CN102295491B - Natural polymer modified coated controlled release fertilizer and preparation method thereof - Google Patents
Natural polymer modified coated controlled release fertilizer and preparation method thereof Download PDFInfo
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- CN102295491B CN102295491B CN201110204883.4A CN201110204883A CN102295491B CN 102295491 B CN102295491 B CN 102295491B CN 201110204883 A CN201110204883 A CN 201110204883A CN 102295491 B CN102295491 B CN 102295491B
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- 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
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- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
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Abstract
The invention discloses a natural polymer modified coated controlled release fertilizer and a preparation method thereof. The fertilizer comprises a fertilizer core layer and a coated layer positioned on the outside of the fertilizer core, wherein the material of the fertilizer core layer is formed from fertilizer particles, and the coated layer which is one layer or two layers and is a two layered coated controlled release fertilizer is a cellulose layer and a hydrophobic film. The coated controlled release fertilizer provided by the invention has a good controlled release performance, and simultaneously the film material has biodegradability, so an environmental problem brought by the controlled release film material is solved. A natural product cellulose is adopted to get rid of the dependence of the coated material on a petrochemical resource, so the sustainable development of the coated material is realized. The coated controlled release fertilizer, which has the advantages of improvement of the fertilizer utilization rate, environment pollution reduction, sustainable development, and the like, has a wide application prospect.
Description
Technical field
The present invention relates to a kind of coated fertilizer and production method thereof, relate in particular to coated fertilizer of a kind of natural macromolecule modification and preparation method thereof.
Background technology
Fertilizer is one of most important production means of agriculture production, is the material base of plant growth.Chemical fertilizer replaces farm manure to play great function to agricultural, livestock industry, developing rapidly of aquaculture, solid matenal support is provided also to the development of human society.China Shi Yige large agricultural country, all will be used a large amount of fertilizer every year.Along with explosive population growth, the minimizing of ploughing, grain imbalance between supply and demand increasingly sharpens, and causes agriculture production to depend on fertilizer unduly, causes fertilizer excessively to use.Most of fertilizer varieties of the present production and application of China are all water miscible quick-acting fertilizers.Readily avaiable fertilizer is because easily run off, decompose and fix, and utilization ratio is very low, adds excessive use, causes a large amount of losses of fertilizer nutrient, not only suffers a loss economically, and excessive use chemical fertilizer also causes crop quality to decline and large-area pollution of area source.Therefore how improving utilization rate of fertilizer is the significant task that China faces.
Slowly/controlled releasing fertilizer can delay or control the release of nutrient, and nutrient release is matched with crop demand, thereby has improved the utilization ratio of fertilizer, reduces loss and the pollution to environment of nutrient, therefore in agricultural, is widely used.
The type of film-coated controlled release fertilizer mainly contains inorganics coated fertilizer and organic polymer coated fertilizer both at home and abroad at present.
Inorganics coated fertilizer is mainly to using sulphur, fused(calcium magnesium)phosphate, ground phosphate rock, talcum powder, terra alba, flyash and inorganic cementitious material etc. as coated fertilizer (CN1396143, CN1634808, CN1524832, CN1696080, CN1884228, US3295950, CN1854111), these inorganic coating fertilizer low prices, make simple, and can not cause environmental pollution, its coating layer also can provide nutrient to crop, but its water resisting property is poor, nutrient controlled release properties is poor, coating is easily broken in transportation, makes the utilization ratio of fertilizer still very low.Use at present more sulfur coated fertilizer life-time service also likely to cause soil acidification both at home and abroad.
Organic synthetic polymer coated fertilizer can be divided into thermoplastic resin and the large class of thermosetting resin two, and this fertilizer control release is functional.It is representative that thermoplastic resin membrane wrapping control-releasing fertilizer material be take Japan " Meister ", and it is representative that thermohardening resin coated controlled-release fertilizer material mainly be take " Osmocote " and Canadian " ESN " of the U.S..The most of technique of this class coated fertilizer product is with adopting fluidized-bed coating after dissolution with solvents by coating resin.This technique coating is even, but energy consumption is high, and solvent majority is poisonous and be difficult to recovery, and production efficiency is low, and complex process is difficult to realize production in enormous quantities (CN101037371).Canada Agrium Inc. is sprayed into fertiliser granulates surface direct reaction film forming with polyvalent alcohol and polyisocyanates in rotary drum, and this technique is without adopting solvent, and reactionless by product, has realized the serialization of safety non-toxic and produced (CN101068628A).Relevant reaction in－situ polyurethanes coated fertilizer is shown in serial United States Patent (USP) (US5538531, US5851261, US6358296131, US2003/0051523A1, US2004/0016276A1, US2007/0137274A1).Domestic thermoplastic polymer coated fertilizer is mainly that polyethylene, polystyrene are main (CN101050148, CN101462907, CN1603288, CN101372434), then is aided with the additives such as paraffin, inorganic mineral.Thermohardening resin coated fertilizer be take epoxy resin as main (CN1569773), and in addition suitably modification, adds suitable additives.The domestic also Patents (CN101323545) of visible polyurethane material coating controlled-release fertilizer.
The common shortcoming of organic polymer coated fertilizer is: 1, production cost is high, it is applicable that to make object plane narrow, be only applicable to the high crops of added value such as garden crop, golf course, ornamental plant, to solving the land for growing field crops excessive problems such as financial loss and environmental pollution that cause of fertilising, there is no help; 2, the biological non-degradable of coated fertilizer, life-time service easily causes " white pollution "; 3, rely on the Nonrenewable resources such as oil, be difficult to long-term sustainable sexual development.
Summary of the invention
The object of this invention is to provide coated fertilizer of a kind of natural macromolecule modification and preparation method thereof.
Coated fertilizer of natural macromolecule modification provided by the invention and preparation method thereof (being also cellulose modified film-coated controlled release fertilizer), is comprised of fertilizer core layer and the coating layer being positioned at outside described fertilizer core layer; Wherein, the material that forms described fertilizer core layer is fertiliser granulates; Described coating layer comprises cellulose layer;
The material that forms described cellulose layer is by least one composition in Mierocrystalline cellulose and following compound: linking agent, catalyzer and softening agent stripping auxiliary agent.
Described coating layer comprises hydrophobicity rete; The material that forms described hydrophobicity rete is film coalescence aid.
Described coating layer is one deck, by described cellulose layer and described hydrophobicity rete, is mixed.
Described coating layer is two-layer, and wherein one deck is described cellulose layer, and another layer is described hydrophobicity rete.
In above-mentioned film-coated controlled release fertilizer, the particle diameter of described fertiliser granulates is 2～6mm, preferably 3～5mm; Described fertiliser granulates is selected from urea, volatile salt, ammonium nitrate, ammonium sulfate, vitriolate of tartar, Repone K, saltpetre, Secondary ammonium phosphate, primary ammonium phosphate, contains micro-fertilizer and at least one in Chemical Mixed Fertilizer, preferably at least one in urea, ammonium sulfate, vitriolate of tartar, Repone K, saltpetre, Secondary ammonium phosphate and primary ammonium phosphate; Wherein, described in contain in micro-fertilizer, at least one in described micro-chosen from Fe, manganese, boron, zinc, copper and molybdenum; Described Chemical Mixed Fertilizer is commercially available various conventional compound manure.
Described Mierocrystalline cellulose is selected from paper pulp, Microcrystalline Cellulose, hemicellulose, methylcellulose gum, ethyl cellulose, propyl cellulose, methylethyl cellulose, Walocel MT 20.000PV, Natvosol, hydroxypropylcellulose, Type 3U, cyanoethyl cellulose, ethyl-cyanoethyl cellulose, hydroxyethylmethyl-cellulose, Vltra tears, carboxymethyl cellulose, soluble cotton, phosphorylated cotton, cellulose acetate, at least one of cellulose acetate propionate and cellulose acetate butyrate, preferred cellulose, Microcrystalline Cellulose, methylcellulose gum, ethyl cellulose, Walocel MT 20.000PV, Type 3U, hydroxyethylmethyl-cellulose, carboxymethyl cellulose, soluble cotton, phosphorylated cotton, at least one in cellulose acetate and cellulose acetate propionate, wherein, described paper pulp is selected from least one in bardwood pulp, softwood pulp, jute pulp and bamboo pulp, described cellulosic mean polymerisation degree is 150～15000, preferably 200～10000, most preferably 350～7000,
Described linking agent is selected from formaldehyde, oxalic dialdehyde, glutaraldehyde, Alpha-hydroxy hexanedial, four polyoxymethylene, trimeric cyanamide, terpolycyantoamino-formaldehyde resin, methane amide, ethanamide, N,N methylene bis acrylamide, N hydroxymethyl acrylamide, divinyl sulfone, oxyethane, propylene oxide, epoxy chloropropane, acrylate chloride, oxalyl chloride, diallyl amine, oxalic acid, hexanodioic acid, maleic acid, 1,2,3,4-fourth tetracid, polymaleic acid, polyacrylic acid, succsinic acid, oxalic acid acid anhydride, Tetra hydro Phthalic anhydride, Succinic anhydried, ethylene two (N-methylol carbamate), tolylene diisocyanate, diphenylmethanediisocyanate, liquefaction diphenylmethanediisocyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, to phenylmethane vulcabond, Isosorbide-5-Nitrae-bicyclohexane vulcabond, xylylene diisocyanate, cyclohexanedimethyleterephthalate vulcabond, Methylcyclohexyl diisocyanate, norbornene alkyl diisocyanate, polymethylene multi-phenenyl isocyanate, toluene diisocyanate dimer, toluene diisocyanate trimer, tolylene diisocyanate-hexamethylene diisocyanate mixing polymer, hexamethylene diisocyanate trimer, at least one in hexamethylene diisocyanate biuret and isoflurane chalcone diisocyanate tripolymer, preferably formaldehyde, oxalic dialdehyde, glutaraldehyde, terpolycyantoamino-formaldehyde resin, N,N methylene bis acrylamide, oxalic acid, hexanodioic acid, oxyethane, epoxy chloropropane, acrylate chloride, Tetra hydro Phthalic anhydride, tolylene diisocyanate, diphenylmethanediisocyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate, polymethylene multi-phenenyl isocyanate, to phenylmethane vulcabond, toluene diisocyanate dimer, at least one in toluene diisocyanate trimer and isoflurane chalcone diisocyanate tripolymer,
Described catalyzer is selected from perchloric acid, the vitriol oil, phosphoric acid, hydrochloric acid, tosic acid, sodium dihydrogen phosphite, Tetrafluoroboric acid zinc, dibutyl tin laurate, stannous octoate, triethylamine, dimethyl cetylamine, ceric ammonium nitrate, two dimethyl aminoethyl ether, diethylenetriamine, diethylenetriamine, tetrabutyl butane diamines, N-Ethylmorphine quinoline, N, N-dimethylcyclohexylamine, trolamine, methyldiethanolamine, dimethylethanolamine, pyridine, N, N-lutidine, 1, 2, 4-tri methyl piperazine, at least one in two ketoimines and α-mercaptobenzimidazole, the preferred vitriol oil, phosphoric acid, tosic acid, dibutyl tin laurate, stannous octoate, triethylamine, ceric ammonium nitrate, N, N-dimethylcyclohexylamine, trolamine, pyridine and N, at least one in N-lutidine,
Described softening agent is selected from least one in polyvinyl alcohol, glycerine, dioctyl phthalate (DOP), dibutyl phthalate and diheptyl phthalate, at least one in preferably polyethylene alcohol, glycerine, dioctyl phthalate (DOP) and diheptyl phthalate; Wherein, the mean polymerisation degree of described polyvinyl alcohol is 700～1800, preferably 900～1500;
Described film coalescence aid is selected from least one in paraffin, rosin, petroleum resin, turps, sulphur, clorafin, sulfonation paraffin and terpine resin, preferably at least one in paraffin, sulfonation paraffin, turps and petroleum resin.
The mass ratio of described coating layer and described fertilizer core layer is 0.02～0.13, preferably 0.03～0.10, most preferably 0.1;
Described linking agent and described cellulosic mass ratio are 0.5%～70%, specifically can be 33-63%, 37-62%, 39-60% or 55-63%, preferably 5%～70%, most preferably be 5%～40%;
Described catalyzer and described cellulosic mass ratio are 0.02%～0.07%, specifically can be 0.03-0.07% or 0.04-0.07%, preferably 0.03%～0.04%;
Described softening agent and described cellulosic mass ratio are 0.5%～20%, specifically can be 19-20%, preferably 0.5%～10%;
Described film coalescence aid and described cellulosic mass ratio are 0.5%～36%, specifically can be 13-18%, 18-26% or 18-36%, preferably 0.5%～7%.
The nitrogen initial stage solubility rate of described cellulose modified coated release-controlled rate is 4.2-9.8%, and the controlled release phase of nitrogen is 26-64 days, and the film rate of weight loss of 12 months is 26-62%.
The method of the described cellulose modified film-coated controlled release fertilizer of preparation provided by the invention, comprises the steps:
1) at least one in described Mierocrystalline cellulose and following compound mixed and obtain coating liquid a in solvent: described linking agent, described catalyzer and described softening agent;
Described film coalescence aid is mixed and obtains coating liquid b in described solvent;
Or, at least one in described Mierocrystalline cellulose, described film coalescence aid and following compound mixed to the mixture that obtains coating liquid a and coating liquid b in solvent: described linking agent, described catalyzer and described softening agent;
2) the described fertiliser granulates in fluidized state is carried out after preheating; by described step 1) after described fertiliser granulates after gained coating liquid a and/or coating liquid b and preheating mixes; step 1 described in atomization) gained coating liquid a and/or coating liquid b; make it evenly be sprayed on described fertiliser granulates surface, coolingly after insulation reaction obtain described cellulose modified film-coated controlled release fertilizer.
Described step 1) mix in step, temperature is 30～100 ℃, preferably 50～90 ℃, and most preferably 65～90 ℃; This mixes in step, can adopt mixing apparatus to realize the well blend of high viscosity liquid; In this step, Mierocrystalline cellulose under the effect of catalyzer with the substance reactions such as linking agent, complete cellulosic chemical modification;
Described step 2) in, the described described water soluble fertilizer particle in fluidized state, makes described water soluble fertilizer particle in fluidized state with centrifugal blower, and the frequency of described centrifugal blower is 35-45Hz, preferably 38～42Hz, more preferably 40Hz; In described pre-heating step, temperature is 50-90 ℃, and preferably 65～90 ℃, this step can be carried out in rotary drum or fluidized-bed, and the rotary drum of various routines and fluidized-bed are all applicable, as can be fluidizer or drum device; Described coating liquid a and/or coating liquid b specifically can be delivered to the nozzle place of atomisation unit, described step 1 under the effect of transferpump) transfer rate of gained coating liquid a and/or coating liquid b is 10～200mL*min
-1, specifically can be 30-130mL*min
-1, 40-80mL*min
-1, 60-130mL*min
-1, preferred 20～150mL*min
-1; In described atomization steps, pressure is 0.05～0.75MPa, specifically can be 0.15-0.4MPa, 0.2-0.4MPa or 0.25-0.4MPa, preferably 0.10～0.50MPa.
Described solvent is selected from dimethyl sulfoxide (DMSO), etamon chloride, paraformaldehyde, N-methylmorpholine-N-oxide compound, 1-butyl-3-Methylimidazole chlorine, 1-allyl group-3-Methylimidazole chlorine, tetracol phenixin, zellon, ethyl acetate, butylacetate, isobutyl acetate, ethyl formate, methyl alcohol, ethanol, benzene, toluene, ethylbenzene, dimethylbenzene, acetone, hexanaphthene, normal hexane, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, water, ammoniacal liquor, at least one in formic acid and acetic acid, preferred dimethyl sulfoxide (DMSO), etamon chloride, N-methylmorpholine-N-oxide compound, 1-allyl group-3-Methylimidazole chlorine, zellon, ethyl acetate, ethanol, benzene, dimethylbenzene, acetone, hexanaphthene, N, N-N,N-DIMETHYLACETAMIDE, at least one in water and ammoniacal liquor, the mass percentage concentration of described ammoniacal liquor is 25-28%, the mass ratio of described Mierocrystalline cellulose and described solvent is 1%～6.5%, specifically can be 1.8-6.3%, 2.3-5.4% or 3.5-6.3%, preferably 3%～5%.
The present invention has adopted cellulose material to carry out modification coating, take rotary drum or fluidized-bed coating process is preparation method, solved the environment-stress problem that current film-coated controlled release fertilizer film material non-degradable causes edatope, the controlled release properties that improves cellulose materials in existing Mierocrystalline cellulose coated fertilizer invention makes it reach service requirements, specifically has the following advantages:
1) take cellulose materials as film material main component, to it, carry out chemical crosslinking modified, make coated fertilizer there is network molecular structure, hinder the release of fertilizer nutrient, realize the good controlled release properties of coated fertilizer, and make it have complete environmental degradability, the rete staying can be degradable in 2～3 years, and film material degraded product can not bring secondary pollution to crop and soil, has realized the environment friendly of film-coated controlled release fertilizer.
2) coated fertilizer be take cellulose material as film material main component, and raw material has advantages of wide material sources, cheap, and the film-coated controlled release fertilizer of preparation is lower than other polymer coating controlled release fertilizer cost, promotes field crop use and has economic feasibility.
3) use stripping auxiliary agent to control porosity and the pore size of polymer coating, realize the regulation and control of film material controlled release properties.
4) adopt rotary drum or fluidized-bed coating process, microfluid spraying coating improves the distribution uniformity of coated fertilizer on fertiliser granulates, and reaction conditions is gentle, solvent recoverable.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.
Following embodiment all evaluates controlled release properties and the degradation property of the cellulose modified film-coated controlled release fertilizer of gained by the following method:
Adopt GB/T 23348-2009 recommend method, concrete operations are as follows: the about 10g of film-coated controlled release fertilizer (claiming accurate to 0.01g) that takes preparation puts into the pouch that 100 order nylon gauzes are made, after sealing, pouch is put into 250mL vial or Plastic Bottle, add 200mL water, seal, be placed in respectively the biochemical constant incubator of 25 ℃ or 40 ℃, be 24h, 3d, 5d, 7d, 10d, 14d, 28d, 42d sample time, the timed interval of sampling is 28d later, until accumulation nutrient solubility rate reaches more than 80%, is considered as discharging completely.During sampling, bottle is turned upside down three times, make the strength of fluid in bottle consistent, move in 250mL volumetric flask, be settled to scale after being cooled to room temperature, in order to measuring nutrient, use.Then, to being equipped with in the bottle of test portion pouch, add again 200mL water, after sealing, put into biochemical constant incubator and continue to cultivate.Wherein, N element determination adopts the method for GB/T 8572-2001.
The controlled release properties evaluation index of film-coated controlled release fertilizer:
Initial stage solubility rate η
t1=M
t1/ M*100%, differential solubility rate η
t=(η
tn-η
t1)/(t
n-t
1) * 100%, accumulative total release rate η=∑ (η
tn), fertilizer releasing period T=1+ (80%-η
t1)/η
tn, t wherein
nbe n days, t
1be the 1st day, η
tnbe n days accumulative total release rates, η
t1for initial stage solubility rate, M
t1be the amount of nutrients of stripping in the 1st day, M is the total nutrient content in coated fertilizer.
Film-coated controlled release fertilizer film material degradation property is evaluated:
Accurately take the film-coated controlled release fertilizer coated fertilizer of preparation, imbed in natural soil environment, length of embedment is 10cm.Every 1 month, get sample one time, clean up material surface earth, dry weighing, Calculating material rate of weight loss.Material rate of weight loss W
l=W
0-W
t/ W
0* 100%, W
0for material initial mass, W
tthe quality of materials of constantly removing from soil for t.
Embodiment 1
1) take 55.4g carboxymethyl cellulose (purchased from traditional Chinese medicines group chemical reagent Beijing Company, product coding 68004180), in 2000mL distilled water, dissolve the aqueous solution that obtains carboxymethyl cellulose; Take again 34.6g linking agent N, the miscible linking agent N that obtains in 200mL distilled water of N-methylene-bisacrylamide and 0.02g catalyzer ceric ammonium nitrate, the aqueous solution of N-methylene-bisacrylamide and catalyzer ceric ammonium nitrate, and above-mentioned two aqueous solution are mixed, coating liquid a obtained;
Separately taking 10g film coalescence aid paraffin and 10g film coalescence aid turps is dissolved in and in 200mL ethyl acetate, obtains coating liquid b;
2) take the granular urea 1kg of particle diameter 3mm, be placed in fluidized-bed, open fluidized-bed air inducing switch and heating is preheated to 75 ℃ by this granular urea, then the air inducing frequency by regulating centrifugal blower makes it be fluidized state to 40Hz, by step 1) gained coating liquid b is with 40mL*min
-1speed by atomizing nozzle, make its atomization and be delivered in fluidized-bed, pressurized air atomizing pressure is 0.10Mpa, spraying 5min stop spraying, on fertiliser granulates surface, obtain hydrophobicity rete;
Again by step 1) gained coating liquid a makes its atomization and is delivered in fluidized-bed by atomizing nozzle, and wherein, the aqueous solution of carboxymethyl cellulose is with 40mL*min
-1speed by atomizing nozzle, be delivered in fluidized-bed, the aqueous solution of linking agent N,N methylene bis acrylamide and catalyzer ceric ammonium nitrate is with 20mL*min
-1speed by atomizing nozzle, be delivered in fluidized-bed, pressurized air atomizing pressure is 0.15Mpa, spraying 50min stops spraying, cooling down after 75 ℃ of insulation reaction 10min, in gained hydrophobicity rete outside, obtain cellulose layer, also obtain cellulose modified film-coated controlled release fertilizer provided by the invention.
The film-coated controlled release fertilizer that the invention described above provides is comprised of the fertiliser granulates of as fertilizer sources core layer, the cellulose layer that is wrapped in the hydrophobicity rete of described fertiliser granulates outside and is wrapped in described hydrophobicity rete outside.Wherein, the fertiliser granulates that forms fertilizer core layer is the granular urea of particle diameter 3mm, the material that forms hydrophobicity rete is that mass ratio is paraffin and the turps of 1: 1, the material that forms cellulose layer is that carboxymethyl cellulose is (purchased from traditional Chinese medicines group chemical reagent Beijing Company, product coding 68004180, the polymerization degree is 350-7000), linking agent N,N methylene bis acrylamide and catalyzer ceric ammonium nitrate.The mass ratio of the above-mentioned coating layer being comprised of hydrophobicity rete and cellulose layer and fertilizer core core is 0.1, linking agent N, the mass ratio of N-methylene-bisacrylamide and carboxymethyl cellulose is 62%, the mass ratio of catalyzer ceric ammonium nitrate and carboxymethyl cellulose is 0.04%, and the film coalescence aid paraffin that mass ratio is 1: 1 and the mass ratio of terebinthine gross weight and carboxymethyl cellulose are 36%.
Adopt water-extraction method to measure the controlled release properties of this film-coated controlled release fertilizer, initial stage solubility rate is 4.2%, and the controlled release phase is 35 days, 12 months rate of weight loss 34% of polymeric membrane material.
Embodiment 2
1) taking 76g mean polymerisation degree is that 350～7000 Microcrystalline Cellulose is (purchased from traditional Chinese medicines group chemical reagent Beijing Company, product coding 68005882), in the anhydrous N-methylmorpholine-N-of 1500mL solvent oxide compound (purchased from Shanghai He Yi Chemical Co., Ltd., product coding 72), dissolve the N-methylmorpholine-N-oxide solution that obtains Microcrystalline Cellulose.Separately take 45.6g linking agent epoxy chloropropane and be dissolved in the xylene solution that 500mL dimethylbenzene obtains linking agent epoxy chloropropane.Above-mentioned two solution are mixed, obtain coating liquid a;
Separately taking 10g film coalescence aid paraffin is dissolved in and in 200mL ethyl acetate, obtains coating liquid b;
2) take the granular urea 1kg of particle diameter 5mm, be placed in the rotary drum of drum device, opening the air inducing frequency of gas blower by regulating centrifugal blower makes fertiliser granulates be fluidized state to 38Hz, and heating is preheated to after 90 ℃ fertiliser granulates, by step 1) gained coating liquid a is delivered in rotary drum by atomizing nozzle, wherein, N-methylmorpholine-N-oxide solution of Microcrystalline Cellulose is with 30mL*min
-1speed by atomizing nozzle, make its atomization and be delivered in rotary drum, the xylene solution of linking agent epoxy chloropropane is with 10mL*min
-1speed by atomizing nozzle, make its atomization and be delivered in rotary drum, pressurized air atomizing pressure is 0.15Mpa, spraying 50min, stop spraying, after 90 ℃ of insulation reaction 30min are cooling, on granular urea surface, obtain cellulose layer;
Again by step 1) gained coating liquid b is with 40mL*min
-1speed by atomizing nozzle, be delivered in rotary drum, pressurized air atomizing pressure is 0.10Mpa, spraying 5min stops spraying, at cellulose layer, obtains hydrophobicity rete outward after cooling, also obtains cellulose modified film-coated controlled release fertilizer provided by the invention.
The film-coated controlled release fertilizer that the invention described above provides is comprised of the fertiliser granulates of as fertilizer sources core layer, the hydrophobicity rete that is wrapped in the cellulose layer of described fertiliser granulates outside and is wrapped in described cellulose layer outside.Wherein, the fertiliser granulates that forms fertilizer core layer is the granular urea of particle diameter 5mm, the material that forms hydrophobicity rete is paraffin, the material that forms cellulose layer is Microcrystalline Cellulose (purchased from traditional Chinese medicines group chemical reagent Beijing Company, product coding 68005882) and linking agent epoxy chloropropane.The mass ratio of the above-mentioned coating layer being comprised of hydrophobicity rete and cellulose layer and fertilizer core core is 0.1, and the mass ratio of linking agent epoxy chloropropane and Microcrystalline Cellulose is 60%, and the mass ratio of film coalescence aid paraffin and Microcrystalline Cellulose is 13%.
Adopt water-extraction method to measure the controlled release properties of this film-coated controlled release fertilizer, initial stage solubility rate is 5.4%, and the controlled release phase is 64 days, 12 months rate of weight loss 26% of polymeric membrane material.
Embodiment 3
1) taking mean polymerisation degree is that 350～7000 softwood pulp (purchased from waveguide technology company limited before Beijing) 76g, linking agent glutaraldehyde 15g and linking agent terpolycyantoamino-formaldehyde resin are (purchased from Taixing, Beijing Jia He commerce and trade company limited, product coding MF-40, viscosity-average molecular weight 3000～5000) 15g, miscible in 2000mL solvent distilled water, then obtain coating liquid a after adding catalyzer tosic acid 0.02g to mix;
Take 20g film coalescence aid sulphur and be dissolved in 200mL solvent tetracol phenixin, obtain coating liquid b;
2) take the granular urea 1kg of particle diameter 3mm, be placed in fluidized-bed, open fluidized-bed air inducing switch and heating is preheated to 80 ℃ by fertiliser granulates, then the air inducing frequency by regulating centrifugal blower is after fluidized state fertiliser granulates to 35Hz, by step 1) gained coating liquid b is with 20mL*min
-1speed by atomizing nozzle, be delivered in fluidized-bed, pressurized air atomizing pressure is 0.10Mpa, spraying 10min stop spraying, on granular urea surface, obtain hydrophobicity rete;
Again by step 1) gained coating liquid a is with 40mL*min
-1speed by atomizing nozzle, make its atomization and be delivered in fluidized-bed, pressurized air atomizing pressure is 0.25Mpa, spraying 50min stops after spraying, cooling down after 80 ℃ of insulation reaction 10min, in hydrophobicity rete outside, obtain cellulose layer, also obtain cellulose modified film-coated controlled release fertilizer provided by the invention.
The film-coated controlled release fertilizer that the invention described above provides is comprised of the fertiliser granulates of as fertilizer sources core layer, the cellulose layer that is wrapped in the hydrophobicity rete of described fertiliser granulates outside and is wrapped in described hydrophobicity rete outside.Wherein, the fertiliser granulates that forms fertilizer core layer is the granular urea of particle diameter 3mm, the material that forms hydrophobicity rete is sulphur, the material that forms cellulose layer is that softwood pulp (purchased from waveguide technology company limited before Beijing), linking agent glutaraldehyde and linking agent terpolycyantoamino-formaldehyde resin are (purchased from Taixing, Beijing Jia He commerce and trade company limited, product coding MF-40, viscosity-average molecular weight 3000～5000).The mass ratio of the above-mentioned coating layer being comprised of hydrophobicity rete and cellulose layer and fertilizer core core is 0.1, mass ratio is that the linking agent glutaraldehyde of 1: 1 and the gross weight of linking agent terpolycyantoamino-formaldehyde resin and the mass ratio of softwood pulp are 39%, the mass ratio of catalyzer tosic acid and softwood pulp is 0.03%, and the mass ratio of film coalescence aid sulphur and softwood pulp is 26%.
Adopt water-extraction method to measure the controlled release properties of this film-coated controlled release fertilizer, initial stage solubility rate is 8.3%, and the controlled release phase is 26 days, 12 months rate of weight loss 47% of polymeric membrane material.
Embodiment 4
1) taking mean polymerisation degree is that 350～7000 carboxymethyl cellulose is (purchased from traditional Chinese medicines group chemical reagent Beijing Company, product coding 68004180) 76g, linking agent glutaraldehyde 28g, softening agent glycerine 15g, be dissolved in 3000mL distilled water, then add catalyzer tosic acid 0.02g to mix to obtain coating liquid a;
Take 10g film coalescence aid paraffin and be dissolved in 200mL ethyl acetate, obtain coating liquid b;
2) take the granular urea 1kg of particle diameter 3mm, be placed in fluidized-bed, open fluidized-bed air inducing switch and heat fertiliser granulates is preheated to 80 ℃, then by regulating the air inducing frequency of centrifugal blower to 42Hz, fertiliser granulates being after fluidized state, by step 1) gained coating liquid b is with 40mL*min
-1speed by atomizing nozzle, be delivered in fluidized-bed, pressurized air atomizing pressure is 0.10Mpa, spraying 5min, stop spraying, on granular urea surface, obtain hydrophobicity rete;
Again by step 1) gained coating liquid a is with 130mL*min
-1speed by atomizing nozzle, make its atomization and be delivered in fluidized-bed, pressurized air atomizing pressure is 0.40Mpa, spraying 30min stops spraying, cooling down after 80 ℃ of insulation reaction 10min, in hydrophobicity rete outside, obtain cellulose layer, also obtain cellulose modified film-coated controlled release fertilizer provided by the invention.
The film-coated controlled release fertilizer that the invention described above provides is comprised of the fertiliser granulates of as fertilizer sources core layer, the cellulose layer that is wrapped in the hydrophobicity rete of described fertiliser granulates outside and is wrapped in described hydrophobicity rete outside.Wherein, the fertiliser granulates that forms fertilizer core layer is the granular urea of particle diameter 3mm, the material that forms hydrophobicity rete is paraffin, the material that forms cellulose layer is carboxymethyl cellulose (purchased from traditional Chinese medicines group chemical reagent Beijing Company, product coding 68004180), linking agent glutaraldehyde, softening agent glycerine and catalyzer tosic acid.The mass ratio of the above-mentioned coating layer being comprised of hydrophobicity rete and cellulose layer and fertilizer core core is 0.1, the mass ratio of linking agent glutaraldehyde and carboxymethyl cellulose is 37%, the mass ratio of softening agent glycerine and carboxymethyl cellulose is 19%, the mass ratio of catalyzer tosic acid and carboxymethyl cellulose is 0.03%, and the mass ratio of film coalescence aid paraffin and carboxymethyl cellulose is 13%.
Adopt water-extraction method to measure the controlled release properties of this film-coated controlled release fertilizer, initial stage solubility rate is 9.8%, and the controlled release phase is 27 days, 12 months rate of weight loss 62% of polymeric membrane material.
Embodiment 5
1) taking mean polymerisation degree is that 350～7000 hydroxypropylcellulose is (purchased from traditional Chinese medicines chemical reagents corporation, molecular weight 80,000, production code member A43500702) 76g, linking agent Tetra hydro Phthalic anhydride 25g, softening agent mean polymerisation degree is that 900～1500 polyvinyl alcohol is (purchased from traditional Chinese medicines group chemical reagent Beijing Company, product coding 30153194, weight-average molecular weight 1750) 15g, after mixing, adding distil water 4000mL adds again catalyzer 0.05g sodium dihydrogen phosphite NaH
2pO
2h
2o mixes, and obtains coating liquid a;
Take 10g paraffin and be dissolved in 200mL ethyl acetate, obtain coating liquid b;
2) take composite fertilizer of 16-16-16 Fuji (the chemical fertilizer company limited of Shandong Fuji that particle diameter is 3mm, lot number 201051209404) 1kg, be placed in fluidized-bed, open fluidized-bed air inducing switch and heat fertiliser granulates is preheated to 80 ℃, then by regulating the air inducing frequency of centrifugal blower to 40Hz, fertiliser granulates being after fluidized state, by step 1) gained coating liquid b is with 40mL*min
-1speed by atomizing nozzle, make its atomization and be delivered in fluidized-bed, pressurized air atomizing pressure is 0.10Mpa, spraying 5min stop spraying, on compound fertilizer granules surface, obtain hydrophobicity rete;
Again by step 1) gained coating liquid a is with 80mL*min
-1speed by atomizing nozzle, make its atomization and be delivered in fluidized-bed, pressurized air atomizing pressure is 0.20Mpa, spraying 50min stops spraying, cooling down after 80 ℃ of insulation reaction 10min, in hydrophobicity rete outside, obtain cellulose layer, also obtain cellulose modified film-coated controlled release fertilizer provided by the invention.
The film-coated controlled release fertilizer that the invention described above provides is comprised of the fertiliser granulates of as fertilizer sources core layer, the cellulose layer that is wrapped in the hydrophobicity rete of described fertiliser granulates outside and is wrapped in described hydrophobicity rete outside.Wherein, the fertiliser granulates that forms fertilizer core layer is composite fertilizer of 16-16-16 Fuji (the chemical fertilizer company limited of Shandong Fuji of particle diameter 3mm, lot number 201051209404), the material that forms hydrophobicity rete is paraffin, and the material that forms cellulose layer is hydroxypropylcellulose, linking agent Tetra hydro Phthalic anhydride, softening agent polyvinyl alcohol and catalyzer sodium dihydrogen phosphite.The mass ratio of the above-mentioned coating layer being comprised of hydrophobicity rete and cellulose layer and fertilizer core core is 0.1, the mass ratio of linking agent Tetra hydro Phthalic anhydride and carboxy-propyl cellulose is 33%, the mass ratio of softening agent polyvinyl alcohol and carboxy-propyl cellulose is 20%, the mass ratio of catalyzer sodium dihydrogen phosphite and carboxy-propyl cellulose is 0.07%, and the mass ratio of film coalescence aid paraffin and carboxy-propyl cellulose is 13%.
Adopt water-extraction method to measure the controlled release properties of this film-coated controlled release fertilizer, initial stage solubility rate is 7.5%, and the controlled release phase is 42 days, 12 months rate of weight loss 41% of polymeric membrane material.
Embodiment 6
1) taking mean polymerisation degree is 350～7000 softwood pulp (purchased from waveguide technology company limited before Beijing) 76g, measure solvent N-methylmorpholine-N-oxide compound (purchased from Shanghai He Yi Chemical Co., Ltd., product coding 72) 1200mL adds 10g film coalescence aid turps after dissolving this Mierocrystalline cellulose of swelling again, mixes and obtains coating liquid 1; Take after linking agent hexamethylene diisocyanate 42g and 200mL solvent hexanaphthene mix and add again catalyst of triethylamine 0.05g, obtain coating liquid 2;
2) take composite fertilizer of 16-16-1616-16-16 Fuji that particle diameter is 3mm (purchased from chemical fertilizer company limited of Shandong Fuji, lot number 201051209404) 1kg, be placed in the rotary drum of drum device, open gas blower by regulating the air inducing frequency of centrifugal blower to 40Hz, make fertiliser granulates be fluidized state, and 85 ℃ of this fertiliser granulates of preheating, by step 1) gained coating liquid 1 and coating liquid 2 be respectively with 60mL*min
-1and 10mL*min
-1speed by atomizing nozzle, make its atomization and be delivered in rotary drum, pressurized air atomizing pressure is 0.20Mpa, after all spraying 20min, stop spraying, cooling down after 80 ℃ of insulation reaction 10min, obtains cellulose modified film-coated controlled release fertilizer provided by the invention.
The film-coated controlled release fertilizer that the invention described above provides is comprised of with the cellulose layer that is wrapped in described fertiliser granulates outside the fertiliser granulates of as fertilizer sources core layer.Wherein, the fertiliser granulates that forms fertilizer core layer is that the composite fertilizer of 16-16-1616-16-16 Fuji of particle diameter 3mm is (purchased from chemical fertilizer company limited of Shandong Fuji, lot number 201051209404), the material of formation cellulose layer is softwood pulp (purchased from waveguide technology company limited before Beijing), linking agent hexamethylene diisocyanate.The mass ratio of the above-mentioned coating layer being comprised of hydrophobicity rete and cellulose layer and fertilizer core core is 0.1, and the mass ratio of linking agent hexamethylene diisocyanate and softwood pulp is 55%, and the mass ratio of film coalescence aid turps and softwood pulp is 13%.
Adopt water-extraction method to measure the controlled release properties of this film-coated controlled release fertilizer, initial stage solubility rate is 4.7%, and the controlled release phase is 56 days, 12 months rate of weight loss 29% of polymeric membrane material.
Embodiment 7
1) taking mean polymerisation degree is 350～7000 the 76g of bardwood pulp (purchased from waveguide technology company limited before Beijing), then takes solvent 1-butyl-3-Methylimidazole chlorine 2000g and be heated to 80 ℃ of meltings, obtains coating liquid 1; Take linking agent toluene diisocyanate trimer 48g, be dissolved in 1000mL toluene, then add catalyzer dibutyl tin laurate 0.05g, obtain coating liquid 2; This coating liquid 1 and coating liquid 2 are mixed, obtain coating liquid a;
Take 12g film coalescence aid paraffin and be dissolved in 200mL ethyl acetate, obtain coating liquid b;
2) take composite fertilizer of 16-16-16 Fuji (the chemical fertilizer company limited of Shandong Fuji that particle diameter is 3mm, lot number 201051209404) 1kg, be placed in fluidized-bed, open fluidized-bed air inducing switch and heating and make this fertiliser granulates be preheated to 90 ℃, then the air inducing frequency by regulating centrifugal blower makes fertiliser granulates be fluidized state to 40Hz.By step 1) prepare gained coating liquid 1 and 2 respectively with 20mL*min
-1speed by atomizing nozzle, make its atomization and be delivered in fluidized-bed, pressurized air atomizing pressure is 0.20Mpa, all sprays after 50min and stops spraying, cooling down after 90 ℃ of insulation reaction 10min, obtains cellulose layer on fertiliser granulates surface;
Again by step 1) gained coating liquid b is with 40mL*min
-1speed by atomizing nozzle, make its atomization and be delivered in fluidized-bed, pressurized air atomizing pressure is 0.10Mpa, spraying 5min stops after spraying, cooling down after 80 ℃ of insulation 3min, in cellulose layer outside, obtain hydrophobicity rete, also obtain cellulose modified film-coated controlled release fertilizer provided by the invention.
The film-coated controlled release fertilizer that the invention described above provides is comprised of with the cellulose layer that is wrapped in described fertiliser granulates outside the fertiliser granulates of as fertilizer sources core layer.Wherein, the fertiliser granulates that forms fertilizer core layer is composite fertilizer of 16-16-16 Fuji (the chemical fertilizer company limited of Shandong Fuji of particle diameter 3mm, lot number 201051209404), the material of formation cellulose layer is bardwood pulp (purchased from waveguide technology company limited before Beijing), linking agent toluene diisocyanate trimer and catalyzer dibutyl tin laurate.The mass ratio of the above-mentioned coating layer being comprised of hydrophobicity rete and cellulose layer and fertilizer core core is 0.1, the mass ratio of linking agent toluene diisocyanate trimer and bardwood pulp is 63%, and the mass ratio of catalyzer dibutyl tin laurate and bardwood pulp is 0.07%.
Adopt water-extraction method to measure the controlled release properties of this film-coated controlled release fertilizer, initial stage solubility rate is 7.9%, and the controlled release phase is 33 days, 12 months rate of weight loss 53% of polymeric membrane material.
Claims (9)
1. a cellulose modified film-coated controlled release fertilizer, is comprised of fertilizer core layer and the coating layer being positioned at outside described fertilizer core layer; It is characterized in that: the material that forms described fertilizer core layer is fertiliser granulates; Described coating layer comprises cellulose layer and hydrophobicity rete;
The material that forms described cellulose layer is by least one composition in Mierocrystalline cellulose, linking agent, catalyzer and following compound: softening agent and stripping auxiliary agent;
The material that forms described hydrophobicity rete is film coalescence aid;
The preparation method of described cellulose modified film-coated controlled release fertilizer, comprises the steps:
1) at least one in described Mierocrystalline cellulose, linking agent, catalyzer and following compound mixed and obtain coating liquid a in solvent: softening agent and stripping auxiliary agent; This mixes in step, adopts mixing apparatus to realize the well blend of high viscosity liquid; Mierocrystalline cellulose reacts with linking agent under the effect of catalyzer, completes cellulosic chemical modification;
Described film coalescence aid is mixed and obtains coating liquid b in described solvent;
Or, at least one in described Mierocrystalline cellulose, described linking agent, catalyzer, described film coalescence aid and following compound mixed to the mixture that obtains coating liquid a and coating liquid b in solvent: softening agent and stripping auxiliary agent;
2) the described fertiliser granulates in fluidized state is carried out after preheating, after described fertiliser granulates after described step 1) gained coating liquid a and/or coating liquid b and preheating is mixed, step 1) gained coating liquid a and/or coating liquid b described in atomization, make it evenly be sprayed on described fertiliser granulates surface, coolingly after insulation reaction obtain described cellulose modified film-coated controlled release fertilizer;
Described step 1) mixes in step, and temperature is 30～100 ℃;
Described step 2), in, the described described fertiliser granulates in fluidized state, makes described fertiliser granulates in fluidized state with centrifugal blower; In described pre-heating step, temperature is 50-90 ℃; Described mixing in step, the transfer rate of described step 1) gained coating liquid a and/or coating liquid b is 10～200mL/min; In described atomization steps, pressure is 0.05～0.75MPa;
Described step 2), in, the frequency of described centrifugal blower is 35～45Hz;
Described solvent is selected from dimethyl sulfoxide (DMSO), etamon chloride, paraformaldehyde, N-methylmorpholine-N-oxide compound, 1-butyl-3-Methylimidazole chlorine, 1-allyl group-3-Methylimidazole chlorine, tetracol phenixin, zellon, ethyl acetate, butylacetate, isobutyl acetate, ethyl formate, methyl alcohol, ethanol, benzene, toluene, ethylbenzene, dimethylbenzene, acetone, hexanaphthene, normal hexane, N, at least one in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, water, ammoniacal liquor, formic acid and acetic acid; The mass percentage concentration of described ammoniacal liquor is 25-28%; The mass ratio of described Mierocrystalline cellulose and described solvent is 1%～6.5%.
2. fertilizer according to claim 1, is characterized in that: described coating layer is one deck, by described cellulose layer and described hydrophobicity rete, is mixed.
3. fertilizer according to claim 1, is characterized in that: described coating layer is two-layer, and wherein one deck is described cellulose layer, and another layer is described hydrophobicity rete.
4. according to the arbitrary described fertilizer of claim 1-3, it is characterized in that: the particle diameter of described fertiliser granulates is 2～6mm; Described fertiliser granulates is selected from urea, volatile salt, ammonium nitrate, ammonium sulfate, vitriolate of tartar, Repone K, saltpetre, Secondary ammonium phosphate, primary ammonium phosphate, contains micro-fertilizer and at least one in Chemical Mixed Fertilizer; Wherein, described in contain in micro-fertilizer, at least one in described micro-chosen from Fe, manganese, boron, zinc, copper and molybdenum;
Described Mierocrystalline cellulose is selected from paper pulp, Microcrystalline Cellulose, hemicellulose, methylcellulose gum, ethyl cellulose, propyl cellulose, methylethyl cellulose, Walocel MT 20.000PV, Natvosol, hydroxypropylcellulose, Type 3U, cyanoethyl cellulose, ethyl-cyanoethyl cellulose, hydroxyethylmethyl-cellulose, Vltra tears, carboxymethyl cellulose, soluble cotton, phosphorylated cotton, cellulose acetate, at least one of cellulose acetate propionate and cellulose acetate butyrate, wherein, described paper pulp is selected from least one in bardwood pulp, softwood pulp, jute pulp and bamboo pulp, described cellulosic mean polymerisation degree is 150～15000,
Described linking agent is selected from formaldehyde, oxalic dialdehyde, glutaraldehyde, Alpha-hydroxy hexanedial, four polyoxymethylene, trimeric cyanamide, terpolycyantoamino-formaldehyde resin, methane amide, ethanamide, N,N methylene bis acrylamide, N hydroxymethyl acrylamide, divinyl sulfone, oxyethane, propylene oxide, epoxy chloropropane, acrylate chloride, oxalyl chloride, diallyl amine, oxalic acid, hexanodioic acid, maleic acid, 1,2,3,4-fourth tetracid, polymaleic acid, polyacrylic acid, succsinic acid, oxalic acid acid anhydride, Tetra hydro Phthalic anhydride, Succinic anhydried, ethylene two (N-methylol carbamate), tolylene diisocyanate, diphenylmethanediisocyanate, liquefaction diphenylmethanediisocyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, to phenylmethane vulcabond, Isosorbide-5-Nitrae-bicyclohexane vulcabond, xylylene diisocyanate, cyclohexanedimethyleterephthalate vulcabond, Methylcyclohexyl diisocyanate, norbornene alkyl diisocyanate, polymethylene multi-phenenyl isocyanate, toluene diisocyanate dimer, toluene diisocyanate trimer, tolylene diisocyanate-hexamethylene diisocyanate mixing polymer, hexamethylene diisocyanate trimer, at least one in hexamethylene diisocyanate biuret and isoflurane chalcone diisocyanate tripolymer,
Described catalyzer is selected from perchloric acid, the vitriol oil, phosphoric acid, hydrochloric acid, tosic acid, sodium dihydrogen phosphite, Tetrafluoroboric acid zinc, dibutyl tin laurate, stannous octoate, triethylamine, dimethyl cetylamine, ceric ammonium nitrate, two dimethyl aminoethyl ether, diethylenetriamine, diethylenetriamine, tetrabutyl butane diamines, N-Ethylmorphine quinoline, N, N-dimethylcyclohexylamine, trolamine, methyldiethanolamine, dimethylethanolamine, pyridine, N, N-lutidine, 1, 2, 4-tri methyl piperazine, at least one in two ketoimines and α-mercaptobenzimidazole,
Described softening agent is selected from least one in polyvinyl alcohol, glycerine, dioctyl phthalate (DOP), dibutyl phthalate and diheptyl phthalate; Wherein, the mean polymerisation degree of described polyvinyl alcohol is 700～1800;
Described film coalescence aid is selected from least one in paraffin, rosin, petroleum resin, turps, sulphur, clorafin, sulfonation paraffin and terpine resin;
The mass ratio of described coating layer and described fertilizer core layer is 0.02～0.13;
Described linking agent and described cellulosic mass ratio are 0.5%～70%;
Described catalyzer and described cellulosic mass ratio are 0.02%～0.07%;
Described softening agent and described cellulosic mass ratio are 0.5%～20%;
Described film coalescence aid and described cellulosic mass ratio are 0.5%～36%.
5. fertilizer according to claim 4, is characterized in that: the particle diameter of described fertiliser granulates is 3～5mm; Described fertiliser granulates is selected from least one in urea, ammonium sulfate, vitriolate of tartar, Repone K, saltpetre, Secondary ammonium phosphate and primary ammonium phosphate;
Described Mierocrystalline cellulose is selected from least one in Mierocrystalline cellulose, Microcrystalline Cellulose, methylcellulose gum, ethyl cellulose, Walocel MT 20.000PV, Type 3U, hydroxyethylmethyl-cellulose, carboxymethyl cellulose, soluble cotton, phosphorylated cotton, cellulose acetate and cellulose acetate propionate; Described cellulosic mean polymerisation degree is 200～10000;
Described linking agent be selected from formaldehyde, oxalic dialdehyde, glutaraldehyde, terpolycyantoamino-formaldehyde resin, N,N methylene bis acrylamide, oxalic acid, hexanodioic acid, oxyethane, epoxy chloropropane, acrylate chloride, Tetra hydro Phthalic anhydride, tolylene diisocyanate, diphenylmethanediisocyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate, polymethylene multi-phenenyl isocyanate, at least one in phenylmethane vulcabond, toluene diisocyanate dimer, toluene diisocyanate trimer and isoflurane chalcone diisocyanate tripolymer;
Described catalyzer is selected from the vitriol oil, phosphoric acid, tosic acid, dibutyl tin laurate, stannous octoate, triethylamine, ceric ammonium nitrate, N, N-dimethylcyclohexylamine, trolamine, pyridine and N, at least one in N-lutidine;
Described softening agent is selected from least one in polyvinyl alcohol, glycerine, dioctyl phthalate (DOP) and diheptyl phthalate; Wherein, the mean polymerisation degree of described polyvinyl alcohol is 900～1500;
Described film coalescence aid is selected from least one in paraffin, sulfonation paraffin, turps and petroleum resin;
The mass ratio of described coating layer and described fertilizer core layer is 0.03～0.10;
Described linking agent and described cellulosic mass ratio are 5%～70%;
Described catalyzer and described cellulosic mass ratio are 0.03%～0.04%;
Described softening agent and described cellulosic mass ratio are 0.5%～10%;
Described film coalescence aid and described cellulosic mass ratio are 0.5%～7%.
6. fertilizer according to claim 4, is characterized in that: the nitrogen initial stage solubility rate of described cellulose modified coated release-controlled rate is 4.2-9.8%, and the controlled release phase of nitrogen is 26-64 days, and the film rate of weight loss of 12 months is 26-62%.
7. a method of preparing the arbitrary described cellulose modified film-coated controlled release fertilizer of claim 1-6, comprises the steps:
1) at least one in described Mierocrystalline cellulose, linking agent, catalyzer and following compound mixed and obtain coating liquid a in solvent: softening agent and stripping auxiliary agent; This mixes in step, adopts mixing apparatus to realize the well blend of high viscosity liquid; Mierocrystalline cellulose reacts with linking agent under the effect of catalyzer, completes cellulosic chemical modification;
Described film coalescence aid is mixed and obtains coating liquid b in described solvent;
Or, at least one in described Mierocrystalline cellulose, described linking agent, catalyzer, described film coalescence aid and following compound mixed to the mixture that obtains coating liquid a and coating liquid b in solvent: softening agent and stripping auxiliary agent;
2) the described fertiliser granulates in fluidized state is carried out after preheating, after described fertiliser granulates after described step 1) gained coating liquid a and/or coating liquid b and preheating is mixed, step 1) gained coating liquid a and/or coating liquid b described in atomization, make it evenly be sprayed on described fertiliser granulates surface, coolingly after insulation reaction obtain described cellulose modified film-coated controlled release fertilizer;
Described step 1) mixes in step, and temperature is 30～100 ℃;
Described step 2), in, the described described fertiliser granulates in fluidized state, makes described fertiliser granulates in fluidized state with centrifugal blower; In described pre-heating step, temperature is 50-90 ℃; Described mixing in step, the transfer rate of described step 1) gained coating liquid a and/or coating liquid b is 10～200mL/min; In described atomization steps, pressure is 0.05～0.75MPa;
Described step 2), in, the frequency of described centrifugal blower is 35～45Hz;
Described solvent is selected from dimethyl sulfoxide (DMSO), etamon chloride, paraformaldehyde, N-methylmorpholine-N-oxide compound, 1-butyl-3-Methylimidazole chlorine, 1-allyl group-3-Methylimidazole chlorine, tetracol phenixin, zellon, ethyl acetate, butylacetate, isobutyl acetate, ethyl formate, methyl alcohol, ethanol, benzene, toluene, ethylbenzene, dimethylbenzene, acetone, hexanaphthene, normal hexane, N, at least one in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, water, ammoniacal liquor, formic acid and acetic acid; The mass percentage concentration of described ammoniacal liquor is 25-28%; The mass ratio of described Mierocrystalline cellulose and described solvent is 1%～6.5%.
8. method according to claim 7, is characterized in that: described step 1) mixes in step, and temperature is 50～90 ℃;
Described step 2), in, in described pre-heating step, temperature is 65～90 ℃; Described mixing in step, the transfer rate of described step 1) gained coating liquid a and/or coating liquid b is 20～150mL/min; In described atomization steps, pressure is 0.10～0.50MPa;
Described step 2), in, the frequency of described centrifugal blower is 38～42Hz.
9. according to the method described in claim 7 or 8, it is characterized in that: described solvent is selected from least one in dimethyl sulfoxide (DMSO), etamon chloride, N-methylmorpholine-N-oxide compound, 1-allyl group-3-Methylimidazole chlorine, zellon, ethyl acetate, ethanol, benzene, dimethylbenzene, acetone, hexanaphthene, N,N-dimethylacetamide, water and ammoniacal liquor; The mass ratio of described Mierocrystalline cellulose and described solvent is 3%～5%.
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