CN104140332B - A kind of Water soluble fertilizer Synergistic additives and preparation method thereof - Google Patents
A kind of Water soluble fertilizer Synergistic additives and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of Water soluble fertilizer Synergistic additives, and the weight part of this Water soluble fertilizer Synergistic additives consists of: white carbon black 70-80 part, acrylate 15-20 part, polyvinyl alcohol 10-15 part, stablizer 1-2 part, initiator 0.2-0.5 part, dispersion agent 0.2-0.3 part; By dry method interpenetrating(polymer)networks, three kinds of materials are wound stable polymkeric substance by interting, original performance before ensure that material IPN, and make three kinds of hydrophilic, absorption, water-soluble material can deficiency in complementary the other side's performance, thus for Water soluble fertilizer, meet hydrophilic, absorption, water-soluble performance simultaneously.Interpenetrating(polymer)networks are by Nutrient absorption water-soluble in Water soluble fertilizer, especially the nutrient ion in acrylate and fertilizer forms stable compound, prevent nutrient loss, the calcium carbonate in water, calcium hydroxide, calcium phosphate are had to excellent Decomposition thus improves Water soluble fertilizer fertilizer efficiency.
Description
Technical field
The present invention relates to the fertile field of synergy, be specifically related to a kind of Synergistic additives for Water soluble fertilizer with and preparation method thereof.
Background technology
Chemical fertilizer, as important agriculture data, plays the important and pivotal role in raising grain yield, although China's fertilizer amount total amount is large, fertilizer utilization efficiency is far below World Developed Countries level.In the fertilizer fertilising that China is traditional utilization rate of nitrogen fertilizer be 30% ~ 35%, phosphate fertilizer this season utilization ratio 8% ~ 20%, potassium utilization rate about 50%, major part nutrition divides along with seepage and drain evaporation are in air and underground water, not only waste is serious, and can cause the pollution of soil, air, underground water.Therefore, carry out modification to fertilizer, improving fertilizer efficiency is reduce fertilizer use, the effective way of increasing operation rate.Such as slow-release or control-release fertilizer is exactly one of effective measure improving chemical fertilizer utilization ratio at present; Interpolation nitrification inhibitor or urease inhibitor also can prevent the loss of nitrogenous fertilizer within the specific limits targetedly.But along with China agriculture production is fast-developing, liquid manure resource consumption is serious, and soil lacks rational element supplements, and causes soil depletion to harden.At present, efficient modernization agricultural forward water-fertilizer integral future development, walks the road of resources effective utilization.The fertilizer efficiency and the utilization ratio that how to improve Water soluble fertilizer are even more important.Therefore traditional slow-release fertilizer cannot meet the demand of water rate integration, and nitrification inhibitor, urease inhibitor etc. are also difficult to the synergy demand meeting many nutrients Water soluble fertilizer.
Water soluble fertilizer is a kind of novel environment friendly fertilizer of the development for adapting to high-efficiency agriculture and sustainable agriculture, easy to use, can spray, rush and execute, and can fill with spray drop and be combined, at raising utilization rate of fertilizer, save agricultural water, reduce ecological environmental pollution, improve crop quality and reduce in labor force etc. and have a clear superiority in.Especially in order to reach, water saving, joint are fertile, the object of saving of labor, the fertigation of water-fertilizer integral, spray fertilising and are extensively applied becoming more meticulous, in large-scale planting.Due to Water soluble fertilizer have instant, specific absorption is high, instant effect, without residue, use the remarkable advantages such as convenient, at drip irrigation system, spray sprinkling irrigation etc. there is remarkable water saving, save the novel fertilizer application mode of fertile function and start to be widely applied, the person that the makes agricultural fertilizer basic change to the noegenesis of fertilizer.Water soluble fertilizer is as the main flow of current fertigation, although can economize on water, save fertilizer, save man-hour, due to the quick water-soluble performance fertilizer efficiency of Water soluble fertilizer, therefore its volatilization is run off, infiltration is run off and the reaction of fertilizer ion and soil more easily occurs.Therefore, existing Water soluble fertilizer instant effect, but utilization rate of fertilizer is still lower.Especially the probability of fertilizer ion generation acid-base reaction, replacement(metathesis)reaction, complexing fixation reaction is larger.
Chinese invention patent application numbers 201310598589.5 discloses a kind of fertilizer synergist and application thereof, and this invention is made up of the polymeric amino acid of 1 ~ 10 weight part and the nitrification inhibitor of 0.5 ~ 2 weight part; Wherein, described nitrification inhibitor is for have inhibiting compound to nitrobacteria, denitrification enzyme in soil.
Chinese invention patent application numbers 201210364444.4 provides a kind of fertilizer synergist, comprises the component of following weight part: poly aspartic acid 7% ~ 15%, trace element 0.5% ~ 2%, wilkinite 30% ~ 40%, Sodium salts humic acids 10% ~ 20%, zeolite 5% ~ 15%, polygorskite 10% ~ 20%, glaukonine 10 ~ 20%, thiocarbamide 2% ~ 4% and nano-sized carbon 0.1% ~ 0.5%.The each composition of this fertilizer synergist promotes mutually, utilizes poly aspartic acid to improve soil, improves effect of crop quality and output.
Chinese invention patent application 201110109999.X discloses a kind of fertilizer synergistic additive and application thereof, and it forms and weight proportion is, polyglutamic acid 1-20%, Trisodium Citrate 1-10%, diatomite 10-30%, zeolite powder 40-60%.The present invention is amino acid whose polymerization purifying substances, and biodegradable one-tenth single amino acid is for plant absorption, and noresidue, pollution, the fertilizer utilizing it to produce is applicable to the soil of various crop and different areas.
Above fertilizer synergist is applied in composite fertilizer, slow-release fertilizer to be had certain building performance, but along with the large-scale promotion of Water soluble fertilizer, these synergistic agent have been difficult to adapt to market application due to factors such as single, indissolubles.By inhibition of Chemical Reaction agent, due to urease inhibitors and nitrification inhibitor very easily polluted-water, therefore use and be restricted.In order to prevent, fertilizer nutrient from volatilizing, seepage, nutrient is fixed by the sorbing material of porous material, because porous material is insoluble in water, therefore Water soluble fertilizer is not suitable for, even if use polyamino acid to carry out complexing, fixing of nutrient is also extremely limited, can only possess complexing action to part nutrient ion, and polyamino acid cost is high, not easily big area uses.
Summary of the invention
For current Water soluble fertilizer in use volatile, the seepage of the effective constituent defect that causes fertilizer efficiency utilization ratio to reduce, the invention provides a kind of Water soluble fertilizer Synergistic additives, this Water soluble fertilizer Synergistic additives is the composition polymer of the network structure of being polymerized by white carbon black, acrylate, polyvinyl alcohol IPN and being formed, this composition polymer has the property held to all kinds of chemical fertilizer nutrient, especially to soluble salt, there is the property held, for can be quickly dissolved into water during Water soluble fertilizer and enrichment nutrient prevents nutrient loss.
Further aim of the present invention is to provide the preparation method of this Water soluble fertilizer Synergistic additives, by interpenetrating(polymer)networks under dry method state, three kinds of materials are wound stable polymkeric substance by interting, original performance before greatly ensure that material IPN, and make three kinds of hydrophilic, absorption, water-soluble material can deficiency in complementary the other side's performance, thus for Water soluble fertilizer, meet hydrophilic, absorption, water-soluble performance simultaneously.。
A kind of Water soluble fertilizer of the present invention Synergistic additives adopts following technical scheme to realize:
A kind of Water soluble fertilizer Synergistic additives, is characterized in that a kind of IPN is wound around the stabilization of polymer of network structure, is made up of following weight part:
White carbon black 70-80 part,
Acrylate 15-20 part,
Polyvinyl alcohol 10-15 part,
Stablizer 1-2 part,
Initiator 0.2-0.5 part,
Dispersion agent 0.2-0.3 part,
Wherein, the stabilization of polymer structure of described IPN winding network structure is the network structure of Semi-IPN formula, wound form, shell core formula, wherein acrylate and white carbon black adsorb Semi-IPN, are wound around after initiated polymerization with polyvinyl alcohol, form the shell nuclear network structure of polyvinyl alcohol voluble wrapping; Described white carbon black is thermal silica, and particle diameter is less than the gluey nanoparticle of 100nm; The middle polymerization degree powdery polyethylene alcohol of alcoholysis degree 88%, molecular weight 12-15 ten thousand selected by described polyvinyl alcohol; The one in iron(ic) chloride, hydrogen peroxide iron, hydrogen peroxide copper selected by described initiator; Described dispersion agent selects the one in stearic acid sorbitan ester, single palmitinic acid sorbitan ester, sorbitan monooleate, polyoxyethylene sorbitan monooleate, polyoxyethylene glycol, polydimethylsiloxane; The one in polyacrylic acid, polymethyl acrylic acid, poly-2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid, 2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid and acrylic acid multipolymer selected by described stablizer.
Acrylate described above be molecular weight 1000-1500 containing methyl or not methylic acrylate, following structural formula:
Not methylic acrylate:
；
Acrylate containing methyl:
; One in preferred methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, propyl acrylate, propyl methacrylate, there is autohemagglutination, stable compound can be formed with fertilizer particle, to insolubless such as calcium carbonate, calcium hydroxide, calcium phosphate in water, there is excellent Decomposition.
A kind of Water soluble fertilizer Synergistic additives of the present invention, is characterized in that preparation method carries out in the following manner:
(1) polyvinyl alcohol of the acrylate of the white carbon black of 70-80 weight part, 15-20 weight part, 10-20 weight part, 0.2-0.3 parts per weight dispersing agent are sent into reflection-type pulverizer after mixing in high-speed mixer to be clashed into mutually by mechanical disintegration and gas, form the powder of inierpeneirating network structure;
(2) reactor sent into by powder step (2) obtained and the initiator of 0.2-0.5 weight part, passes into nitrogen protection, be heated to 60-80 DEG C under dry powder, and high-speed stirring reaction 30-45min, obtains composition polymer;
(3) a kind of Water soluble fertilizer Synergistic additives is obtained after composition polymer step (2) obtained and the stablizer of 1-2 weight part are mixed.
Reflection-type pulverizer described in above-mentioned preparation process (1) is eddy airstream reflection pulverizer, clashed into mutually by mechanical disintegration and gas, thus reach the object of dispersion, dispersed material enters graded region with air-flow, makes material form the powder of inierpeneirating network structure by the rate of dispersion of 1200-1500rpm.
Above-mentioned preparation process (2) described reactor is normal-pressure reaction kettle, is wherein provided with high speed planet stirring mechanism, and rotating speed of agitator is 400-900rpm, carries out initiation and connect under dry powder suspended state.
The network structure composition polymer that a kind of Water soluble fertilizer Synergistic additives of the present invention is wound around polymerization by white carbon black, acrylate, polyvinyl alcohol IPN under dry method state and is formed, its interpenetrating polymer networks is mutually wound around by three kinds of materials and runs through and formed, and has hydrophilic, absorption, water-soluble characteristic.Three kinds of materials make to force mutual tolerance by interspersed winding by interpenetrating(polymer)networks, even if first three kind material of IPN has different character, thus greatly ensure that original performance before material IPN, also stable polymkeric substance can be formed after IPN, and make three kinds of hydrophilic, absorption, water-soluble material can deficiency in complementary the other side's performance, thus for Water soluble fertilizer, meet hydrophilic, absorption, water-soluble performance simultaneously.The present invention is interted mutually by structural, to obtain the complementation in performance, for can be water-soluble during Water soluble fertilizer, polyvinyl alcohol is the macromolecular compound containing great amount of hydroxy group, therefore wetting ability is extremely strong, water can be dissolved in, and the network that acrylate and white carbon black are formed is by Nutrient absorption water-soluble in Water soluble fertilizer, especially the nutrient ion in acrylate and fertilizer forms stable compound, prevent nutrient loss, to insolubless such as calcium carbonate, calcium hydroxide, calcium phosphate in water, there is excellent Decomposition thus improve Water soluble fertilizer fertilizer efficiency.
The present invention utilizes adsorptivity, the fixed characteristic of interpenetrating(polymer)networks, collect hydrophilic, absorption, dissolution, fixed nitrogen, be transmitted in one, can effectively collect nutrition and transmission path is provided, prevent fertilizer efficiency to run off, raising utilization rate of fertilizer.Can apply fertilizer as rushed with all kinds of water soluble fertilizer, fertilizer is composite uses for drip irrigation fertilizer, compound Water soluble fertilizer etc., form Water soluble fertilizer for nutrient system at plant root.
A kind of Water soluble fertilizer Synergistic additives of the present invention and preparation method thereof, compared with prior art outstanding feature and useful effect are:
1, a kind of Water soluble fertilizer Synergistic additives of the present invention is polymerized and the composition polymer that formed by white carbon black, acrylate, polyvinyl alcohol dry method IPN, there is hydrophilic, absorption, water-soluble characteristic, for Water soluble fertilizer to the nutrition of dissolving divide have hold, fix, transmitting effect, avoid the defect that Water soluble fertilizer is volatile, seepage causes fertilizer efficiency utilization ratio to reduce
2, the preparation method of a kind of Water soluble fertilizer Synergistic additives of the present invention, utilize dry method interpenetrating(polymer)networks, polyvinyl alcohol is containing great amount of hydroxy group, wetting ability is extremely strong, and the network that acrylate and white carbon black are formed is by Nutrient absorption water-soluble in Water soluble fertilizer, especially the nutrient ion in acrylate and fertilizer forms stable compound, prevents nutrient loss, and calcium carbonate, calcium hydroxide, calcium phosphate in water are had to excellent Decomposition thus improves Water soluble fertilizer fertilizer efficiency.
3, a kind of Water soluble fertilizer Synergistic additives of the present invention and preparation method, obvious to Water soluble fertilizer synergy, cost is low, easy to use, and preparation technology is easily controlled, and is suitable for large-scale production application.
Accompanying drawing explanation
Fig. 1 is that a kind of Water soluble fertilizer Synergistic additives of the present invention passes the IPN schematic diagram being wound around network mutually.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following example.When not departing from aforesaid method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all should be within the scope of the present invention.
Embodiment 1
(1) polymerization degree polyvinyl alcohol, 0.2 weight part polydimethylsiloxane dispersion agent in the methyl acrylate of gluey for the gas-phase silica of 70 weight part particle diameter 50nm nanoparticle, 20 weight part molecular weight 1000-1500,10 weight part molecular weight 120,000, alcoholysis degree 88% are sent into reflection-type pulverizer after mixing in high-speed mixer and clashed into mutually by mechanical disintegration and gas, make material form the powder of inierpeneirating network structure by the rate of dispersion of 1200rpm.
(2) powder step (2) obtained and the hydrogen peroxide copper of 0.2 weight part send into reactor, pass into nitrogen protection, be heated to 60-80 DEG C under dry powder, and rotating speed of agitator is 400rpm high-speed stirring reaction 45min, obtains composition polymer;
(3) a kind of Water soluble fertilizer Synergistic additives is obtained after the poly-2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid of composition polymer step (2) obtained and 2 weight parts is mixed.
The Water soluble fertilizer Synergistic additives 0.5% that the present embodiment is obtained with 99.5% Water soluble fertilizer mix after apply fertilizer, carry out fertilizer efficiency synergy test, test result is as follows:
By test result, under equal rate of fertilizer application condition, add the yield and quality that Synergistic additives of the present invention can promote grape in Water soluble fertilizer, vintage is than direct use Water soluble fertilizer output increased 12%, and grape gloss appearance, grain are homogeneous greatly.Especially by the soil testing after plantation, synergistic agent decomposable asymmetric choice net of the present invention also impels the absorption of phosphorus, and in soil, insoluble phosphorus content declines; And for the potassium of solubility, there is the good property held, effectively prevent the water-soluble Loss by leaching of potassium, ensure potassium content higher in wine-growing soil.
Thus, synergistic agent of the present invention under equal Water soluble fertilizer consumption condition, can reach significantly building performance, can directly promote Water soluble fertilizer plant recovery of nutrient more than 20%.
Embodiment 2
(1) polymerization degree polyvinyl alcohol, 0.3 parts by weight of polyoxyethylene polyoxyethylene-sorbitan mono-oleate dispersion agent in the β-dimethyl-aminoethylmethacrylate of gluey for the gas-phase silica of 75 weight part particle diameter 80nm nanoparticle, 18 weight part molecular weight 1000-1500,20 weight part molecular weight 130,000, alcoholysis degree 88% are sent into reflection-type pulverizer after mixing in high-speed mixer and clashed into mutually by mechanical disintegration and gas, make material form the powder of inierpeneirating network structure by the rate of dispersion of 1300rpm.
(2) reactor sent into by powder step (2) obtained and the hydrogen peroxide iron of 0.2 weight part, passes into nitrogen protection, be heated to 60-80 DEG C under dry powder, and rotating speed of agitator is 500rpm high-speed stirring reaction 40min, obtains composition polymer;
(3) a kind of Water soluble fertilizer Synergistic additives is obtained after composition polymer step (2) obtained and the polymethyl acrylic acid of 1 weight part are mixed.
Embodiment 3
(1) polymerization degree polyvinyl alcohol, 0.2 weight part list palmitinic acid sorbitan ester dispersion agent in the propyl acrylate of gluey for the gas-phase silica of 80 weight part particle diameter 60nm nanoparticle, 15 weight part molecular weight 1000-1500,15 weight part molecular weight 150,000, alcoholysis degree 88% are sent into reflection-type pulverizer after mixing in high-speed mixer and clashed into mutually by mechanical disintegration and gas, make material form the powder of inierpeneirating network structure by the rate of dispersion of 1500rpm.
(2) powder step (2) obtained and the iron(ic) chloride of 0.5 weight part send into reactor, pass into nitrogen protection, be heated to 60-80 DEG C under dry powder, and rotating speed of agitator is 500rpm high-speed stirring reaction 30min, obtains composition polymer;
(3) a kind of Water soluble fertilizer Synergistic additives is obtained after composition polymer step (2) obtained and the 2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid of 2 weight parts and acrylic acid multipolymer are mixed.
Embodiment 4
(1) polymerization degree polyvinyl alcohol, 0.2 weight part stearic acid sorbitan ester dispersion agent in the propyl methacrylate of gluey for the gas-phase silica of 72 weight part particle diameter 20nm nanoparticle, 18 weight part molecular weight 1000-1500,12 weight part molecular weight 120,000, alcoholysis degree 88% are sent into reflection-type pulverizer after mixing in high-speed mixer and clashed into mutually by mechanical disintegration and gas, make material form the powder of inierpeneirating network structure by the rate of dispersion of `1200rpm.
(2) powder step (2) obtained and the hydrogen peroxide copper of 0.5 weight part send into reactor, pass into nitrogen protection, be heated to 60-80 DEG C under dry powder, and rotating speed of agitator is 800rpm high-speed stirring reaction 40min, obtains composition polymer;
(3) a kind of Water soluble fertilizer Synergistic additives is obtained after the poly-2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid of composition polymer step (2) obtained and 1 weight part is mixed.
Embodiment 5
(1) 75 weight part particle diameters are less than polymerization degree polyvinyl alcohol, 0.3 weight part sorbitan monooleate dispersion agent in the gluey nanoparticle of gas-phase silica of 100nm, the ethyl propenoate of 20 weight part molecular weight 1000-1500,13 weight part molecular weight 140,000, alcoholysis degree 88% to send into reflection-type pulverizer after mixing in high-speed mixer and clashed into mutually by mechanical disintegration and gas, make material form the powder of inierpeneirating network structure by the rate of dispersion of `1500rpm.
(2) powder step (2) obtained and the hydrogen peroxide copper of 0.4 weight part send into reactor, pass into nitrogen protection, be heated to 60-80 DEG C under dry powder, and rotating speed of agitator is 900rpm high-speed stirring reaction 45min, obtains composition polymer;
(3) a kind of Water soluble fertilizer Synergistic additives is obtained after composition polymer step (2) obtained and the polymethyl acrylic acid of 1.5 weight parts are mixed.
Claims (4)
1. a Water soluble fertilizer Synergistic additives, is characterized in that the IPN be prepared into by following raw materials in part by weight is wound around the stabilization of polymer of network structure:
White carbon black 70-80 part,
Acrylate 15-20 part,
Polyvinyl alcohol 10-15 part,
Stablizer 1-2 part,
Initiator 0.2-0.5 part,
Dispersion agent 0.2-0.3 part,
Wherein, described white carbon black is thermal silica, is less than the gluey nanoparticle of 100nm in particle diameter; Described acrylate is molecular weight 1000-1500; The middle polymerization degree pva powder of alcoholysis degree 88%, molecular weight 12-15 ten thousand selected by described polyvinyl alcohol; The one in iron(ic) chloride, hydrogen peroxide iron, hydrogen peroxide copper selected by described initiator; Described dispersion agent selects the one in stearic acid sorbitan ester, single palmitinic acid sorbitan ester, sorbitan monooleate, polyoxyethylene sorbitan monooleate, polyoxyethylene glycol, polydimethylsiloxane; The one in polyacrylic acid, polymethyl acrylic acid, poly-2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid, 2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid and acrylic acid multipolymer selected by described stablizer; The stabilization of polymer structure of described IPN winding network structure is the network structure of Semi-IPN formula, wound form, shell core formula, wherein acrylate and white carbon black adsorb Semi-IPN, be wound around with polyvinyl alcohol after initiated polymerization, form the shell nuclear network structure of polyvinyl alcohol voluble wrapping; Described Water soluble fertilizer Synergistic additives prepares by the following method and obtains:
(1) polyvinyl alcohol of the acrylate of the white carbon black of 70-80 weight part, 15-20 weight part, 10-20 weight part, the dispersion agent of 0.2-0.3 weight part are sent into reflection-type pulverizer after mixing in high-speed mixer and clashed into mutually by mechanical disintegration and gas, form the powder of inierpeneirating network structure;
(2) reactor sent into by powder step (2) obtained and the initiator of 0.2-0.5 weight part, passes into nitrogen protection, be heated to 60-80 DEG C under dry powder, and high-speed stirring reaction 30-45min, obtains composition polymer;
(3) a kind of Water soluble fertilizer Synergistic additives is obtained after composition polymer step (2) obtained and the stablizer of 1-2 weight part are mixed.
2. a kind of Water soluble fertilizer Synergistic additives according to claim 1, is characterized in that described acrylate is the one in methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, propyl acrylate, propyl methacrylate.
3. Water soluble fertilizer Synergistic additives according to claim 1, it is characterized in that: the reflection-type pulverizer described in preparation process (1) is eddy airstream reflection pulverizer, clashed into mutually by mechanical disintegration and gas, thus reach the object of synchronous dispersion IPN, dispersed material enters graded region with air-flow, makes material form the powder of inierpeneirating network structure by the rate of dispersion of 1200-1500rpm.
4. Water soluble fertilizer Synergistic additives according to claim 1, it is characterized in that: the reactor described in preparation process (2) is normal-pressure reaction kettle, wherein be provided with high speed planet stirring mechanism, rotating speed of agitator is 400-900rpm, carries out initiation and connect under the complete suspended state of dry powder.
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| CN105622255A (en) * | 2015-12-23 | 2016-06-01 | 成都新柯力化工科技有限公司 | Synergist for fertilizer special for wheat and preparation method for synergist |
| CN106565313A (en) * | 2016-10-25 | 2017-04-19 | 成都新柯力化工科技有限公司 | Preparation method of polymerization chelating water-soluble fertilizer |
| CN112125760A (en) * | 2020-08-19 | 2020-12-25 | 洲际环境科学研究院(广州)有限公司 | Environment-friendly method for reducing nitrification of ammonia nitrogen in soil |
| CN115005032B (en) * | 2022-06-15 | 2023-07-25 | 西藏自治区农牧科学院农业研究所 | Planting method for interplanting common turnip with winter wheat |
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| JP2011162425A (en) * | 2010-02-15 | 2011-08-25 | Kuretake Co Ltd | Colored fertilizer for plant |
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| CN101016219A (en) * | 2007-02-14 | 2007-08-15 | 湖北农本化工有限公司 | Pharmaceutical bottom fertilizer granule for preventing cotton sprout plant diseases and insect pests |
| CN102557810A (en) * | 2010-12-09 | 2012-07-11 | 王海炜 | Degradable slow-release fertilizer coating agent |
| WO2013035106A1 (en) * | 2011-09-07 | 2013-03-14 | Indo Gulf Fertilizers | A process for manufacturing a composite fertilizer |
| CN103102218A (en) * | 2013-01-27 | 2013-05-15 | 成都科利隆生化有限公司 | Pesticide-fertilizer mixer for controlling rice stem borers and preparation method of pesticide-fertilizer mixer |
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Inventor after: Jiang Hao Inventor before: Chen Qing Inventor before: Zeng Juntang |
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Effective date of registration: 20180418 Address after: 620031 4 Jin Lei Road, Jinxiang Industrial Park, Meishan, Sichuan. Patentee after: Jiang Hao Address before: Qingyang District of Chengdu City, Sichuan province 610091 Dragon Industrial Port East Road 4 Patentee before: CHENDU NEW KELI CHEMICAL SCIENCE Co.,Ltd. CHINA |
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Granted publication date: 20160406 Termination date: 20210808 |