CN100558682C - A kind of polymer coating controlled release fertilizer and production method thereof and dedicated capsule material - Google Patents
A kind of polymer coating controlled release fertilizer and production method thereof and dedicated capsule material Download PDFInfo
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- CN100558682C CN100558682C CNB2007100991447A CN200710099144A CN100558682C CN 100558682 C CN100558682 C CN 100558682C CN B2007100991447 A CNB2007100991447 A CN B2007100991447A CN 200710099144 A CN200710099144 A CN 200710099144A CN 100558682 C CN100558682 C CN 100558682C
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Abstract
The invention discloses a kind of polymer coating controlled release fertilizer and production method thereof and dedicated capsule material.The coated fertilizer of this release and release control fertilizer, comprise molecular-weight average at branched chain type new LDPE (film grade) between the 20000-30000 dalton and molecular-weight average the linear low density polyethylene between 20000-30000 dalton; The ratio of quality and the number of copies of described branched chain type new LDPE (film grade) and linear low density polyethylene is 1: 0.33-1.This polymer coating controlled release fertilizer is made up of the coated fertilizer among water miscible fertilizer and the claim 1-4; Described coated fertilizer is coated on described water miscible fertilizer.The controlled release properties of coated fertilizer of the present invention is good, the complete processing safety non-toxic, can be used for cash crop such as lawn, flowers and vegetables.
Description
Technical field
The present invention relates to a kind of polymer coating controlled release fertilizer and production method thereof and dedicated capsule material.
Background technology
After granulated fertilizer adopts polymer capsule, fertilizer nutrient releases that can be controlled effectively, it is obvious that the fertilizer that wraps up with inorganic materials and the slow release fertilizer of chemosynthesis are compared controlled release properties.In the complete processing of polymer coated fertilizer, extensively a kind of scheme that adopts is: polymkeric substance and additive thereof are dissolved in certain solvent, adopt the spraying precipitated phase to transform the legal system film then, in this processing scheme, the film forming properties of polymkeric substance itself, the polymkeric substance solubility property in solvent is the factor that at first will consider, according to the solubility value of polymkeric substance and solvent, can search out some available polymer solution system.
Chissoasahi fertilizer Co. in 1974, Ltd. Shen Qing United States Patent (USP) " production method of coated fertilizer " (U.S.Pat.No.4019890) in, use benzene, toluene, trieline and zellon dissolving polyolefine have been introduced, the method for allotment coating formulations prepared from solutions release and release control fertilizer.Subsequently, the said firm in 1988 the application patent " coated granule fertilizer " (U.S.Pat.No.5147442) in, introduced a kind of fertilizer with degradation property mulch film, the claimed coated fertilizer of this patent is: the mixture that comprises a kind of polyolefin resin and rubber resin or ethane-acetic acid ethyenyl-carbon monoxide multipolymer; 1989 the application patent " coated granule fertilizer " (U.S.Pat.No.5147442) in, claimed: with polyolefine and 1,2 epoxy prapane is the coated fertilizer prescription of main raw.The claimed content of two special trains in back was also applied for three the patents (Chinese patent: 87105398,87105467,89101193) of knowing clearly relevant with 1989 in China in 1987.The related material of these patents is still based on polyolefine, solvent is mainly trieline or zellon, the weak point of these patents is that the material of selecting for use is difficult for obtaining, price is expensive, zellon belongs to 6.1 class low-toxic solvents, for this reason, present research work needs the place of key breakthrough to be: polymkeric substance and avirulent solvent that searching extensively is easy to get, price is low.
Around novel material and the nontoxic or low poison solvent that is complementary of solubility property with it, the patent of having applied at present comprises: calendar year 2001 Shenyang Inst. of Applied Ecology, Chinese Academy of Sciences apply for be main raw, be the coating liquid system (Chinese patent: 01133415.0) of solvent with ethanol and toluene etc. with acrylic resin and Mierocrystalline cellulose; China Agricultural University had applied in 2003: be the patent (Chinese patent: 03155813.5) of main coated fertilizer with polyolefine and turps; Shandong Agricultural University had applied in 2004: to reclaim the patent (Chinese patent: 200410035783.3) that waste thermoplastic resin (polystyrene resin and polyvinyl resin) is dissolved in zellon and methylene dichloride configuration coating liquid system; Had invented the Beijing City Agriculture and Forestry Institute in 2005: be dissolved in terebinthine coated fertilizer system (Chinese patent: 200510000039.4) to reclaim macromolecular material (polypropylene).These patents have increased some mould material prescriptions that release and release control fertilizer is produced that can be used for, particularly adopt waste or used plastics as polymeric film material, reduced the polymkeric substance cost greatly, but, because making, the polyolefin component complexity that waste or used plastics in the market comprises, the difference of material be difficult to carry out strict quality of production control.With regard to the solvent of selecting for use, still still fundamentally do not solve the toxicity problem (as: zellon, and methyl chloride, toluene) of solvent, the new turps that adopts because of it has bad smell, has limited its industry development.
Above-mentioned solvent is organic solvent, and in order to seek cheap solvent, the research that has is developed new coated fertilizer system around water as solvent.Some use the technical scheme of water soluble resin exploitation coated fertilizer to obtain license, adopt water soluble resin to be dissolved in the aqueous solution of acetic acid such as Fan Xiaolin and produce release and release control fertilizer (Chinese patent, 03140097.3), because the water absorbing properties of water soluble resin is stronger, be that the coated release-controlled fertilizer production technology of putting of mould material manufacturing is still waiting perfect with this base polymer.
Theoretically, as long as suitable solvent or method for distinguishing are arranged with the high molecular polymer dissolving with disperse, just can by certain chemical engineering means with its parcel (Encapsule) to particle surface; If other subsidiary conditions are suitable, polymer molecule then can solidify to form the film with a fixed structure again on the fertiliser granulates surface; If the film that forms has porousness, so this polymer materials and working method just can be used for preparing release and release control fertilizer.Situation from reality, a large amount of research can have been carried out experiment screening by mass-produced various polymkeric substance with regard at present industrial, as indicated above, be used to make the encapsulated material of fertiliser granulates to comprise polyolefine (T.Fujita etc., 1974), epoxy polymer (A.P.Hudson, 1994), urethane (A.J.Geiger etc., 2000), polyvinyl alcohol (Fan Xiaolin, 2003) and polysulfones (M.Tomaszewska etc., 2006) or the like high molecular polymer.From these results, the polymkeric substance that can be used for fertilizer coating is a lot, if but these materials and working method are carried out comprehensive assessment, can find, itself can not form good release-controlled film the material that has, the polymkeric substance that has costs an arm and a leg, and the solvent that uses in the processing that has is undesirable, complete processing that the needs that have are special or the like.
Summary of the invention
In order to solve to the preparation material of above-mentioned film-coated controlled release fertilizer problem such as mixed and disorderly and preparation solvent for use toxicity, the invention provides a kind of polymer coating controlled release fertilizer and production method thereof and dedicated capsule material.
The coated fertilizer of film-coated controlled release fertilizer provided by the present invention, comprise molecular-weight average at branched chain type new LDPE (film grade) between the 20000-30000 dalton and molecular-weight average the linear low density polyethylene between 20000-30000 dalton; The ratio of quality and the number of copies of described branched chain type new LDPE (film grade) and linear low density polyethylene is 1: 0.33-1.
It is among 1F7B, 1C7A and the LD100 one or more that described branched chain type new LDPE (film grade) is selected from the trade mark.
The described linear low density polyethylene trade mark is one or more among DFDA-7042, DNDA7144 and the DNDA7145.
Described chain new LDPE (film grade) and described linear low density polyethylene melting index (MI) are 5 ~ 10g/10min.
Comprise also in the described material that ratio of quality and the number of copies is 1: the paraffin of 0.1-0.15.
Film-coated controlled release fertilizer provided by the present invention is made up of water miscible fertilizer and coated fertilizer; Described coated fertilizer is coated on described water miscible fertilizer surface.Described coated fertilizer comprise molecular-weight average at branched chain type new LDPE (film grade) between the 20000-30000 dalton and molecular-weight average the linear low density polyethylene between 20000-30000 dalton; The ratio of quality and the number of copies of branched chain type new LDPE (film grade) and linear low density polyethylene is 1: 0.33-1.
The volume ratio that rises of the kilogram-mass of described water soluble fertilizer and coated fertilizer is 1: 0.8-1.2; Described water soluble fertilizer comprises volatile salt, ammonium nitrate, ammonium sulfate, urea, and diammonium phosphate, primary ammonium phosphate, vitriolate of tartar, Repone K, potassiumphosphate or the like also comprise the fertilizer that contains various trace elements (iron, manganese, copper, zinc, molybdenum, boron); Can be straight fertilizer, also can be composite fertilizer; Described water soluble fertilizer is a particulate state, and particle diameter is 2-4mm; As adopt small particle urea, can be used to process orange and produce golf lawn fruit mountain range special-purpose control-release fertilizer.Adopt granular urea and composite fertilizer, granular urea sieves earlier, and the control particle diameter is in the 2-4mm scope; Composite fertilizer: N-P
2O
5-K
2O content is 16-16-16.
The method of above-mentioned polymer coating controlled release fertilizer provided by the present invention may further comprise the steps:
1) organic solvent and above-mentioned any coated fertilizer are added in the reactor, the post-heating that stirs is made coating solution; The ratio of quality and the number of copies of described organic solvent and described coated fertilizer is 100: 6-8, described organic solvent are one or more in octane, hexanaphthene and the perhydronaphthalene;
2) feed the gas of temperature in 90-110 ℃ of scope to the fluidized-bed bottom, the flow of described gas is 20-40m/sec; Simultaneously water miscible fertilizer is sent into fluidized-bed, make fertilizer be in ciculation fluidized state;
3) with the coating solution atomization to the fertiliser granulates surface, make film-coated controlled release fertilizer.
In the described method, the Heating temperature in the described step 1) is 70-120 ℃, and be 20-50 minute heat-up time.
In the described method, described step 2) gas in is air; Provide by Root's blower; In the described step 3) with the coating solution atomization to the fertiliser granulates surface, be to adopt air compressor and two fluid shower nozzles to realize.
Organic solvent described in the described method can be by condenser and air-cooler cooling, recycling.
Method of the present invention adopts all energy polyethylene dissolving granule materials of octane, hexanaphthene and perhydronaphthalene, nontoxicity, production safety.
Method of the present invention adopt suitability for industrialized production amount maximum plastics---polyethylene can solve the raw material problem as material, also avoid adopting the problem of the unstable properties that multiple polymers brings.Adopt molecular-weight average at the daltonian polyethylene of 20000-30000, make its degradation capability stronger, and be easy to process in order to strengthen the reactive force between the polyethylene molecule, the method of production coated fertilizer of the present invention adopts low-molecular-weight linearity and branched chain type new LDPE (film grade) as coated fertilizer, guarantee that polymer materials is suitable for making release-controlled film, in the controlled release properties that improves film, also as a kind of regulating measure.Advantage is: form simply, be easy to control, set of dispense can be regulated controlled release properties than changing.
The present invention only adopts paraffin as supplementary additive, utilizes its rheological property as internal lubricant change coating liquid, improves the masterbatch processing fluidity, helps masterbatch and disperses more equably in matrix resin.
The advantage of the solvent that method of the present invention adopts has nontoxic, low inflammable, non-stimulated smell, the security that has improved processing and used.
In a word, method of the present invention is used above-mentioned materials and solvent system, and the dissolving mixing can be produced release period at individual month coated fertilizer of 3-12 under the situation of heating.Adopt spraying precipitated phase conversion method, in the spray-fluidized bed apparatus, make release and release control fertilizer.Method of the present invention can increase controlled release properties, the complete processing safety non-toxic of coated fertilizer.Release and release control fertilizer of the present invention can be used for cash crop such as lawn, flowers and vegetables.
Description of drawings
Fig. 1 produces the coating process schema of coated fertilizer for the present invention
Fig. 2 is that the different proportionings with the branched chain type polyethylene of line style are handled the nutrient cumulative release curve of coat fertilizer in water
Embodiment
Method among the following embodiment if no special instructions, is ordinary method.
The processing unit (plant) of used coated fertilizer is conventional equipment among the following embodiment, and Root's blower is available from Tianjin gas blower head factory, model WL20～5/0.20 as shown in fig. 1; Under meter is available from Beijing's five metals main office, model LZB-100; Oil pump is available from Beijing's five metals main office, and model is BRY; Air compressor is available from Beijing Jin Huan Compressors Factory, model: V-0.14/10C; All the other devices are all available from Beijing's five metals main office.
Adopting the polyethylene of relative low price is main coated fertilizer, the first, regulate and control film forming properties and controlled release properties by the new LDPE (film grade) of selecting different molecular-weight average, molecule secondary structure for use.The controlled release properties of the coated fertilizer system of research new LDPE (film grade) and linear low density polyethylene combining and configuring, development of new coated fertilizer prescription.Second, principle according to polymkeric substance " similar mixing ", solubility parameters with reference to polyolefine (polyethylene), selection solubility value is close, the solvent of low toxicity (with reference to hazardous chemical standard compilation organic chemical industry volume) experimentizes, the screening solubility property is good, the solvent of low toxicity, searching is polyethylene dissolving well, can meet the solvent of spraying precipitated phase conversion method filming technology requirement again.
The polyolefine that the present invention selects for use is a vinyon, and the screening principle of polymer materials is: rheological is good, be easy to make film, selects its melting index (MI) should be more than 2 for this reason, and molecular-weight average is being advisable below 30000.In the actual production, different according to polymerization mechanism and working pressure, produce polyethylene three kinds of methods are arranged, wherein: radical polymerization obtains having the new LDPE (film grade) linear molecule of side chain under the High Temperature High Pressure, the molecular weight of its polymer molecule is little, be fit to the system film, and other two kinds of methods: with transition heavy metal oxide and Ziegler-Natta initiator (TiCl
4-Al (C
2H
5)
3) coordination polymerization process that causes, the molecular weight of polyethylene of production big (＞50000), be not suitable for making film production.The present invention selects for use molecular weight distribution about 30000 for this reason, and MI is the new LDPE (film grade) (LDPE) of 5-10 (g/10min).
In order to strengthen the reactive force between the polyethylene molecule, can select linear low density polyethylene (LLDPE) for use.Linear low density polyethylene makes molecular chain relatively unfold because there is not side chain, and the molecule tertiary structure is more prone to the line of a bending around knot, and the reactive force between the molecular chain also can strengthen.When it is dissolved in organic solvent, when becoming the polymer true solution, intermolecularly just there is a part solderless wrapped connection, after spraying was deposited to the fertiliser granulates surface, solvent was subjected to thermal evaporation, intermolecularly thisly twined that connect can be tightr, and institute's film forming has better toughness and hole.If but use separately, can be big because of Intermolecular Forces, and make its viscosity increase, cause the adhesion between the fertiliser granulates.There is a lot of side chains in general high voltage new LDPE (film grade) molecule, and numerous side chains makes that molecule self solderless wrapped connection is a ball of string shape, and the reactive force between the molecule reduces, and the structural strength that shows is not as linear low density polyethylene.If linear polyethylene with exist the polyethylene of side chain to be used, then ball of string shape molecule is filled between the linear molecule, gained film and good network structure is arranged has certain space again, has good space multistory structure as controlled-release material; Be used problems such as to overcome adhesion, satisfy needed processing characteristics.For this reason, the method for production coated fertilizer of the present invention adopts low-molecular-weight linearity and branched chain type new LDPE (film grade) as coated fertilizer, guarantees that polymer materials is suitable for making release-controlled film.
Wherein the new LDPE (film grade) trade mark is: 1F7B, 1C7A, LD100 (Yanshan Petrochemical) etc., the melting point resin of these trades mark is low, melt flow rate (MFR) is high.The trade mark of linear low density polyethylene is: DFDA-7042 (Qilu Petrochemical), DNDA7144 and DNDA7145 (Daqing petrochemical) etc.As index, preparation mass fraction ratio has reasonable processing characteristics in the scope of 1/3-1/1 with the ratio of LLDPE/LDPE, and ratio is little, and linear molecule is few, and the film space is many, and ratio increases, and linear molecule increases, and reduce in the film space.According to this principle, the permeability of controlling diaphragm, the controlled release properties of regulation and control coated fertilizer (concrete mass fraction proportioning select as embodiment 3 as described in).
By different solvents poly solubility property experiment screening is produced the solvent of coated fertilizer, according to poly solubility parameters value: 16.2-16.6 (J/cm
3)
1/2, determine that the solubility parameters value of the solvent of use should be at 13-20 (J/cm
3)
1/2Between, look into the common solvent parameter list, have an appointment the solubility parameters value of 40 kinds of solvents in this scope, look into " solvent handbook (Cheng Nenglin again, 2002), filter out: octane, hexanaphthene, perhydronaphthalene, hexane, acetoacetic ester carry out further screening as described below as making the poly solvent of primary dcreening operation.
Measure octane (n-Octane, the CH of 100.00ml respectively
3(CH
2)
6CH
3, molecular weight 114.23, the inflammable colourless transparent liquid of middle flash-point, the solubility parameters value is 15.4 (J/cm
3)
1/2, 125.7 ℃ of boiling points (101.3kPa), fusing point-56.79 ℃; Stable performance under the normal temperature and pressure, water-soluble hardly, hazardous substance gauge number: 32008, available from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group), (the solubility parameters value is 14.9J to normal hexane
1/2/ cm
3/2, 69.0 ℃ of boiling points), hexanaphthene (Cyclohenxane, C
6H
12, molecular weight 84.2, the inflammable colourless transparent liquid of low-flash has like smell of petrol, and the solubility parameters value is 16.8 (J/cm
3)
1/2, 80.7 ℃ of boiling points (101.3kPa), 6.5 ℃ of fusing points.Stable performance under the normal temperature and pressure, water-soluble hardly, hazardous substance gauge number: 31004, available from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group), (the solubility parameters value is 18.6J to ethyl acetate
1/2/ cm
3/2, 77.1 ℃ of boiling points) and perhydronaphthalene (Decalin, C
10H
18, molecular weight 138.25, the inflammable colourless transparent liquid of high flash point, little band mentha camphor smell,, the solubility parameters value is 20 (J/cm
3)
1/2, 195.8 ℃ of cis-isomeride boiling points (101.3kPa), fusing point-42.98 ℃; Stable performance under the normal temperature and pressure, water insoluble, hazardous substance gauge number: 33550; Available from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group) in two mouthfuls of reaction flasks of 500ml in, (trade mark is respectively 1C7A (No.1 Chemical Industry Plant, Yanhua Petrochemical Co., Ltd., Beijing's product) and DNDA7144 (Daqing petrochemical) all to add 5.00 gram new LDPE (film grade)s in every kind of solvent, their ratio of quality and the number of copies is 1: 0.5,), the heating of use heating jacket is put into churned mechanically stirring rod and is stirred, the control solvent temperature, the record dissolution time is observed poly dissolution rate and dissolving situation.
The result is as shown in table 1, and the result shows:
1) octane: add heating jacket, when slowly being warmed up to boiling point, LDPE dissolves fast.Solution is transparent low viscosity, takes out with the sticking solution of getting of glass stick, can form the complete film of one deck, and film has good ductility.Polyethylene solution is placed into 70 ℃, and solution still keeps clear, and when being chilled to 60 ℃, the beginning feculence becomes milk-white coloured suspension, drops to below 50 ℃ gelation shape colloid.
2) perhydronaphthalene: stirred 30 minutes down in room temperature (31 ℃), observe and find that LDPE is not dissolved in the perhydronaphthalene.Add heating jacket, when slowly being warmed up to 60-70 ℃, LDPE begins dissolving, and when continuing to be heated to 100 ℃, LDPE dissolves fast.Solution is transparent low viscosity, takes out after getting solution with glass stick is sticking, and in air, solvent evaporates is rapid, forms the complete film of one deck on glass stick, and polyethylene film is ductile.Polyethylene solution is placed into 70 ℃, and solution still keeps clear, and when being chilled to 60 ℃, the beginning feculence becomes milk-white coloured suspension, drops to below 50 ℃ gelation shape colloid.
3) hexanaphthene: stirred 30 minutes down in room temperature (31 ℃), observe and find that LDPE does not dissolve.Add heating jacket, when slowly being warmed up to boiling point, LDPE begins swelling, continues to be heated to 40 minutes, and the LDPE dissolving fully.Solution is transparent low viscosity, takes out after getting solution with glass stick is sticking, and in air, solvent evaporates is rapid, forms the complete film of one deck on glass stick, and polyethylene film is ductile.Polyethylene solution is placed into 70 ℃, and solution still keeps clear, and when being chilled to 60 ℃, the beginning feculence becomes milk-white coloured suspension, drops to below 50 ℃ gelation shape colloid.
4) normal hexane and ethyl acetate being heated under the situation of boiling point, all can only make the polyethylene swelling as solvent, can not be configured to the polymer true solution.
This shows that at normal temperatures, above-mentioned solvent all can not dissolve the polyethylene that the trade mark is 1F7B, but the different solvents dissolution rate is variant under the situation of heating, the molecular weight of solvent is big more, and boiling point is high more, and solute effect is good more.Octane, hexanaphthene and perhydronaphthalene be energy polyethylene dissolving granule materials all, comprehensive examination, perhydronaphthalene and octane superior solubility, but on the high side, fusing point hangs down difficult solvent recovery, and the hexanaphthene solubility property is poor slightly, but low price, fusing point are 6.5 ℃ to be reclaimed easily; In a word, perhydronaphthalene, octane and hexanaphthene can be used to dispose the coating solution of polyethylene dissolving, and normal hexane and ethyl acetate be polyethylene dissolving fully, can not be used for the configuration of coating solution.
Table 1. different solvents is to poly solubility property
Annotate: perhydronaphthalene and octane are that Shanghai organic reagent company of traditional Chinese medicines group produces in the table, and hexanaphthene, normal hexane and ethyl acetate are that Beijing reagent company produces, and are analytical pure.LDPE is 1F7B, and No.1 Chemical Industry Plant, Yanhua Petrochemical Co., Ltd., Beijing produces.
Embodiment 2, perhydronaphthalene, octane and hexanaphthene polyethylene dissolving gained coating system prepare the controlled release properties experiment of coated fertilizer
The processing unit (plant) of coated fertilizer and process flow sheet be as shown in Figure 1: wherein, 1 is Root's blower (model WL20～5/0.20) among Fig. 1, and 2 is surge tank, 3 is that under meter (model LZB-100) 4 is electric heater, 5 is fluidized-bed, and 6 is shell-and tube condenser, and 7 and 8 is air-cooler; 9 for looking handleless cup; 10 solvent susceptors, 11 is solvent barrel, 12 are oil pump (model is BRY), 13 storage tank, 14 and 15 are reactor, and 16 is two fluid shower nozzles, and 17 is that (model: V-0.14/10C), 18 is automatic feeder to air compressor, and 19 is hopper.
Utilize processing unit (plant) as shown in Figure 1, the process flow steps of employing is:
The first step: coated fertilizers such as organic solvent and polymkeric substance are added in the reactor (14 or 15), stir.
Second step: preset the coating liquid temperature, start the reactor heating system, in the automatic controlling system still in the temperature of charge setting range (70-120 ℃ kept 20-50 minute).Dissolving is complete gradually in reactor for polymkeric substance, becomes the coating solution of homogeneous.
The 3rd step: use Root's blower (1) and surge tank (3) that smooth air is provided, regulate air flow quantity with under meter (3), air communication is crossed electric heater (4) and is heated afterwards, and be transferred to bottom the fluidized-bed (5), spray into fluidized-bed through awl bucket end mouth, provide that to set off air flow rate by contrast be 20-40m/see, set off gas temperature by contrast and be controlled in the 90-110 ℃ of scope.
The 4th step: use electric screw bar (18) that the fertiliser granulates in the hopper (19) is sent into fluidized-bed, in setting off by contrast under the drainage with guide of warm air, fertiliser granulates is in ciculation fluidized state.
The 5th step: utilize air compressor (17) and two fluid shower nozzles (16) that coating liquid is atomised to the fertiliser granulates surface, promote solvent evaporates, polymer precipitation, the preparation coated fertilizer.
The 6th step: the warm air that contains organic solvent enters shell-and tube condenser (6) and air-cooler (7 and 8), and gaseous solvent progressively is cooled to liquid state, and solvent is stored in the solvent barrel (11) through susceptor (9), recycling.
The 7th step: coating quantity reaches: fertilizer quality (kg): coating liquid (L)=1: 0.8-1: 1.2 o'clock, shut-off nozzle drew off fertilizer, complete operation.
Adopt different solvent allotment coating liquids, the coating scheme is as shown in table 2, and concrete steps are:
1., the allotment of coating solution: according to the proportioning shown in the table 2 respectively the 1000ml perhydronaphthalene, octane and hexanaphthene add in the constant temperature stirring and dissolving groove reactor (14 or 15), (trade mark is respectively LD100 (Yanshan Petrochemical) and DNDA7145 (Daqing petrochemical) to add the 50g polyethylene when being warming up to 80-90 ℃, their ratio of quality and the number of copies is 1: 0.33), start agitator, continuing to be warming up to 100 ℃ keeps polyethylene being dissolved fully in 20-30 minute, obtain transparent macromolecular solution, add 5g paraffin, 0.1g pigment (extra large regent indigo plant, Germany), continue constant temperature and mix, finely dispersed coating solution just can be used to spray.
2., the processing of film-coated controlled release fertilizer: the control sprinkler pressure is 0.02MPa, and the parcel time is about 40min.
Open heat drying system (comprising equipment 1,2,3 and 4 among Fig. 1), the temperature that makes fluidized-bed (among Fig. 1 5) is between 95-105 ℃; ; Add granulated fertilizer (granular urea, Cangzhou, Hebei bigization stock company product, grain graininess 2-4mm) from opening for feed, regulating under meter (among Fig. 1 3) simultaneously, to make gas flow be 30m/sec, guarantees that granulated fertilizer becomes stable boiling state; Open coating liquid atomizer (16), begin the granulated fertilizer that is in the boiling fluidized state is coated with coating; Quantity for spray makes coating quantity reach fertilizer quality (kg): coating liquid (L)=1: 0.8-1: 1.2 o'clock, and shut-off nozzle.After the coating liquid spraying is finished, continue oven dry 1 minute, orderly close-down constant temperature stirring and dissolving groove, dry wind system, air compressor; Take out coat fertilizer from discharge port, place naturally cooling.
The film-coated controlled release fertilizer of above-mentioned preparation is carried out the controlled release properties evaluation, the evaluation method of coated fertilizer performance:
1., testing method (water-extraction method): take by weighing every kind of coat fertilizer 10.00g, be loaded in the nylon net bag, be placed in the tool lid Plastic Bottle, in bottle, add 200ml distilled water then, build bottle cap, static, the lixiviate of the thermostat container of putting into 25 ℃.Each sample is established three repetitions.During each the sampling, the vat liquor in the Plastic Bottle is all poured out, contained with spool box and get vat liquor, be used for the mensuration of urea N, P, K.The sampling and measuring time is 1 day, 4 days, 7 days, 10 days, 14 days, 21 days, 28 days.Wherein, urea N, P, K measuring method: paradimethy laminobenzaldehyde-spectrophotometry.
2., coated fertilizer nutrient release performance evaluation index:
Initial stage solubility rate (η
T1): η
T1=M
T1/ M * 100%, differential solubility rate (η
Δ t): η
Δ t=(η
Tn-η
Ti)/(t
n-t
i) * 100%, cumulative release rate (η): η=∑ (η
Tn)/M * 100%, fertilizer releasing period (T): T=1+ (80%-η
T1)/η
Tnt
nBe n days, t
iBe the 1st day, η
TnBe n-i days accumulative total release rates, η
T1Be initial stage solubility rate, M
T1Be the amount of nutrients of stripping in the 1st day, M is the total nutrient content in the coat fertilizer.
3., judgement criteria (CEN recommendation):
η
Δ t＜15%, 0.25%＜η
T1＜3.5%, the nutrient of T＞21,80% discharges the model that dynamic process meets linear equations.
The result is as shown in table 2, the result shows, its water-soluble result as can be seen, perhydronaphthalene, octane and three kinds of solvents of hexanaphthene all can prepare the stable coated fertilizer of controlled release properties, three kinds of solvents are when being equipped with identical coated fertilizer, and the initial stage solubility rate of prepared coated fertilizer is respectively 0.9%, 0.7% and 0.6%, and release period is all about 3 months, between do not have significant difference, all accord with the standard that CEN recommends.
Table 2 different solvents coating liquid prepares the controlled release properties of scheme and coated fertilizer
| Numbering | The solvent title | Solvent load (ml) | LDPE consumption (g) | Paraffin (g) | Urea (g) | η t1 | η Δt | |
| 1 | Perhydronaphthalene | 1000 | 50.0 | 10.0 | 1000 | 0.9 ％ | 1.1 ％ | 90 days |
| 2 | Octane | 1000 | 50.0 | 10.0 | 1000 | 0.7 ％ | 1.2 ％ | 83 days |
| 3 | Hexanaphthene | 1000 | 50.0 | 10.0 | 1000 | 0.6 ％ | 1.0 ％ | 99 days |
Annotate: η Δ t is the differential solubility rate, and η t1 is the initial stage solubility rate, and T is a fertilizer releasing period.
Embodiment 3, different linear polyethylene proportioning are to the influence of coated fertilizer nutrient release performance
Preparation method according to embodiment 2 described coated fertilizers, use branched chain type new LDPE (film grade) (LDPE, the trade mark is 1F7B) and linear low density polyethylene (LLDPE, the trade mark is: DFDA-7042) two kinds not the polythene material of synteny (4 ratios are set, as shown in table 3), use cyclohexane give to be solvent, obtain corresponding 4 processing schemes (shown in the table 31,2,3 and 4), each handles three repetitions.Concrete proportional arrangement and other material usage quantity see Table 3, with the polyethene preparation film-coated controlled release fertilizer of different proportionings.
Four kinds of film-coated controlled release fertilizers of above-mentioned preparation are carried out the release performance detection according to the evaluation method of embodiment 2 described coated fertilizer performances respectively, above-mentioned fertilizer at the release performance in the water shown in Fig. 2 and table 3, linear low density polyethylene and side chain new LDPE (film grade) proportioning (LLDPE/LDPE) ratio are in 0.33 to 1 scope as can be seen, increase along with LLDPE/LDPE proportioning ratio, the initial stage solubility rate of coated fertilizer reduces gradually, that is to say increase along with the relative consumption of LLDPE, the control effect of the coated fertilizer of handling improves, and can process to obtain the standard compliant coated fertilizer of initial stage solubility rate in this scope.Corresponding with top two indexs, along with the increase of the relative consumption of LLDPE, the coated fertilizer release rate is slack-off, and its release period can be elongated thereupon.In this scope, can process and obtain release period at individual month film-coated controlled release fertilizer of 1-3.Please indicate that the cumulative release of N shown in ordinate zou speed is coated fertilizer nutrient release performance evaluation index among Fig. 2: cumulative release rate (η): η=∑ (η
Tn)/M * 100%.Among the figure each curve represent respectively to be numbered 1,2,3 and the coated fertilizer of 4 four kind of Processing of Preparation)
The release performance experimental result of the coated fertilizer of the material preparation of table 3. linearity and the different proportionings of branched chain type polyethylene
| Numbering | LLDPE: LDPE (total amount is 100g) | Solvent (L) | Paraffin (g) | Urea | η t1 | η Δt | |
| 1 | 1∶3 | 2 | 20 | 2 | 5.1 | 2.4 | 32 |
| 2 | 1∶2 | 2 | 20 | 2 | 1.5 | 1.3 | 63 |
| 3 | 1∶1.4 | 2 | 20 | 2 | 0.5 | 1.0 | 79 |
| 4 | 1∶1 | 2 | 20 | 2 | 0.7 | 0.8 | 97 |
Annotate: solvent is a hexanaphthene in the table, and reagent company in Beijing produces, analytical pure.The LLDPE trade mark is: DFDA-7042, Qilu Petrochemical; The LDPE trade mark is 1F7B, and No.1 Chemical Industry Plant, Yanhua Petrochemical Co., Ltd., Beijing produces.
Claims (8)
1, a kind of coated fertilizer of release and release control fertilizer, comprise molecular-weight average at branched chain type new LDPE (film grade) between the 20000-30000 dalton and molecular-weight average the linear low density polyethylene between 20000-30000 dalton; The ratio of quality and the number of copies of described branched chain type new LDPE (film grade) and linear low density polyethylene is 1: 0.33-1.
2, material according to claim 1 is characterized in that: the described branched chain type new LDPE (film grade) trade mark is one or more among 1F7B, 1C7A and the LD100.
3, material according to claim 1 is characterized in that: the described linear low density polyethylene trade mark is one or more among DFDA-7042, DNDA7144 and the DNDA7145.
4, a kind of polymer coating controlled release fertilizer is made up of the coated fertilizer among water miscible fertilizer and the claim 1-3; Described coated fertilizer is coated on described water miscible fertilizer.
5, the method for the described polymer coating controlled release fertilizer of a kind of production claim 4 may further comprise the steps:
1) any one coated fertilizer described in organic solvent and the claim 1-3 is added in the reactor, the post-heating that stirs is made coating solution; The ratio of quality and the number of copies of described organic solvent and described coated fertilizer is 100: 6-10, described organic solvent are one or more in octane, hexanaphthene and the perhydronaphthalene;
2) feed the gas of temperature in 90-110 ℃ of scope to the fluidized-bed bottom, the flow of described gas is 20-40m/sec; Simultaneously water miscible fertilizer is sent into fluidized-bed, make fertilizer be in ciculation fluidized state;
3) with the coating solution atomization to the fertiliser granulates surface, make film-coated controlled release fertilizer.
6, method according to claim 5 is characterized in that: the Heating temperature in the described step 1) is 70-120 ℃, and be 20-50 minute heat-up time.
7, according to claim 5 or 6 described methods, it is characterized in that: the gas described step 2) is air; Provide by Root's blower; In the described step 3) coating solution liquid being atomised to the fertiliser granulates surface, is to adopt air compressor and two fluid shower nozzles to realize.
8, according to claim 5 or 6 described methods, it is characterized in that: described organic solvent is by condenser and air-cooler cooling, recycling.
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| CN101302131B (en) * | 2008-05-28 | 2010-11-03 | 北京市农林科学院 | S type controlled-release urea and preparing method thereof |
| CN101665392B (en) * | 2008-09-02 | 2012-07-04 | 北京市农林科学院 | Controlled-release special nitrogen fertilizer for greenhouse muskmelons, and preparation method thereof |
| CN101456775B (en) * | 2009-01-08 | 2012-10-03 | 北京市农林科学院 | Fertilization method of cool season turf and its special coated controlled release fertilizer |
| CN101462907B (en) * | 2009-01-13 | 2012-12-26 | 北京市农林科学院 | Coated compound fertilizer and preparation thereof |
| CN104557323B (en) * | 2015-01-27 | 2017-05-10 | 北京富特来复合肥料有限公司 | Degradable resin coating material and application thereof |
| US10081578B2 (en) * | 2015-05-22 | 2018-09-25 | Honeywell International Inc. | Wax-based fertilizer coatings with polyethylene- or polypropylene-based polymers |
| CN105860980A (en) * | 2016-04-13 | 2016-08-17 | 湖南省土壤肥料研究所 | Slow release oxidant adopting calcium peroxide as matrix and polyethylene as coating film, and preparation method thereof |
| CN110803962B (en) * | 2016-08-31 | 2021-11-26 | 山东农大肥业科技有限公司 | Modified biological wax coating material for preparing controlled release fertilizer |
| CN107056407A (en) * | 2016-12-30 | 2017-08-18 | 华南农业大学 | A kind of film-coated and slow release fertilizer using municipal sludge as raw material and preparation method thereof |
| KR20200062251A (en) | 2017-09-29 | 2020-06-03 | 다이니폰 인사츠 가부시키가이샤 | Sealant film for packaging liquid contents and a laminate comprising the same, and packaging material for liquid contents, package for liquid contents |
| CN111875441A (en) * | 2020-06-28 | 2020-11-03 | 应城市新都化工复合肥有限公司 | Stable long-acting compound fertilizer and preparation method thereof |
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