonated lignin, alkyl naphthalene formaldehyde condensate sulfonates, polymerization of carboxylic acid salt or more than one.
According to nitrogenous fertilizer stabiliser composition of the present invention, preferably, described viscosity-controlling agent is selected from a kind of in xanthan gum, Mierocrystalline cellulose and derivative thereof, PVAC polyvinylalcohol, neusilin salt, wilkinite, polyvinylpyrrolidone PVP.
The present invention also provides the preparation method of above-mentioned nitrogenous fertilizer stabiliser composition, and the method comprises:
A, after 65 ℃ ~ 75 ℃ thawings, add appropriate cyst material to stir Nitrapyrin heating;
B, in water, add in advance emulsifier for mixing even, then add the pre-configured solution that contains Nitrapyrin and cyst material, high speed homogenizing forms stable O/w emulsion;
C, reduction rotating speed, under applicable speed conditions, cyst material monomer is polymerization reaction take place under heating state, and temperature of reaction rises in 20 ℃ ~ 80 ℃, keeps for some time to make cyst material solidify encystation;
D, wait becoming capsule material to solidify completely after encystation, add appropriate dispersion agent, viscosity-controlling agent etc., stir and make Nitrapyrin nitrogenous fertilizer stabiliser composition.
According to the present invention, preferably, temperature of reaction is 50-70 ℃ described in step c.
According to the present invention, preferably, set time is between 2 hours～8 hours described in step c.More preferably, time 5-7 hour.
According to the present invention, preferably, the granularity of described nitrogenous fertilizer stabiliser composition is controlled 0.1um ~ 20um.This granularity has possessed the feature of pesticide suspension concentrate, can be watered Direct spraying and use.
Nitrapyrin microcapsule controlled-release agent content of the present invention can change between 1%～60%, according to its different purposes, formulates different content; Simultaneously can be by becoming the quality of capsule material and active substance Nitrapyrin recently to control wall thickness.
The form that the present invention is not only confined to Nitrapyrin composition liquid occurs, form that also can solid particulate occurs.
Nitrapyrin microcapsule controlled-release agent of the present invention is also a kind of formulation of controlled effective constituent release rate processed simultaneously, therefore according to its purposes, determines that the thickness of softgel shell is controlled release rate, to reach required effect.The present invention is mainly slowly broken by high molecular microcapsule spheroid, or effective constituent outwards discharges Nitrapyrin active substance along the porosity on cyst material.Itself inert substance each other between Nitrapyrin and slow-release material (being cyst material), can not react to each other or chemical bond, therefore can reach slow releasing function.
The water adopting in this production technique: be deionized water or distilled water.
The invention has the beneficial effects as follows:
The present invention has adopted the chloro-6-(trichloromethyl of a kind of suitability for industrialized production 2-) preparation method and the operational path of the composition of pyridine (Nitrapyrin).It is cyst wall lapping that the present invention adopts polystyrene resin or Styrene And Chloroalkyl Acrylates resin material, and the method for employing high molecular polymerization is prepared Nitrapyrin control and released agent, is finally deployed into suspension.
1. by adding Nitrapyrin product, common fertilizer can be played reduce nitrogen leaching and denitrification improves nitrogenous fertilizer service efficiency, simultaneously and various fertilizer, and sterilant, weedicide, sterilant has good compatibility, can mix and use;
2. adopt macromolecule polymeric material parcel effective constituent Nitrapyrin, its effective constituent is slowly discharged, extend the action time to fertilizer of nitrogen stablizer, further promote nitrogen use efficiency;
3. by microcapsule controlled-release technology, effectively reduce Nitrapyrin product toxicity, improve product safety in utilization, to seedling stage crop safer;
4. by the cyst material of Nitrapyrin external parcel, can reduce the volatilization of Nitrapyrin, thereby totally reduce the usage quantity of Nitrapyrin;
5. with the form (content: 1%～60%), be conveniently added in fertilizer, thereby fully grasp the handiness on applying fertilizer of different concns Nitrapyrin product;
6. in using the process of capsule material capsulation, and common packing technique has relatively big difference part to be: no longer with an organic solvent, as toluene, dimethylbenzene, aromatic solvent etc., reduce the pollution of environment and the toxic that reduces product itself;
7. compare with the formulation products of common Nitrapyrin, the Nitrapyrin formulation products in the present invention be take water as dispersant media, to environment safety and environmental protection more, has replaced traditional product and has used organic toxic solvents as the technique of dispersion medium.
The method of producing at present microcapsule is of a great variety, principle, generally can be divided into chemical process, physical method and physico-chemical process.
The present invention adopts chemical polymerization to prepare microcapsule controlled-release agent, good process repeatability, is convenient to control the advantages such as rate of release.Its technological process is as follows: then add suitable polymer cyst material (monomer) to stir effective constituent heating and melting, then the mother liquor that contains effective constituent and cyst material is joined in the aqueous solution that contains suitable emulsifying agent under shearing condition, be emulsified into oil-in-water form, control as required certain granular size.The drop that contains active substance and water molecule reaction form polymer cyst wall.This method generally can be carried out fast, and the cyst wall of formation is more regular, homogeneous, and quality is hard.
Embodiment
Embodiment mono-
After the Nitrapyrin of 1g is heated to fusing point, be melted into liquid state, and then added vinylbenzene 0.1g to stir as activeconstituents mother liquor; Emulsifier tween-60 of 0.5g and the aqueous solution are added in the deionized water of 50g and stir evenly as the aqueous solution; The mother liquor configuring, to entering the aqueous solution and opening high speed homogenizing, is formed to stable O/W emulsion; Open and stir (maintaining 300 turn/min), then the good emulsion of homogenizing is warming up to 30 ℃, maintain stable cyst material solidification value 5 hours, after add the NNO naphthalenesulfonate of 3g, magnesium aluminum silicate (2%) aqueous solution of 20g, moisturizing stirs to 100g, makes the agent of 1%Nitrapyrin microcapsule controlled-release.
Embodiment bis-
After the Nitrapyrin of 10g is heated to fusing point, be melted into liquid state, then added the styrene monomer of the 2g effective constituent mother liquor that stirs; By emulsifying agent fatty alcohol-polyoxyethylene ether AEO-15(Xingtai blue star of 2.0g) add in the deionized water of 50g and stir evenly into the aqueous solution; The mother liquor configuring, to entering in the aqueous solution and opening high speed homogenizing, is formed to stable O/W emulsion; Open and stir (maintaining 450 turn/min), then the good emulsion of homogenizing is warming up to 70 ℃, maintain stable cyst material solidification value 7 hours, after add xanthan gum (2%) aqueous solution of dispersion agent phosphoric acid ester 601P4.0g, 15g, moisturizing stirs to 100g, makes the agent of 10%Nitrapyrin microcapsule controlled-release.
Embodiment tri-
After the Nitrapyrin of 24g is heated to fusing point, be melted into liquid state, then added the vinylbenzene of 6g and the acrylate of the 2g effective constituent mother liquor that stirs; The emulsifying agent fatty alcohol-polyoxyethylene ether AEO-9(Nanjing of 2.0g is changed very much) add in the deionized water of 40g and stir evenly into the aqueous solution; The mother liquor configuring, to entering in the aqueous solution and opening high speed homogenizing, is formed to stable O/W emulsion; Open and stir (maintaining 400 turn/min), then the good emulsion of homogenizing is warming up to 50 ℃, maintain stable cyst material solidification value 5 hours, after add xanthan gum (2%) aqueous solution of the 5.0g of dispersion agent wooden sodium sulfonate, 10g, moisturizing stirs to 100g, makes the agent of 24%Nitrapyrin microcapsule controlled-release.
Embodiment tetra-
After the Nitrapyrin of 40g is heated to fusing point, be melted into liquid state, and then added the acrylate of 10g vinylbenzene and 5g to stir as effective constituent mother liquor; By emulsifying agent PE6800(Germany BASF of 2.0g), PVAC polyvinylalcohol (20%) aqueous solution of 8g adds in the deionized water of 30g and stirs evenly as the aqueous solution; The mother liquor configuring, to entering the aqueous solution and opening high speed homogenizing, is formed to stable O/W emulsion; Open and stir (maintaining 600 turn/min), then the good emulsion of homogenizing is warming up to 60 ℃, maintain stable cyst material solidification value 7 hours, after add the metal carboxylate dispersion agent TERSPERSE2700(Huntsman company of 6.0g), moisturizing stirs to 100g, makes 40% Nitrapyrin microcapsule controlled-release agent.
Embodiment five
After the Nitrapyrin of 60g is heated to fusing point, be melted into liquid state, and then added the vinylbenzene of 5g and the acrylate of 3g to stir as effective constituent mother liquor; By emulsifying agent PE6800(Germany BASF of 3.0g), the PVP of 1g adds in the deionized water of 25g and stirs evenly as the aqueous solution; The activeconstituents mother liquor configuring, to entering the aqueous solution and opening high speed homogenizing, is formed to stable O/W emulsion; Open and stir (maintaining 300 turn/min), then the good emulsion of homogenizing is warming up to 80 ℃, maintain stable cyst material solidification value 4 hours, after add naphthalenesulfonate dispersion agent D-425(Nobel Aksu company of 8.0g) stir, add water and complement to 100g, make the agent of 60%Nitrapyrin microcapsule controlled-release.
Embodiment six
By the liquid in embodiment tetra-, employing filler etc. carries out mixing and absorption, the dry granular preparation that forms.The component of filler can be: wherein a kind of such as kaolin, diatomite, starch, wilkinite, talcum powder, white carbon black or more than; Then the 40%Nitrapyrin sustained release dosage 20g preparing is sprayed and be adsorbed on above filler, dry the solid particle preparation that obtains composition, obtain the sustained release dosage powder granule shape preparation of 20%Nitrapyrin.
Four, effect:
The embodiment tri-24%Nitrapyrin microcapsule controlled-release agent of take are example:
After using nitrogen stablizer to mix with fertilizer in soil, the ammonium nitrogen of soil is improved significantly and extends, by adding the agent of 24%Nitrapyrin microcapsule controlled-release, reduce nitrate-N flux 20%, improved utilization rate of nitrogen fertilizer 30%～40%, increased the content (in Table one) of soil ammonium-state.
Ammonium nitrogen NH in 0～30cm soil (clay) after table one fertilising several weeks
4-N content (mg/KG)
Note: N fertilizer refers to ammonium sulfate fertilizer ASN, (Ammonium sulphate nitrate, content 99.00%, white crystal).It is as shown in the table for the consumption of nitrogen oxidation inhibition stablizer and amount of nitrogen.
Above result is known, and the rear nitrated speed of ammonium of soil ammonium sulfate hydrolysis that does not add nitrogen oxidation retarder is very fast, and adds the nitrated speed of soil hydrolysis ammonium of nitrogen oxidation retarder to slow down.Between incubation period, 1%DMPP, 10%DCD, 0.25%Nitrapyrin(cream preparation), the agent of 0.25%Nitrapyrin(microcapsule controlled-release) the soil effect that all well nitrogen oxidation suppresses processed; But wherein DCD effect can only last till the time of about 9 weeks, and DMPP restraining effect in the time of 9 weeks is obviously not so good as cream preparation and the microcapsule controlled-release agent of Nitrapyrin.To within the 13rd week, only having 24%Nitrapyrin microcapsule controlled-release agent best results.Nitrogen oxidation retarder and nitrogenous fertilizer that 24%Nitrapyrin microcapsule controlled-release agent as fertilizer sources is described mix while using, can not only play the effect of good nitrogen oxidation retarder, simultaneously better than the late effect property of the missible oil product of Nitrapyrin, can effectively reduce consumption and the access times of active substance Nitrapyrin.
Claims (9)
1. a nitrogenous fertilizer stabiliser composition, is characterized in that, described composition consists of the following composition:
Described cyst material is selected from a kind of in polystyrene resin or polystyrene-acrylic resin; Described viscosity-controlling agent is selected from a kind of in xanthan gum, Mierocrystalline cellulose and derivative thereof, PVAC polyvinylalcohol, neusilin salt, wilkinite, polyvinylpyrrolidone PVP;
Described nitrogenous fertilizer stabiliser composition is prepared by following methods:
A, after 65 ℃～75 ℃ thawings, add appropriate cyst material to stir N-serve heating;
B, in water, add in advance emulsifier for mixing even, then add the pre-configured solution that contains N-serve and cyst material, high speed homogenizing forms stable O/w emulsion;
C, reduction rotating speed, under applicable speed conditions, cyst material monomer is polymerization reaction take place under heating state, and temperature of reaction rises in 20 ℃～80 ℃, keeps within 2-8 hour, making cyst material solidify encystation;
D, wait becoming capsule material to solidify completely after encystation, add appropriate dispersion agent, viscosity-controlling agent, stir and make N-serve nitrogenous fertilizer stabiliser composition.
2. nitrogenous fertilizer stabiliser composition according to claim 1, is characterized in that, described polystyrene-acrylic resin is made by polyreaction by vinylbenzene and redundant organism thereof.
3. nitrogenous fertilizer stabiliser composition according to claim 2, is characterized in that, the granularity of described nitrogenous fertilizer stabiliser composition is controlled 0.1um～20um.
4. nitrogenous fertilizer stabiliser composition according to claim 1, it is characterized in that, described emulsifying agent is selected a kind of in aliphatic alcohol polyethenoxy series and derivative phosphoric acid ester, castor oil polyoxyethylene ether, oxyethane and propylene oxide segmented copolymer, sorbitan monolaurate, polyoxyethylene sorbitol acid anhydride monopalmitate or more than one.
5. nitrogenous fertilizer stabiliser composition according to claim 1, it is characterized in that, described dispersion agent is selected a kind of in naphthalenesulfonic acid-formaldehyde condensate, styrene-maleic anhydride copolymer sodium salt, sulfonated lignin, alkyl naphthalene formaldehyde condensate sulfonates, polymerization of carboxylic acid salt or more than one.
6. the preparation method of nitrogenous fertilizer stabiliser composition described in claim 1, is characterized in that, the method comprises:
A, after 65 ℃～75 ℃ thawings, add appropriate cyst material to stir N-serve heating;
B, in water, add in advance emulsifier for mixing even, then add the pre-configured solution that contains N-serve and cyst material, high speed homogenizing forms stable O/w emulsion;
C, reduction rotating speed, under applicable speed conditions, cyst material monomer is polymerization reaction take place under heating state, and temperature of reaction rises in 20 ℃～80 ℃, keeps within 2-8 hour, making cyst material solidify encystation;
D, wait becoming capsule material to solidify completely after encystation, add appropriate dispersion agent, viscosity-controlling agent, stir and make N-serve nitrogenous fertilizer stabiliser composition.
7. the preparation method of nitrogenous fertilizer stabiliser composition according to claim 6, is characterized in that, temperature of reaction is 50-70 ℃ described in step c.
8. the preparation method of nitrogenous fertilizer stabiliser composition according to claim 6, is characterized in that, set time is between 5～7 hours described in step c.
9. the preparation method of nitrogenous fertilizer stabiliser composition according to claim 6, is characterized in that, the granularity of described nitrogenous fertilizer stabiliser composition is controlled 0.1um～20um.
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| CN103524272B (en) * | 2013-11-01 | 2015-09-30 | 九禾股份有限公司 | A kind of high tower long-acting compound fertilizer and preparation method thereof |
| PL3137437T3 (en) * | 2014-05-02 | 2020-04-30 | Dow Agrosciences Llc | Microencapsulated nitrification inhibitor composition |
| CN104276907A (en) * | 2014-10-28 | 2015-01-14 | 浙江奥复托化工有限公司 | Environment-friendly type controlled-release nitrogen fertilizer preparation and preparation method thereof |
| AU2015372557B2 (en) * | 2014-12-31 | 2018-08-30 | Corteva Agriscience Llc | Nitrification inhibitor compositions and methods for preparing the same |
| AU2015372559A1 (en) * | 2014-12-31 | 2017-06-22 | Dow Agrosciences Llc | Microencapsulated nitrification inhibitor compositions |
| CN108238834B (en) * | 2018-02-01 | 2021-03-30 | 黑龙江禾馗农业科技有限公司 | Nitrogen and phosphorus synergist |
| CN110330982A (en) * | 2019-02-11 | 2019-10-15 | 权冉(银川)科技有限公司 | A kind of material of the soil sanitation reparation of adjustable function |
| TW202145895A (en) * | 2020-02-26 | 2021-12-16 | 美商維迪希安生命科學美國公司 | Non-corrosive formulation composition for nitrogen inhibitors |
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| SU1647002A1 (en) * | 1989-04-11 | 1991-05-07 | Институт Химии Ан Узсср | Soil stabilizer for nitrogenous fertilizers |
| CN101693640A (en) * | 2009-09-15 | 2010-04-14 | 广东绿力生物科技有限公司 | Slow-release microcapsule fertilizer and manufacture method thereof |
| CN101759490A (en) * | 2009-11-26 | 2010-06-30 | 范友 | Slowly-controlled-release diammonium phosphate |
| CN102249817A (en) * | 2011-04-21 | 2011-11-23 | 浙江奥复托化工有限公司 | Preparation for inhibiting soil nitrogen loss as well as preparation method and application thereof |
| CN102746073A (en) * | 2012-07-25 | 2012-10-24 | 武秀英 | Nitrogen stabilizing agent and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| SU1647002A1 (en) * | 1989-04-11 | 1991-05-07 | Институт Химии Ан Узсср | Soil stabilizer for nitrogenous fertilizers |
| CN101693640A (en) * | 2009-09-15 | 2010-04-14 | 广东绿力生物科技有限公司 | Slow-release microcapsule fertilizer and manufacture method thereof |
| CN101759490A (en) * | 2009-11-26 | 2010-06-30 | 范友 | Slowly-controlled-release diammonium phosphate |
| CN102249817A (en) * | 2011-04-21 | 2011-11-23 | 浙江奥复托化工有限公司 | Preparation for inhibiting soil nitrogen loss as well as preparation method and application thereof |
| CN102746073A (en) * | 2012-07-25 | 2012-10-24 | 武秀英 | Nitrogen stabilizing agent and application thereof |
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Address after: 226006, Jiangsu, Nantong Province Economic and Technological Development Zone, West revitalization of the South and east of Jiangdong carbon Patentee after: Nantong liannong Jiatian crop Technology Co. Ltd. Address before: 226006 No. 3, Zhenxing West Road, Nantong economic and Technological Development Zone, Jiangsu Patentee before: Nantong Liannong Pesticide Formulation R&D Co., Ltd. |
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Granted publication date: 20141112 Termination date: 20181226 |