CN1854111A - Dressed slow-releasing fertilizer and its production - Google Patents
Dressed slow-releasing fertilizer and its production Download PDFInfo
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- CN1854111A CN1854111A CN 200510038958 CN200510038958A CN1854111A CN 1854111 A CN1854111 A CN 1854111A CN 200510038958 CN200510038958 CN 200510038958 CN 200510038958 A CN200510038958 A CN 200510038958A CN 1854111 A CN1854111 A CN 1854111A
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Abstract
A coated slow-releasing fertilizer and its production are disclosed. The volume fraction of nanometer resistant inorganic filler with average particle size<1 mum is 0.5-80%, volume fraction of polar bonding material is 99.5-20%. It has long total-distance stripping time and excellent slow-releasing performance.
Description
One technical field
The present invention relates to a kind of enveloped slow release fertilizer and preparation method thereof, belong to fertilizer and manufacturing field thereof.
Two background technologies
At present, agrochemical all is instant fertilizer basically, and they are dissolving rapidly in water, the problem that the fertilising initial stage " burns out " root system of plant may occur thus.The effective rate of utilization of instant fertilizer is lower, must excessively use the demand that could guarantee farm crop, and the excessive fertilizer of using is not utilized by crop absorption, but environment is caused serious pollution, surface water and phreatic eutrophication occur such as some area.Particularly the excessive of fertilizer used, and not only increases the agricultural prods cost, and causes residual chemical fertilizer component content severe overweight in farm crop such as cereal, wheat, the vegetables etc., and people's safe diet is constituted grave danger.Development and utilization is slow release fertilizer efficiently, becomes the inexorable trend of countries in the world agrochemical.
At present, slow release fertilizer mainly contains organic synthesis type slow release fertilizer and enveloped slow release fertilizer two classes.
Urea formaldehyde, isobutylidene two ureas, urea acetaldehyde etc. are organic synthesis type slow release fertilizer.The nutrient of such fertilizer discharges slowly, and utilization rate of fertilizer improves, but its nutrient release rate is subjected to the influence of various factorss such as soil moisture, pH value, microorganism, can not control fertilizer nutrient artificially and discharge the rhythm and pace of moving things, and the product cost height, being difficult to extensively promote the use of, development is restricted.
Enveloped slow release fertilizer is at fertiliser granulates surface-coated organic polymer or inorganics, forms fine and close low-permeability coating, to slow down and to control the dissolution rate of fertilizer, reaches the purpose of slowly-releasing.The gas barrier properties of coating are good more, and fertilizer diffusion stripping is just slow more; The gas barrier properties of coating are poor more, and fertilizer diffusion stripping is fast more.By the gas barrier properties of control coating, the dissolution rate of may command fertilizer is realized the slow release of instant fertilizer.
Press the constitutive property of coating material, enveloped slow release fertilizer can be divided into inorganics enveloped slow release fertilizer and organic polymer enveloped slow release fertilizer two big classes.Press the nonpolar nature of coating material, enveloped slow release fertilizer can be divided into polarity enveloped slow release fertilizer and nonpolar enveloped slow release fertilizer two big classes.The inorganics enveloped slow release fertilizer belongs to the polarity enveloped slow release fertilizer more, and organic polymer enveloped slow release fertilizer Semi-polarity enveloped slow release fertilizer and nonpolar enveloped slow release fertilizer are all very important.
Sulfur coated urea is a kind of inorganic enveloped slow release fertilizer with fertilizer bag fertilizer of developing the earliest.But sulphur usually exists " pin hole " or crack as coating material coated fertilizer particle surface well in the coating, and sulphur is more crisp simultaneously, store and transportation in be easy to come off, so the sulfur envelope type slow release fertilizer sustained release performance is not good.Japan prepares inorganic enveloped slow release fertilizer with silicate and metal oxide as coating agent, but because silicate is soluble in water, so the slow-release period of slow release fertilizer is not long yet.To develop with nitrogen phosphorus potassium mud be binding agent in China, urea ammonium nitrate core wrapped up and the Envelope type compound manure that forms with phosphate fertilizer such as fused(calcium magnesium)phosphate, precipitated superphosphate or bone meal.This class fertilizer is immersed in the water, and the urea of core and ammonium nitrate is all strippings in 1.5～2 hours very short time, can not realize slow release.Although by follow-up improvement dissolution time is prolonged to some extent, the omnidistance dissolution time of fertilizer also has only 10～20 days.The gas barrier ability of inorganics coating is generally relatively poor, thus the sustained release performance of inorganics enveloped slow release fertilizer coating not good be a general problem.
Press the nonpolar nature of organic polymer, the organic polymer enveloped slow release fertilizer can be divided into non-polar polymer enveloped slow release fertilizer and polar polymer enveloped slow release fertilizer two classes.Wherein an outstanding problem existing of polar polymer enveloped slow release fertilizer is coating the gas barrier ability is not too high, therefore the omnidistance dissolution time of polar polymer enveloped slow release fertilizer is short partially, it particularly is the polar polymer that contains in the molecular structure than polyoxy, nitrogen isopolarity element, as urea-formaldehyde resin, polyvinyl acetal resin, melamine resin, unsaturated polyester, Resins, epoxy, resol etc., because of its wetting ability strong, the gas barrier ability is low, the omnidistance dissolution time of its enveloped slow release fertilizer was shorter, as several days or more than 20 day.The gas barrier ability that improves the polar polymer coating is the key issue that the polar polymer enveloped slow release fertilizer will solve.
In addition, because the inorganics that the enveloped slow release fertilizer coating is used and the price height of organic polymer, especially the organic polymer price is higher, so that enveloped slow release fertilizer is on the high side, make it be difficult at present obtain to apply on a large scale, therefore reducing cost becomes another key issue that enveloped slow release fertilizer will solve.
Three summary of the invention
The present invention is intended to improve the gas barrier ability of polarity coating, the low polarity enveloped slow release fertilizer of preparation fertilizer dissolution rate, solve the polarity enveloped slow release fertilizer, especially the short partially problem of polar polymer enveloped slow release fertilizer sustained release performance deficiency, omnidistance dissolution time, and reduce the cost of enveloped slow release fertilizer simultaneously, favourable applying.The present invention also provides the preparation method of described enveloped slow release fertilizer.
Realize that the object of the invention technical solution is:
A kind of enveloped slow release fertilizer, coating by fertilizer and fertilizer outside constitutes, coating comprises the gas barrier mineral filler less than 1 μ m of polarity sizing and median size, wherein median size is 0.5%～80% less than the volume fraction of the gas barrier mineral filler of 1 μ m, and the volume fraction of polarity sizing is 99.5%～20%.
Described gas barrier mineral filler can be in lime carbonate, silicon-dioxide, carbon black, magnesiumcarbonate, zinc carbonate, calcium sulfate, barium sulfate, aluminium sesquioxide, titanium dioxide, ferric oxide, magnesium oxide, zinc oxide, aluminium hydroxide, the silicon carbide one or more.It can also be other nano level gas barrier mineral filler.
Described polarity sizing can be the mixed type polarity sizing of polar polymer sizing, the inorganic sizing of polarity or the inorganic sizing of polar polymer sizing-polarity.
Described polar polymer sizing can be urea-formaldehyde resin, polyvinyl acetal resin, melamine resin, unsaturated polyester, urethane, Synolac, Resins, epoxy, resol, unsaturated oil, furane resin, the cyclopentadiene multipolymer, paracril, chloroprene rubber, polyacrylic ester and multipolymer thereof, chlorinatedpolyolefins, polyvinyl chloride and multipolymer thereof, polyvinyl dichloride and multipolymer thereof, ethene-carbon dioxide copolymer, polyvinyl acetate (PVA) and multipolymer thereof, polyacrylonitrile and multipolymer thereof, polymeric amide, thermoplastic polyester, nitrocellulose, rosin, in the chitin derivative one or more.It can also be other polar polymer sizing.
The inorganic sizing of described polarity can be the one of any of following response composite or the multiple sizing that solidify to form arbitrarily: 1. modulus is 1～3 the water glass and the mixed aqueous solution of phosphoric acid; 2. modulus is 1～3 the potassium silicate and the mixed aqueous solution of phosphoric acid; 3. SiO
2Colloidal sol.It can also be other the inorganic sizing of polarity.
Can also contain the adjusting auxiliary agent in the coating of described enveloped slow release fertilizer.Regulate the auxiliary agent scope and comprise tensio-active agent, softening agent, reactive thinner, solidifying agent, promotor, catalyzer, defoamer, organic filler, water-soluble inorganic salt, water-soluble nutriment in a fertilizer and sulphur etc.
A kind of method for preparing described enveloped slow release fertilizer, carry out following steps successively:
The first step is coated on the granulated fertilizer surface with the sizing composition, forms coating on the granulated fertilizer surface;
In second step, the gas barrier mineral filler is sticked on the viscosity coating on granulated fertilizer surface;
In the 3rd step, repeat the first step and second step, until meeting the requirements of membrane wrapping thickness;
The 4th step was solidified until completion of cure the coating of granulated fertilizer, promptly made enveloped slow release fertilizer.
Among the described preparation method of enveloped slow release fertilizer of the present invention, the sizing composition is coated on the granulated fertilizer surface under negative pressure state, carries out with the process that forms coating.
Among the described preparation method of enveloped slow release fertilizer of the present invention, stick to the gas barrier mineral filler on the granulated fertilizer surface viscosity coating after, granulated fertilizer surface viscosity coating is suitably solidified.
Among the described preparation method of enveloped slow release fertilizer of the present invention, after the viscosity coating by the granulated fertilizer surface adheres to the gas barrier mineral filler for the last time, again at granulated fertilizer surface-coated sizing composition.
Among the described preparation method of enveloped slow release fertilizer of the present invention, granulated fertilizer surface viscosity coating adheres to the process of filler to carry out under negative pressure state.
Among the described preparation method of enveloped slow release fertilizer of the present invention, in granulated fertilizer coating solidified process, being solidificated under the negative pressure state before not being clamminess in the granulated fertilizer surface carried out.
Compared with prior art, the present invention has following remarkable advantage: add the gas barrier mineral filler in the coating of (1) enveloped slow release fertilizer of the present invention, can reduce the fertilizer stripping aisle spare of granulated fertilizer coating, reduce the fertilizer dissolution rate thereby reach, so the sustained release performance excellence of enveloped slow release fertilizer of the present invention.(2) the gas barrier mineral filler of the present invention's employing is the nano level gas barrier mineral filler of median size less than 1 μ m, and the nano grade inorganic filler all has tangible enhancing toughening effect usually to polymkeric substance, therefore can reduce membrane wrapping thickness, promptly reduces the coating consumption.(3) membrane wrapping thickness of enveloped slow release fertilizer is generally micron order, therefore can hold tens even more nano level gas barrier inorganic filler particle in the radial direction of micron order coating, the stochastic distribution of nano level gas barrier mineral filler in coating will make fertilizer stripping passage become sinuate detouring, so that fertilizer stripping path is that the actual thickness of effective film thickness rate is much longer, under the situation of same membrane wrapping thickness, the omnidistance dissolution time of enveloped slow release fertilizer of the present invention will be longer, if require specific omnidistance dissolution time, then the membrane wrapping thickness of enveloped slow release fertilizer of the present invention can reduce.(4) the nano level gas barrier mineral filler that has is more much lower than the price of organic polymer and inorganics sizing, and is less than 1/10th of most polymers price, also much lower than the price of inorganics sizing as the price of nano-calcium carbonate.Along with developing rapidly of nano-fabrication technique, the price of nano level gas barrier mineral filler also will further reduce, and will new inexpensive nano level gas barrier mineral filler constantly occur, so enveloped slow release fertilizer cost of the present invention be low.(5) the described preparation method of enveloped slow release fertilizer of the present invention, the coating operation easier is little, the massfraction of nano level gas barrier mineral filler in coating can reach very high, even use the sizing composition of melt form when applying film forming, the massfraction of nano level gas barrier mineral filler in coating also can reach very high, and therefore the time of releasing of the enveloped slow release fertilizer of preparation is long.Simultaneously, the massfraction height of nano level gas barrier mineral filler in coating can reduce the cost of enveloped slow release fertilizer to a greater degree.
Four embodiments
Enveloped slow release fertilizer of the present invention is made of the coating of fertilizer and fertilizer outside, coating comprises the nano level gas barrier mineral filler less than 1 μ m of polarity sizing and median size, wherein median size is 0.5%～80% less than the volume fraction of the nano level gas barrier mineral filler of 1 μ m, and the volume fraction of polarity sizing is 99.5%～20%.
The said gas barrier mineral filler of the present invention is meant that fertilizer seeing through therein can force rate sees through the low mineral filler of ability in simple polarity coating.The nano level gas barrier mineral filler that the present invention adopts can be in lime carbonate, silicon-dioxide, carbon black, magnesiumcarbonate, zinc carbonate, calcium sulfate, barium sulfate, aluminium sesquioxide, titanium dioxide, ferric oxide, magnesium oxide, zinc oxide, aluminium hydroxide, the silicon carbide one or more.It can also be other nano level gas barrier mineral filler.Wherein, nanometer grade calcium carbonate is cheap, and heavy industrialization is to pay the utmost attention to the gas barrier mineral filler of selecting for use at present.Secondly, nanometer grade silica is also heavy industrialization at present, and price is not high, is to pay the utmost attention to the gas barrier mineral filler of selecting for use yet.
The consumption of nano level gas barrier mineral filler can not be too little also should not be too high.Volume fraction is lower than at 0.5% o'clock, and is not too obvious to the enhancing toughening effect of coating, and the gas barrier ability that improves coating there is not effect.The mineral filler of nano level gas barrier is to the enhancing toughening effect of coating, and volume fraction generally shows beginning more than 0.5%.The volume fraction of nano level gas barrier mineral filler in coating surpasses after 80%, sizing and other auxiliary agent can't be bonded together the mineral filler of nano level gas barrier fully densely, to there be a large amount of pores in the coating, the gas barrier ability of the mechanical strength of havoc coating and reduction coating.Therefore, median size is preferably 0.5%～80% less than the volume fraction of the nano level gas barrier mineral filler of 1 μ m in the coating, and the volume fraction of polarity sizing can be 99.5%～20%.
Polarity sizing in the enveloped slow release fertilizer coating of the present invention can be the polar polymer sizing.Here said polar polymer sizing is meant outside de-carbon in the polymer molecular structure, the protium, also contains the polymkeric substance of aerobic, nitrogen isopolarity element.It can be thermosetting polymers such as urea-formaldehyde resin, polyvinyl acetal resin, melamine resin, unsaturated polyester, urethane, Synolac, Resins, epoxy, resol, unsaturated oil, furane resin, cyclopentadiene multipolymer, paracril, chloroprene rubber, thermoset polyacrylic ester and multipolymer thereof; Also can be thermoplastic polymers such as chlorinatedpolyolefins, polyvinyl chloride and multipolymer thereof, polyvinyl dichloride and multipolymer thereof, ethene one carbon dioxide copolymer, polyvinyl acetate (PVA) and multipolymer, polyacrylonitrile and multipolymer thereof, polymeric amide, thermoplastic polyester, nitrocellulose, rosin, chitin derivative.Can be in these polymkeric substance any one or multiple.It can also be other polar polymer.
The polarity sizing can also be the inorganic sizing of polarity.The response composite that forms the inorganic sizing of polarity is the preferably liquid or water soluble and can be made into the aqueous solution preferably of sizing precursor, the sizing precursor forms jello water insoluble but that can absorb water by gelling reaction and brings into play cohesive action, and the inorganic gel thing of formation promptly is inorganic sizing.Can adopt following response composite any one or multiple arbitrarily: 1. modulus is 1～3 the water glass and the mixed aqueous solution of phosphoric acid; 2. modulus is 1～3 the potassium silicate and the mixed aqueous solution of phosphoric acid; 3. SiO
2Colloidal sol.These sizing precursors solidify to form inorganic sizing.It can also be other the inorganic sizing of polarity.
The polarity sizing can also be the mixed type polarity sizing of polar polymer sizing and the inorganic sizing of polarity.Such as, the mixed type polarity sizing that the mixed aqueous solution that the mixed aqueous solution that polyvinyl alcohol (acetal) resin and potassium silicate are formed, urea-formaldehyde resin prepolymer and water glass are formed etc. solidify to form.
In the coating of enveloped slow release fertilizer of the present invention, also can use an amount of adjusting auxiliary agent.For improve the gas barrier mineral filler in sizing or sizing precursor (the said sizing precursor of the present invention is meant response composite or the prepolymer that forms sizing) dispersion effect and strengthen toughening effect, can adopt suitable tensio-active agent to gas barrier mineral filler carry out surface treatment.As a rule, the gas barrier mineral filler is all adopted suitable tensio-active agent to carry out surface treatment and is made the active filler use.Sometimes mechanical property and the coating film forming properties in order to change the coating thing can add softening agent, reactive thinner etc. and regulate auxiliary agent in sizing or sizing precursor.Add a certain amount of softening agent in sizing or sizing precursor, the flowability of sizing or sizing precursor liquid in the time of can improving the toughness of coating thing and apply film forming is as needing to add softening agent usually in polyvinyl chloride and the multipolymer sizing thereof.In sizing or sizing precursor such as Resins, epoxy sizing precursor (custom is called prepolymer), add a certain amount of reactive thinner, can improve the flowability of sizing or sizing precursor liquid and help applying film process.When using thermosetting polymer sizing coating, form coating in order to make sizing precursor (being prepolymer) that crosslinking curing take place, perhaps, also in the sizing precursor, add solidifying agent (or claiming linking agent), promotor and catalyzer etc. in order to adjust sizing precursor crosslinking curing film forming speed.In inorganic sizing precursor, also add a certain amount of curing catalyst and catalyzer etc. sometimes.Sometimes also add a spot of defoamer in sizing or the sizing precursor liquid, so that the bubble that produces in the coating process can be eliminated quickly.In addition, also can contain a certain amount of organic filler, water-soluble inorganic salt, water-soluble nutriment in a fertilizer and sulphur etc. in the coating.Organic filler can be plant powder such as wood powder, straw powder, starch.Water-soluble nutriment in a fertilizer can be by coated fertilizer self or other fertilizer component (such as add a small amount of potash fertilizer, phosphate fertilizer or other micro-nutriment in a fertilizer element in the coating of membrane wrapping sustained-release urea), if in coating, add, then can adjust the initial stage release rate of enveloped slow release fertilizer of the present invention by coated fertilizer itself.In coating, add a certain amount of organic filler, water-soluble inorganic salt and water-soluble nutriment in a fertilizer, all will reduce the gas barrier of coating thing, improve the dissolution rate of fertilizer, therefore they cooperate the sustained release performance that can control coating with the gas barrier mineral filler, reach the requirement of controllable release to a certain extent.In the coating of enveloped slow release fertilizer of the present invention, can also contain sulphur etc.
The fertilizer of enveloped slow release fertilizer of the present invention can be agricultural fertilizers such as nitrogenous fertilizer, phosphate fertilizer, potash fertilizer, compound fertilizer.It is granular that fertilizer should be before coating, can take certain measure (as sneak into sizing or solvent etc. and carry out granulation) to make granular for finely powdered fertilizer.Enveloped slow release fertilizer of the present invention can be formed by coating, coating structure and membrane wrapping thickness wait and regulate its sustained release performance, to satisfy Different Crop and the different slowly-releasing requirements of different application occasion to slow release fertilizer.
Enveloped slow release fertilizer of the present invention, can carry out following steps successively and make:
The first step is coated on the granulated fertilizer surface with the sizing composition, forms coating on the granulated fertilizer surface;
In second step, the gas barrier mineral filler is sticked on the viscosity coating on granulated fertilizer surface;
In the 3rd step, repeat the first step and second step, until meeting the requirements of membrane wrapping thickness;
The 4th step was solidified until completion of cure the coating of granulated fertilizer, promptly made enveloped slow release fertilizer.
Among the described preparation method of enveloped slow release fertilizer of the present invention, the sizing composition that uses when applying film forming, it can be sizing, it also can be the sizing precursor, can also be the mixture of sizing or sizing precursor and gas barrier mineral filler, can also be mixed with in them and regulate auxiliary agent, solvent or dispersion medium etc.When applying film forming, should make the sizing composition become liquid form (as method) so that apply film forming by heating.Can the sizing composition of granulated fertilizer surface-coated liquid state repeatedly after, just stickingly wrap up in the gas barrier mineral filler once.For smooth implementation repeatedly applies, the sizing composition of internal layer can suitably solidify in coating procedure or between twice coating, should guarantee that just granulated fertilizer surface toughness coating layer is to realize adhesion when adhering to the gas barrier mineral filler.After granulated fertilizer surface viscosity coating adheres to the gas barrier mineral filler, the viscosity coating that is stained with the gas barrier mineral filler is suitably solidified after, continue to repeat follow-up coating film forming one again and adhere to the filler step.The degree of " suitably solidifying ", can be that the viscosity of viscosity coating is suitably increased, also can be to be cured to the granulated fertilizer surface not to be clamminess, can also be to continue to solidify appropriate time after not being clamminess in the granulated fertilizer surface again, preferably is cured to the granulated fertilizer surface and is not clamminess.Adhere to the last time after the gas barrier mineral filler, can be again at granulated fertilizer surface-coated sizing composition, so that the superficial film of the enveloped slow release fertilizer of final preparation is a sizing composition rete.
Among the described preparation method of enveloped slow release fertilizer of the present invention, when adopting the sizing composition that granulated fertilizer is applied film forming, the sizing composition can be a melt, also can be solution, can also be emulsion.As unsaturated polyester, Resins, epoxy, when polyurethane coated, in most cases use the reactive component composition (can be described as sizing precursor melt) that forms these polymkeric substance, wherein can comprise the adjusting auxiliary agent, usually do not contain any solvent and do not contain other volatile matter that to remove, the flowability of sizing precursor when applying film forming by improving temperature or selecting initial reaction component specification to adjust; Certainly, the flowability of sizing precursor also adds certain amount of solvent sometimes when applying film forming in order to increase in the reactive component composition that forms polymkeric substance, and what adopted this moment is the solution of reactive component composition.And sizings such as urea-formaldehyde resin, polyvinyl acetal resin, melamine resin are when applying film forming, usually adopt the aqueous solution of its sizing or its prepolymer, as the urea-formaldehyde resin prepolymer aqueous solution, the polyvinyl acetal resin aqueous solution and the melamine resin prepolymer aqueous solution etc.And paracril, chloroprene rubber isopolarity rubber-like sizing are when applying film forming, usually adopt its rubber organic solution, in order to improve the mechanical property of final coating, usually should be with its linear rubber macromolecules cross-linking adult l network macromole, make the macromolecular reaction promoter of linear rubber macromolecules cross-linking adult l network so in its organic solution, contain simultaneously usually, as solidifying agent (or claiming linking agent), promotor and catalyzer etc.When the thermoplastic polymer sizing applies film forming, usually use its organic solution or water miscible liquid, usually be made into the organic solution of plasticizer-containing as polyvinyl chloride, chlorinatedpolyolefins also is made into organic solution usually, and can adopt their water miscible liquid form usually during coating film forming such as polyacrylic ester and multipolymer thereof, polyvinyl acetate (PVA) and multipolymer thereof, also can adopt its organic solution form certainly.For inorganic sizing, what use when applying film forming is the aqueous solution of inorganic sizing precursor reactive component mixture.For the inorganic sizing mixed type of polar polymer sizing-polarity polarity sizing, what use when the system that has applies film forming may be the mixed aqueous solution of inorganic sizing precursor of polarity and polar polymer sizing precursor, and the system that has may be the mixture of the polarity inorganic sizing precursor aqueous solution and polar polymer sizing or sizing precursor water miscible liquid.
Among the described preparation method of enveloped slow release fertilizer of the present invention, when the sizing composition that the coating film forming adopts was the mixture of sizing or sizing precursor and gas barrier mineral filler, mixture can be liquid forms such as melt, solution, emulsion equally.The base-material of forming mixture be sizing or sizing precursor (comprise and regulate auxiliary agent) when form was emulsion, the gas barrier mineral filler can be dispersed in the disperse phase of emulsion, but also suspended dispersed preferably is dispersed in the disperse phase of emulsion in external phase.
Among the described preparation method of enveloped slow release fertilizer of the present invention, applying film forming mode, can be to adopt spraying method that the sizing composition of liquid state is sprayed on the surface of mobile granulated fertilizer; Also can be that the sizing composition is added in the granulated fertilizer, the sizing composition is in a liquid state, flow and the sizing composition of liquid state is coated on the granulated fertilizer surface by granulated fertilizer; Granulated fertilizer can also be immersed and carry out dip-coating in the liquid sizing composition or the sizing composition of liquid state drenched on granulated fertilizer, carrying out showering.Can also be that other applies thin film-forming method.Apply into film formed viscosity coating and become solid-state coating by curing.
When the coating of granulated fertilizer was thermosetting polymer, the viscosity coating that the sizing composition applies granulated fertilizer formation was solidified into solid-state coating by crosslinking reaction.Curing speed is controlled in design by solidifying agent, promotor and selection of catalysts and consumption and solidification value in the sizing composition.If the sizing composition that uses when applying film forming is a pre-polymer solution, the volatilization that then also relates to solvent and other volatile matter crosslinking curing the time is removed.The sizing composition of thermoplastic polymer applies the viscosity coating that granulated fertilizer forms, and normally is solidified into solid-state coating by adding solvent in the heat extraction viscosity coating or dispersion medium water., then solidify during such as, the sizing composition that uses when applying film forming by adding the heat extraction organic solvent as organic solution; And the sizing composition that uses when applying film forming then solidifies by adding heat extraction water during as water miscible liquid.Inorganic sizing precursor applies the viscosity coating that granulated fertilizer forms, and making precursor by heating is that reactive component mixture generation gelling reaction formation jello form is solidified into solid-state coating.And the inorganic sizing mixed type of polar polymer sizing-polarity polarity sizing composition applies the viscosity coating that granulated fertilizer forms, and playing a role jointly by crosslinking reaction (or gelling reaction) and solvent evaporates is solidified into solid-state coating.
When preparing enveloped slow release fertilizer of the present invention, the mode that the different adjustment auxiliary agent is introduced in the slow release fertilizer coating is different.Be used for handling the tensio-active agent of gas barrier mineral filler, normally be attached on the gas barrier inorganic filler surface and introduce in sizing composition or the sizing composition viscosity coating, also can directly sneak in the sizing composition sometimes.Softening agent, reactive thinner, solidifying agent, promotor and catalyzer are normally directly sneaked in the sizing composition.Organic filler can directly be sneaked in the sizing composition usually, also can enter in the sizing composition viscosity coating by adhering to the filler process with mineral filler is blended together.And water-soluble inorganic salt, water-soluble nutriment in a fertilizer and sulphur can directly be sneaked in the sizing composition; Also can enter in the sizing composition viscosity coating by adhering to the filler process with mineral filler is blended together; Can also apply granulated fertilizer separately and form independent coating layer, coating layer can be the internal layer of granulated fertilizer whole coating body separately, also can be a middle layer of granulated fertilizer whole coating body, can also be the top layer of granulated fertilizer whole coating body.
Among the described preparation method of enveloped slow release fertilizer of the present invention, the concrete mode that the gas barrier mineral filler is sticked on the granulated fertilizer surface viscosity coating can be, the granulated fertilizer of surperficial toughness liquid film is flowed in encapsulation tool, in encapsulation tool, add the gas barrier mineral filler, so that the gas barrier mineral filler adheres on the viscosity coating on granulated fertilizer surface.Can add by phased manner, also can add on continuity ground.The mode that adds can be to spray into, splash into and mode such as inflow.
When sticking to the mineral filler of nano level gas barrier on the granulated fertilizer surface viscosity coating, added excessive nano level gas barrier mineral filler in the encapsulation tool in the past, make to glue on the granulated fertilizer surface viscosity coating to wrap closely knit nano level gas barrier mineral filler, in the granulated fertilizer coating, to form the nano level gas barrier mineral filler layer of highly dense.When adhering to the filler process, if in encapsulation tool, added excessive nano level gas barrier mineral filler, before the granulated fertilizer surface applies the viscosity coating once more, the excessive filler that does not adhere in the encapsulation tool on the granulated fertilizer surface viscosity coating should be screened out.Because the nano level gas barrier mineral filler layer of highly dense can be brought into play good gas barrier effect, so the enveloped slow release fertilizer that has the nano level gas barrier mineral filler layer of highly dense in the coating has excellent sustained release performance.Therefore, when adhering to the filler process, adding excessive nano level gas barrier mineral filler in encapsulation tool, to form this preparation scheme of the nano level gas barrier mineral filler layer of highly dense in the granulated fertilizer coating, is one of preferred version of preparation enveloped slow release fertilizer of the present invention.
In being added with the encapsulation tool of granulated fertilizer, adding the sizing composition applies film forming on one side, the viscosity coating of formation is solidified, and also adding the continuous coating method of gas barrier mineral filler in this whole process or part process wherein on one side, is the described preparation method's of enveloped slow release fertilizer of the present invention special case.This continuous coating preparation method can make the volume of nano level gas barrier mineral filler in the coating reach very high, is another preferred version of the described preparation method of enveloped slow release fertilizer of the present invention.
Among the described preparation method of enveloped slow release fertilizer of the present invention, coating film process and adhesion filler process are preferably under the negative pressure state carries out.After applying film forming and after adhering to filler, can make viscosity coating deaeration for some time under negative pressure state.
Among the described preparation method of enveloped slow release fertilizer of the present invention, in granulated fertilizer coating solidified process, the curing before not being clamminess in the granulated fertilizer surface is preferably under the negative pressure state.After not being clamminess in the granulated fertilizer surface, the pressure that preferably raises immediately, curing after this is preferably in normal pressure or adds to depress to be carried out.Glue and poly-group because of its surface viscosity coating constantly becomes sticky in solidification process for fear of granulated fertilizer, in solidification process, should make granulated fertilizer be in flow state.Making granulated fertilizer mobile mode, can be to stir granulated fertilizer, vibrate granulated fertilizer, blow granulated fertilizer or rotate encapsulation tool to make granulated fertilizer rolling etc.
When preparing enveloped slow release fertilizer of the present invention, also can earlier gas barrier mineral filler and sizing, adjusting auxiliary agent, solvent or dispersion medium etc. be mixed and made into the sizing mixture, adopt the sizing mixture to apply film forming then, by once, repeatedly or the successive mode that applies film forming-solidification process prepare enveloped slow release fertilizer of the present invention.
Enveloped slow release fertilizer of the present invention, when needing that repeatedly coating just can reach the coating requirement, each sizing that adopts or sizing precursor, gas barrier mineral filler, regulating auxiliary agent and their proportioning etc. can be identical, also can be incomplete same.Sizing that is adopted when each time coating or sizing precursor, gas barrier mineral filler, regulate auxiliary agent and their proportioning when incomplete same, the coating of the enveloped slow release fertilizer that then makes is a multi-layer compound structure.Equally, when continuously the coating mode prepared enveloped slow release fertilizer of the present invention, sizing or sizing precursor, gas barrier mineral filler in coating process continuously, regulating auxiliary agent and their proportioning etc. can be constant always, also can change.
With membrane wrapping sustained-release urea and be prepared as example, invention thought of the present invention, implementation method and invention effect are described below.
The present invention adopts the sustained release performance of solubility rate method evaluation membrane wrapping sustained-release urea in the water.The solubility rate method is to measure the dissolution rate of urea in water in the membrane wrapping sustained-release urea in the water, and specific practice is: take by weighing 10 gram membrane wrapping sustained-release ureas and be soaked in 200 milliliters the water, 25 ℃ of constant temperature soak, and measure initial stage solubility rate and average differential solubility rate.The initial stage solubility rate is meant the urea solubility rate that begins at first in the dissolved 24h, and average differential solubility rate then is from the average solubility rate in the 2nd day to the 7th day sky.What the initial stage solubility rate reflected is the shared massfraction of the incomplete urea particle of coating in the membrane wrapping sustained-release urea, and average differential solubility rate then is a massfraction of estimating complete average stripping every day of the membrane wrapping sustained-release urea particle urea of coating.According to initial stage solubility rate ψ
lWith average differential solubility rate ψ
m, by following formula calculate the omnidistance dissolution time of membrane wrapping sustained-release urea or claim release period t (my god):
Embodiment 1
The employing unsaturated polyester resin is a sizing, nanometer CaCO
3(median size is 80nm, down together) is the gas barrier mineral filler, the preparation membrane wrapping sustained-release urea.Nanometer CaCO
3Adopt tensio-active agent to carry out surface treatment and make nano active CaCO
3Use.
With unsaturated polyester resin prepolymer (trade mark is A400-972, and Nanjing, Nanjing DSM company produces, down with), initiator dibenzoyl peroxide and catalyzer xylidine mixing, it is stand-by to be made into sizing composition and deaeration.In the sizing composition, the quality consumption of dibenzoyl peroxide and xylidine is respectively 1.5% and 0.8% of unsaturated polyester resin prepolymer.
Granular Urea is added in the fluidized-bed encapsulation tool, and make Granular Urea be in boiling state, make that the Granular Urea temperature remains on 70 ℃ in the fluidized-bed.The sizing composition constantly is sprayed at urea surface, constantly sprays into nano active CaCO simultaneously
3, the nano active CaCO that sprays into
3Be bonded on the unsaturated polyester resin.Control sizing composition and nano active CaCO
3The speed that sprays into, make unsaturated polyester resin and nanometer CaCO in the coating
3Mass ratio be 30: 70.Coating quantity up to Granular Urea reaches 30%.At last, the outer coating of Granular Urea is solidified fully, promptly make membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 50 days.
Embodiment 2
The employing unsaturated polyester resin is a sizing, nanometer CaCO
3Be the gas barrier mineral filler, the preparation membrane wrapping sustained-release urea.Nanometer CaCO
3Adopt tensio-active agent to carry out surface treatment and make nano active CaCO
3Use.
With unsaturated polyester resin prepolymer, initiator dibenzoyl peroxide, catalyzer xylidine and nano active CaCO
3Mixing, it is stand-by to be made into sizing composition and deaeration.In the sizing composition, the quality consumption of dibenzoyl peroxide and xylidine is respectively 1.5% and 0.8% of unsaturated polyester resin prepolymer, unsaturated polyester resin prepolymer: nanometer CaCO
3Mass ratio be 95: 5.
Granular Urea is added in the rotary drum encapsulation tool of 70 ℃ of temperature controls, rotate rotary drum (rotating speed 50r/min) Granular Urea is flowed in rotary drum.After being evacuated in the rotary drum overbottom pressure and being about 10kPa, feeding styrene gas is 0.1MPa and pressurize until pressure to the rotary drum coating machine, slowly continuously the sizing composition is added in the rotary drum, reaches 20% until the coating quantity of Granular Urea.At last, the outer coating of Granular Urea is solidified fully, promptly make membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 29 days.
Embodiment 3
The employing unsaturated polyester resin is a sizing, nanometer CaCO
3Be the gas barrier mineral filler, the preparation membrane wrapping sustained-release urea.Nanometer CaCO
3Adopt tensio-active agent to carry out surface treatment and make nano active CaCO
3Use.
With unsaturated polyester resin prepolymer, initiator dibenzoyl peroxide and catalyzer xylidine mixing, it is stand-by to be made into sizing composition and deaeration.In the sizing composition, the quality consumption of dibenzoyl peroxide and xylidine is respectively 1.5% and 0.8% of unsaturated polyester resin prepolymer.
It is in 30 ℃ the stirring-type encapsulation tool that Granular Urea is added temperature control, be evacuated to about overbottom pressure 10kPa and maintenance, start agitator Granular Urea is flowed, the sizing composition of disposable adding Granular Urea quality 2%, the excessive nano active CaCO of disposable adding behind the formation uniform coating
3, fully superscribe nano active CaCO
3Back release is with the excessive nano active CaCO that does not adhere to
3Screen out.Then, it is in 70 ℃ the rotary drum encapsulation tool that the Granular Urea of above-mentioned coating is added temperature control, rotating rotary drum (rotating speed 50r/min) flows Granular Urea in rotary drum, be evacuated to about overbottom pressure 10kPa and maintenance, the sizing composition that adds Granular Urea quality 3%, be cured to until the viscosity coating that forms and be not clamminess, normal pressure solidifies 5min more then.Repeat to vacuumize-Jia sizing composition-solidified process 8 times, the add-on of each sizing composition is 3% of a Granular Urea quality again.At last, the outer coating normal pressure of Granular Urea is cured to fully, promptly makes membrane wrapping sustained-release urea.The coating quantity of actual measurement membrane wrapping sustained-release urea is 26.5%, nanometer CaCO in the coating
3Massfraction be about 19.2%.The release period of obtained membrane wrapping sustained-release urea is 38 days.
Embodiment 4
The employing unsaturated polyester resin is a sizing, nanometer CaCO
3Be the gas barrier mineral filler, the preparation membrane wrapping sustained-release urea.Nanometer CaCO
3Adopt tensio-active agent to carry out surface treatment and make nano active CaCO
3Use.
With unsaturated polyester resin prepolymer, initiator dibenzoyl peroxide, catalyzer xylidine and nano active CaCO
3Mixing, it is stand-by to be made into sizing composition and deaeration.In the sizing composition, the quality consumption of dibenzoyl peroxide and xylidine is respectively 1.5% and 0.8% of unsaturated polyester resin prepolymer, unsaturated polyester resin prepolymer: nanometer CaCO
3Mass ratio be 25: 75.
Granular Urea is added in the rotary drum encapsulation tool of 70 ℃ of temperature controls, rotate rotary drum (rotating speed 50r/min) Granular Urea is flowed in rotary drum.After being evacuated in the rotary drum overbottom pressure and being about 10kPa, feeding styrene gas is 0.1MPa and pressurize until pressure to the rotary drum coating machine, slowly continuously the sizing composition is added in the rotary drum, reaches 30% until the coating quantity of Granular Urea.At last, the outer coating of Granular Urea is solidified fully, promptly make membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 54 days.
Embodiment 5
The employing urea-formaldehyde resin is a sizing, nanometer CaCO
3Be the gas barrier mineral filler, the preparation membrane wrapping sustained-release urea.Nanometer CaCO
3Adopt tensio-active agent to carry out surface treatment and make nano active CaCO
3Use.
The urea-formaldehyde resin prepolymer of employing 20% (preparation is filled a prescription: urea is 1: 1.3 with the formaldehyde ratio, the two-step process preparation of adopting urea to add at twice, the quality of the 1st adding urea is 65% of adding urea total mass) aqueous solution and nano active CaCO
3, solidifying agent ammonium chloride mixing, it is stand-by to be made into sizing composition and deaeration.In the sizing composition, the quality consumption of ammonium chloride is 0.05% of a urea-formaldehyde resin prepolymer, urea-formaldehyde resin prepolymer and nanometer CaCO
3Mass ratio be 16: 84.
Granular Urea is added in the rotary drum encapsulation tool of 95 ℃ of temperature controls, rotate rotary drum (rotating speed 50r/min) Granular Urea is flowed in rotary drum.Slowly continuously the sizing composition is added in the rotary drum, reach 30% until the coating quantity of Granular Urea.At last, the outer coating of Granular Urea is solidified fully, promptly make membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 26 days.
Embodiment 6
Employing urethane is sizing, nanometer CaCO
3Be the gas barrier mineral filler, the preparation membrane wrapping sustained-release urea.
By-NCO :-OH=1.1: 1 takes by weighing MDI, polypropylene glycol (M
n=3000) and butyleneglycol (the quality consumption of butyleneglycol be polypropylene glycol 0.5%), and add the dibutyl tin dilaurate mixing and make the sizing composition, deaeration is stand-by.In the sizing composition, the quality consumption of dibutyl tin dilaurate is 0.05% of a sizing composition.
It is in 70 ℃ the rotary drum encapsulation tool that Granular Urea is added temperature control, rotates rotary drum (rotating speed 50r/min) Granular Urea is flowed in rotary drum.Be evacuated to also maintenance about overbottom pressure 10kPa in the rotary drum, add the sizing composition of Granular Urea quality 3%, be cured to until the viscosity coating that forms and be not clamminess, solidify 5min again at normal pressure.Repeat above-mentioned vacuumizing-Jia sizing composition-solidified process 1 time, the add-on of sizing composition is a Granular Urea quality 3%.Be evacuated to also maintenance about overbottom pressure 10kPa in the rotary drum again, add the sizing composition of Granular Urea quality 3%, slowly at the uniform velocity add the nanometer CaCO of Granular Urea quality 6% behind the 2min
3, add in the 2min, solidify after urea surface is not clamminess, unload and be depressed into normal pressure and solidify 5min again.And then repeat above-mentioned vacuumizing-Jia sizing composition-Jia nanometer CaCO
3-solidified process 3 times, each sizing composition and nanometer CaCO
3Add-on all be respectively Granular Urea quality 3% and 6%.At last, the outer coating normal pressure of Granular Urea is cured to fully, promptly makes membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 28 days.
Embodiment 7
Employing urethane is sizing, nanometer CaCO
3Be the gas barrier mineral filler, the preparation membrane wrapping sustained-release urea.Nanometer CaCO
3Adopt tensio-active agent to carry out surface treatment and make nano active CaCO
3Use.
By-NCO :-OH=1.1: 1 takes by weighing MDI, polypropylene glycol (M
n=3000) and butyleneglycol (the quality consumption of butyleneglycol be polypropylene glycol 0.5%), and add the dibutyl tin dilaurate mixing and make the sizing composition, deaeration is stand-by.In the sizing composition, the quality consumption of dibutyl tin dilaurate is 0.05% of a sizing composition.
It is in 40 ℃ the stirring-type encapsulation tool that Granular Urea is added temperature control, be evacuated to about overbottom pressure 10kPa and maintenance, start agitator Granular Urea is flowed, the sizing composition of disposable adding Granular Urea quality 3%, the excessive nano active CaCO of disposable adding behind the formation uniform coating
3, fully superscribe nano active CaCO
3Back release is with the excessive nano active CaCO that does not adhere to
3Screen out.And then will be coating Granular Urea once to add temperature control be in 40 ℃ the stirring-type encapsulation tool, be evacuated to about overbottom pressure 10kPa and maintenance, starting agitator flows Granular Urea, the sizing composition of disposable adding Granular Urea quality 3%, the excessive nano active CaCO of disposable adding behind the formation uniform coating
3, fully superscribe nano active CaCO
3Back release is with the excessive nano active CaCO that does not adhere to
3Screen out.Then, again will be the Granular Urea of twice of coating to add temperature control be in 70 ℃ the rotary drum encapsulation tool, rotating rotary drum (rotating speed 50r/min) flows Granular Urea in rotary drum, be evacuated to about overbottom pressure 10kPa and maintenance, the sizing composition that adds Granular Urea quality 3%, be cured to until the viscosity coating that forms and be not clamminess, be forced into 0.12MPa then and solidify 5min again.Repeat to vacuumize-Jia sizing composition-solidified process 3 times, the add-on of each sizing composition is 3% of a Granular Urea quality again.At last, the coating outside the Granular Urea is solidified fully, promptly make membrane wrapping sustained-release urea.The coating quantity of actual measurement membrane wrapping sustained-release urea is 25.8%, nanometer CaCO in the coating
3Massfraction be about 48.8%.The release period of obtained membrane wrapping sustained-release urea is 36 days.
Embodiment 8
Adopt urethane and two kinds of sizings of unsaturated polyester resin, nanometer CaCO
3Be the gas barrier mineral filler, the preparation membrane wrapping sustained-release urea.Nanometer CaCO
3Adopt tensio-active agent to carry out surface treatment and make nano active CaCO
3Use.
By-NCO :-OH=1.1: 1 takes by weighing MDI, polypropylene glycol (M
n=3000) and butyleneglycol (the quality consumption of butyleneglycol be polypropylene glycol 0.5%), and add dibutyl tin dilaurate and nano active CaCO
3Mixing is made the viscoelastic polyurethane feed composition, and deaeration is stand-by.In the viscoelastic polyurethane feed composition, the quality consumption of dibutyl tin dilaurate is 0.05% of a sizing composition, nanometer CaCO
3The quality consumption be 30% of sizing composition.
With unsaturated polyester resin prepolymer, dibenzoyl peroxide, xylidine and nano active CaCO
3Mixing is made into unsaturated polyester resin prepolymer sizing composition, and deaeration is stand-by.In the unsaturated polyester resin prepolymer sizing composition, the quality consumption of dibenzoyl peroxide and xylidine is respectively 1.5% and 0.8% of unsaturated polyester resin prepolymer, unsaturated polyester resin prepolymer: nanometer CaCO
3Mass ratio be 25: 75.
It is in 70 ℃ the rotary drum encapsulation tool that Granular Urea is added temperature control, rotates rotary drum (rotating speed 50r/min) Granular Urea is flowed in rotary drum.Being evacuated to the interior overbottom pressure of rotary drum is about 10kPa and maintenance, adds the viscoelastic polyurethane feed composition of Granular Urea quality 4%, slowly at the uniform velocity adds the nano active CaCO of Granular Urea quality 4% behind the 2min
3, add in the 2min.Curing is unloaded and is depressed into normal pressure and solidifies 5min again after urea surface is not clamminess.And then repeat the active CaCO of above-mentioned vacuumizing-Jia urethane sizing composition-Jia nanometer
3-solidified process 2 times, each viscoelastic polyurethane feed composition and nano active CaCO
3Add-on all be respectively 4% and 4% of Granular Urea quality.Then, being evacuated to the interior overbottom pressure of rotary drum again is about 10kPa and maintenance, adds the unsaturated polyester resin prepolymer sizing composition of Granular Urea quality 5%, is cured to until the viscosity coating that forms and is not clamminess, again normal pressure curing 5min.Repeat to vacuumize-Jia unsaturated polyester resin prepolymer sizing composition-solidified process 2 times, the add-on of each unsaturated polyester resin prepolymer sizing composition is 5% of a Granular Urea quality again.At last, the outer coating normal pressure of Granular Urea is cured to fully, promptly makes membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 54 days.
Embodiment 9
The employing polyvinyl chloride is a sizing, nanometer SiO
2(median size is 50nm) is the gas barrier mineral filler, the preparation membrane wrapping sustained-release urea.Nanometer SiO
2Adopt tensio-active agent to carry out surface treatment and make nano active SiO
2Use.
Polyvinyl chloride is dissolved in the cyclohexanone solvent, and adds plasticizer phthalic acid dioctyl ester and nano active SiO
2, being made into the polyvinyl chloride mass concentration and being 5% polyvinyl chloride solution type sizing composition, deaeration is stand-by.In the sizing composition, the quality amount ratio of polyvinyl chloride and dioctyl phthalate (DOP) is 3: 2, nano active SiO
2With the quality amount ratio of polyvinyl chloride be 4: 1.
Granular Urea is added in the rotary drum encapsulation tool of 105 ℃ of temperature controls, rotate rotary drum (rotating speed 50r/min) Granular Urea is flowed in rotary drum.Slowly continuously the sizing composition is added in the rotary drum, vacuumize simultaneously the cyclohexanone solvent volatilization is steamed, reach 30% until the coating quantity of Granular Urea.At last, the cyclohexanone solvent volatilization in the Granular Urea peplos is eliminated, promptly make membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 31 days.
Embodiment 10
The employing polyvinyl acetate (PVA) is a sizing, nanometer Al
2O
3(median size is 80nm) is the gas barrier mineral filler, the preparation membrane wrapping sustained-release urea.Nanometer Al
2O
3Adopt tensio-active agent to carry out surface treatment and make nano active Al
2O
3Use.
Press vinyl acetate and nanometer Al
2O
3Mass ratio is 1: 2 a ratio, with vinyl acetate and nanometer Al
2O
3Mix as oil phase, carry out letex polymerization and make oil phase and contain nanometer Al
2O
3Aqueous polyvinyl acetate emulsion, this emulsion is promptly carried out coating as the sizing composition and is prepared membrane wrapping sustained-release urea.
Granular Urea is added in the rotary drum encapsulation tool of 95 ℃ of temperature controls, rotate rotary drum (rotating speed 50r/min) Granular Urea is flowed in rotary drum.Slowly continuously the sizing composition is added in the rotary drum, reach 30% until the coating quantity of Granular Urea.At last, the outer coating of Granular Urea is solidified fully, promptly make membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 29 days.
Embodiment 11
Employing silicate is sizing, nano-TiO
2(median size is 50nm) is the gas barrier mineral filler, the preparation membrane wrapping sustained-release urea.
With modulus be the aqueous solution that is mixed with of 1～3 water glass, phosphoric acid and water as the sizing composition, carry out coating and prepare membrane wrapping sustained-release urea.In the sizing composition, the mass concentration of water glass is 20%, and the mass concentration of phosphoric acid is 25%.
Granular Urea is added in the fluidized-bed encapsulation tool, and make Granular Urea be in boiling state, make that the Granular Urea temperature remains on 95 ℃ in the fluidized-bed.The sizing composition constantly is sprayed at urea surface, constantly sprays into nano-TiO simultaneously
2, the nano-TiO that sprays into
2Be bonded on the sizing composition.Control sizing composition and nano-TiO
2The speed that sprays into, make coating mesosilicic acid salt sizing and nano-TiO
2Mass ratio be 50: 50.Coating quantity up to Granular Urea reaches 30%, and the outer coating of Granular Urea is solidified fully, promptly makes membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 17 days.
Embodiment 12
Adopting polyvinyl acetal resin and silicate is sizing, and nano SiC (median size is 50nm) is the gas barrier mineral filler, the preparation membrane wrapping sustained-release urea.Nano SiC adopts tensio-active agent to carry out surface treatment and makes nano active SiC use.
Polyvinyl acetal resin, water glass, nano active SiC and water are mixed with the suspension mixture, as the sizing composition, carry out coating and prepare membrane wrapping sustained-release urea with this suspension mixture.In the sizing composition, the mass concentration of water glass is 10%, and the mass concentration of polyvinyl acetal resin is 10%, and the mass concentration of nano active SiC is 30%.
Granular Urea is added in the rotary drum encapsulation tool of 95 ℃ of temperature controls, rotate rotary drum (rotating speed 50r/min) Granular Urea is flowed in rotary drum.Slowly continuously the sizing composition is added in the rotary drum, reach 30% until the coating quantity of Granular Urea.At last, the outer coating of Granular Urea is solidified fully, promptly make membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 22 days.
Comparative example 1
Adopt the unsaturated polyester resin sizing to coat Granular Urea and prepare membrane wrapping sustained-release urea.With unsaturated polyester resin prepolymer, initiator dibenzoyl peroxide and catalyzer xylidine mixing, be made into the sizing composition, deaeration is stand-by.In the sizing composition, the quality consumption of dibenzoyl peroxide and xylidine is respectively 1.5% and 0.8% of unsaturated polyester resin prepolymer.
Granular Urea is added in the fluidized-bed encapsulation tool, and make Granular Urea be in boiling state, make that the Granular Urea temperature remains on 70 ℃ in the fluidized-bed.The sizing composition constantly is sprayed at urea surface, reaches 25%, the outer coating of Granular Urea is solidified fully, promptly make membrane wrapping sustained-release urea up to the coating quantity of Granular Urea.The release period of obtained membrane wrapping sustained-release urea is 26 days.
Comparative example 2
Adopt the viscoelastic polyurethane material package to cover Granular Urea and prepare membrane wrapping sustained-release urea.By-NCO :-OH=1.1: 1 takes by weighing MDI, polypropylene glycol (M
n=3000) and butyleneglycol (the quality consumption of butyleneglycol be polypropylene glycol 0.5%), and add the dibutyl tin dilaurate mixing and make the sizing composition, deaeration is stand-by.In the sizing composition, the quality consumption of dibutyl tin dilaurate is 0.05% of a sizing composition.
It is in 70 ℃ the rotary drum encapsulation tool that Granular Urea is added temperature control, rotates rotary drum (rotating speed 50r/min) Granular Urea is flowed in rotary drum.Be evacuated to also maintenance about overbottom pressure 10kPa in the rotary drum, add the sizing composition of Granular Urea quality 3%, be cured to until the viscosity coating that forms and be not clamminess, normal pressure solidifies 5min again.Then, repeat above-mentioned vacuumizing-Jia sizing composition-solidified process again 9 times, the add-on of each sizing composition all is a Granular Urea quality 3%.At last, the coating outside the Granular Urea is solidified fully, promptly make membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 14 days.
Comparative example 3
Adopt the urea-formaldehyde resin sizing to coat Granular Urea and prepare membrane wrapping sustained-release urea.(the preparation prescription: urea is 1: 1.3 with the formaldehyde ratio to urea-formaldehyde resin prepolymer 40%, the two-step process preparation of adopting urea to add at twice, the quality that adds urea for the 1st time for add the urea total mass 65%) in the aqueous solution, the solidifying agent ammonium chloride mixing that adds urea-formaldehyde resin prepolymer quality 0.05%, be made into the sizing composition, deaeration is stand-by.
Granular Urea is added in the rotary drum encapsulation tool of 95 ℃ of temperature controls, rotate rotary drum (rotating speed 50r/min) Granular Urea is flowed in rotary drum.Slowly continuously the sizing composition is sprayed in the rotary drum, reach 25% until the coating quantity of Granular Urea.At last, the outer coating of Granular Urea is solidified fully, promptly make membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 8 days.
Comparative example 4
Adopt the polyvinyl chloride sizing to coat Granular Urea and prepare membrane wrapping sustained-release urea.Polyvinyl chloride is dissolved in the cyclohexanone solvent, and adds the dioctyl phthalate (DOP) softening agent, be made into the polyvinyl chloride mass concentration and be 5% polyvinyl chloride solution type sizing composition, deaeration is stand-by.In the sizing composition, the quality amount ratio of polyvinyl chloride and dioctyl phthalate (DOP) is 3: 2.
Granular Urea is added in the rotary drum encapsulation tool of 105 ℃ of temperature controls, rotate rotary drum (rotating speed 50r/min) Granular Urea is flowed in rotary drum.Slowly continuously the sizing composition is added in the rotary drum, and vacuumize the cyclohexanone solvent volatilization is steamed, reach 25% until the coating quantity of Granular Urea.At last, the cyclohexanone solvent volatilization in the Granular Urea peplos is eliminated, promptly make membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 16 days.
Comparative example 5
Adopt the polyvinyl acetate (PVA) sizing to coat Granular Urea and prepare membrane wrapping sustained-release urea.Vinyl acetate is carried out letex polymerization as oil phase, make aqueous polyvinyl acetate emulsion, this emulsion is promptly carried out coating as the sizing composition and is prepared membrane wrapping sustained-release urea.
Granular Urea is added in the rotary drum encapsulation tool of 95 ℃ of temperature controls, rotate rotary drum (rotating speed 50r/min) Granular Urea is flowed in rotary drum.Slowly continuously the sizing composition is added in the rotary drum, reach 25% until the coating quantity of Granular Urea.At last, the outer coating of Granular Urea is solidified fully, promptly make membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 15 days.
Comparative example 6
Adopt the silicate sizing to coat Granular Urea and prepare membrane wrapping sustained-release urea.With modulus be the aqueous solution that is mixed with of 1～3 water glass, phosphoric acid and water as the sizing composition, carry out coating and prepare membrane wrapping sustained-release urea.In the sizing composition, the mass concentration of water glass is 20%, and the mass concentration of phosphoric acid is 25%.
Granular Urea is added in the fluidized-bed encapsulation tool, make Granular Urea be in boiling state, and make that the Granular Urea temperature remains on 95 ℃ in the fluidized-bed.The sizing composition constantly is sprayed at urea surface, reaches 30%, the outer coating of Granular Urea is solidified fully, promptly make membrane wrapping sustained-release urea up to the coating quantity of Granular Urea.The release period of obtained membrane wrapping sustained-release urea is 9 days.
Comparative example 7
Adopt two kinds of sizings of polyvinyl acetal resin and silicate to coat Granular Urea and prepare membrane wrapping sustained-release urea.Polyvinyl acetal resin, water glass and water are mixed with mixed aqueous solution, as the sizing composition, carry out coating and prepare membrane wrapping sustained-release urea with this mixed aqueous solution.In the sizing composition, the mass concentration of water glass is 15%, and the mass concentration of polyvinyl acetal resin is 15%.
Granular Urea is added in the rotary drum encapsulation tool of 95 ℃ of temperature controls, rotate rotary drum (rotating speed 50r/min) Granular Urea is flowed in rotary drum.Slowly continuously the sizing composition is sprayed in the rotary drum, reach 30% until the coating quantity of Granular Urea.At last, the outer coating of Granular Urea is solidified fully, promptly make membrane wrapping sustained-release urea.The release period of obtained membrane wrapping sustained-release urea is 15 days.
Claims (13)
1, a kind of enveloped slow release fertilizer, coating by fertilizer and fertilizer outside constitutes, it is characterized in that: coating comprises the gas barrier mineral filler less than 1 μ m of polarity sizing and median size, wherein median size is 0.5%～80% less than the volume fraction of the gas barrier mineral filler of 1 μ m, and the volume fraction of polarity sizing is 99.5%～20%.
2, enveloped slow release fertilizer according to claim 1 is characterized in that: the gas barrier mineral filler is one or more in lime carbonate, silicon-dioxide, carbon black, magnesiumcarbonate, zinc carbonate, calcium sulfate, barium sulfate, aluminium sesquioxide, titanium dioxide, ferric oxide, magnesium oxide, zinc oxide, aluminium hydroxide, the silicon carbide.
3, enveloped slow release fertilizer according to claim 1 is characterized in that: the polarity sizing is the mixed type polarity sizing of polar polymer sizing, the inorganic sizing of polarity or the inorganic sizing of polar polymer sizing-polarity.
4, enveloped slow release fertilizer according to claim 3 is characterized in that: the polar polymer sizing is a urea-formaldehyde resin, polyvinyl acetal resin, melamine resin, unsaturated polyester, urethane, Synolac, Resins, epoxy, resol, unsaturated oil, furane resin, the cyclopentadiene multipolymer, paracril, chloroprene rubber, polyacrylic ester and multipolymer thereof, chlorinatedpolyolefins, polyvinyl chloride and multipolymer thereof, polyvinyl dichloride and multipolymer thereof, ethene-carbon dioxide copolymer, polyvinyl acetate (PVA) and multipolymer thereof, polyacrylonitrile and multipolymer thereof, polymeric amide, thermoplastic polyester, nitrocellulose, rosin, in the chitin derivative one or more.
5, enveloped slow release fertilizer according to claim 3 is characterized in that: the inorganic sizing of polarity is the one of any of following response composite or the multiple sizing that solidify to form arbitrarily: 1. modulus is 1～3 the water glass and the mixed aqueous solution of phosphoric acid; 2. modulus is 1～3 the potassium silicate and the mixed aqueous solution of phosphoric acid; 3. SiO
2Colloidal sol.
6, enveloped slow release fertilizer according to claim 1 is characterized in that: contain the adjusting auxiliary agent in the coating.
7, enveloped slow release fertilizer according to claim 6 is characterized in that: the adjusting auxiliary agent is one or more in tensio-active agent, softening agent, reactive thinner, solidifying agent, promotor, catalyzer, defoamer, organic filler, water-soluble inorganic salt, water-soluble nutriment in a fertilizer, the sulphur.
8, a kind of method for preparing the described enveloped slow release fertilizer of claim 1 is characterized in that: carry out following steps successively:
The first step is coated on the granulated fertilizer surface with the sizing composition, forms coating on the granulated fertilizer surface;
In second step, the gas barrier mineral filler is sticked on the viscosity coating on granulated fertilizer surface;
In the 3rd step, repeat the first step and second step, until meeting the requirements of membrane wrapping thickness;
The 4th step was solidified until completion of cure the coating of granulated fertilizer, promptly made enveloped slow release fertilizer.
9, the preparation method of enveloped slow release fertilizer according to claim 8 is characterized in that: the sizing composition is coated on the granulated fertilizer surface carries out under negative pressure state with the process that forms coating.
10, the preparation method of enveloped slow release fertilizer according to claim 8 is characterized in that: after sticking to the gas barrier mineral filler on the granulated fertilizer surface viscosity coating, granulated fertilizer surface viscosity coating is suitably solidified.
11, the preparation method of enveloped slow release fertilizer according to claim 8 is characterized in that: after the viscosity coating by the granulated fertilizer surface adheres to the gas barrier mineral filler for the last time, again at granulated fertilizer surface-coated sizing composition.
12, the preparation method of each described enveloped slow release fertilizer in 11 according to Claim 8, it is characterized in that: granulated fertilizer surface viscosity coating adheres to the process of filler to carry out under negative pressure state.
13, the preparation method of each described enveloped slow release fertilizer in 11 according to Claim 8, it is characterized in that: in granulated fertilizer coating solidified process, being solidificated under the negative pressure state before not being clamminess in the granulated fertilizer surface carried out.
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