A kind of chitosan sustained-release fertilizer microballoon and preparation method thereof
Technical field
The invention belongs to slow release fertilizer field, particularly one is mixed with slow release fertilizer microballoon and preparation method thereof with chitosan and chemical fertilizer.
Background technology
China is large agricultural country, and along with the improvement of agriculture production technology and the raising of output, the degree of dependence for chemical fertilizer is more and more higher.But it is 46.3% that traditional chemical only offers rate in the tribute that grain increases, well below World Developed Countries level.Utilization rate of fertilizer is lowly the problem that always annoying people, cause the low chief reason of utilization rate of fertilizer to be leaching loss and the volatilization of fertilizer, a large amount of leaching losses of fertilizer not only make soil fertility decline, and crop reduces, cause a large amount of financial losses, but also can environmental pollution be caused.Therefore, need to develop a kind of new-type fertilizer.
Slow release fertilizer is a kind of recent tendency of chemical fertilizer development, its nutrient releasing speed and quantity have certain controllability, can need Releasing nutrient according to plant growth, make it permanently effective within the whole vegetative period of farm crop, greatly can improve the utilization ratio of fertilizer, reduce consumption and application times.
Slow release fertilizer domestic is at present fertile mainly with envelope type slow release greatly and be main without slow release fertilizer.Envelope type slow release fertilizer is the surface utilizing vulcanization bed or rotary drum coating machine etc. slow-release material to be wrapped in fertiliser granulates, its complex manufacturing of this product and expensive, be only applicable to the field that the economic worth such as flowers, vegetables is higher, some coated fertilizer is not easily degraded simultaneously, contaminated soil environment, the large face in farmland that is therefore not suitable for uses.Fertilizer nutrient is disperseed equably or is adsorbed in certain specific function material without slow release fertilizer, fertilizer nutrient discharges gradually in the degradation process of functional materials, and utilization ratio is high, and manufacturing process is simple, production cost is low, and slow-release material is easy to degraded, suit large area to popularize use.
China Patent Publication No. is that CN103254024A discloses a kind of Attapulgite mineral powder slow-release fertilizer, this slow-release fertilizer is prepared from through fermentation by Attapulgite mineral powder and poultry manure, can decreasing pollution and optimize edatope, but using attapulgite as sustained release dosage, amount makes slow release effect not obvious less, amount is many can make nutrient releasing speed too slow, and the water-absorbent of attapulgite is very strong, this slow-release fertilizer is applied in soil, the attapulgite very soon moisture absorbed in soil makes fertilizer dissolve, and does not reach long-term sustained release effect.
China Patent Publication No. is that to disclose a kind of take perlite as the compound slow release fertilizer of carrier to CN102826920A, this slow-release fertilizer take perlite as carrier, sulfuric acid, nitrogenous fertilizer, potash fertilizer aqueous solution are sprayed on perlite particle, spray phosphorus powder fertilizer simultaneously and form ternary remarry slow release fertilizer, utilize perlitic adsorptivity that fertilizer slow release is discharged; Because perlite has very strong water-absorbent, in soil, be easy to absorb the fertilizer that moisture makes load in porous dissolve release, sustained release rate is relatively very fast, can not reach the effect that nutrient discharges for a long time, is not suitable for longer plant growth in vegetative period.
China Patent Publication No. is that CN1470485A discloses carrier type slow-release fertilizer and preparation method thereof, and chemical fertilizer and carrier substance are uniformly mixed by the method, add linking agent and fully react and obtain.Directly by macromolecule organic carrier as polyvinyl alcohol, polyoxyethylene glycol mix with fertilizer solution, part fertilizer molecule can only be polymerized with macromolecular material by linking agent, need the consumption increasing carrier substance and linking agent could increase the charge capacity of fertilizer, but cost also increase to some extent; The polymer carrier simultaneously adopted has certain solvability in water, and the rate of release of fertilizer nutrient, than very fast, effectively can not delay the solvability of fertilizer.
According to above-mentioned, the slow-release fertilizer being slow-release material with inorganics and macromolecule organic, fertilizer charge capacity is little, the nutrients release of fertilizer is relatively more very fast than coated fertilizer, does not reach the slow release effect in ideal.Chitosan is a kind of biodegradable macromolecular material, has good absorption property, as a kind of biological microbe fertilizer, can play the effect of improvement soil and coordinate plant growth after it is degradable; But chitosan is readily dissolved in the lower aqueous solution of pH, cause a large amount of losses of chitosan, can not directly be used for preparing slow-release fertilizer, therefore need to carry out modification to chitosan, improve its using value in slow release fertilizer field.
Summary of the invention
The present invention is directed to the deficiency and defect that exist in above-mentioned slow release fertilizer technology, provide a kind of chitosan sustained-release fertilizer microballoon, this fertilizer for main raw material(s), utilizes ion crosslinking agent to aggregate into microballoon with chitosan, polyvinyl alcohol, chemical fertilizer, sodium alginate.Chitosan microball is a kind of spherical porous microsphere, there is larger specific surface area and stronger adsorptive power, fertilizer is blended in chitosan solution, under the effect of linking agent, chitosan is solidified into microballoon, in the process, be combined between fertilizer with chitosan by intermolecular polar attraction power, fertilizer molecule is fixed on chitosan microball to be had in cancellated crosslinked micropore.Execute in soil by slow release fertilizer microballoon, microballoon absorbs the moisture in soil, the fertilizer nutrient of microsphere surface load dissolves release, and one deck sodium alginate dielectric substrate due to microsphere surface load, slows down the rate of release of surperficial fertilizer nutrient; Along with the prolongation of time, microballoon water absorption and swelling, the fertilizer nutrient be fixed in microballoon network structure starts slow releasing, and when microballoon water regain is tending towards saturated, fertilizer nutrient can only discharge along with the slowly-releasing degraded of chitosan microball, reaches the object of sustained-release and controlled release.
Further aim of the present invention is to provide a kind of preparation method of chitosan sustained-release fertilizer microballoon, the method is dissolved in acetic acid solution by chitosan, get chemical fertilizer and polyvinyl alcohol dissolution in chitosan acetic acid solution, add ion crosslinking agent and obtain microballoon, microballoon is placed in sodium alginate soln sonic oscillation, forms chitosan sustained-release fertilizer microballoon.Be cross-linked into the process of microballoon, fertilizer molecule coheres, be wrapped in the cross-linked network micropore of chitosan microball, nutrient is along with the degraded slow releasing of chitosan microball, and simultaneously microsphere surface has wrapped up one deck sodium alginate dielectric film, be conducive to reducing nutrient the release initial stage produce prominently release phenomenon.
A kind of chitosan sustained-release fertilizer of the present invention microballoon, it is characterized in that this slow release fertilizer microballoon is made up of the sodium alginate of the chemical fertilizer of 60-80 weight part, the chitosan of 10-20 weight part, the polyvinyl alcohol of 1.0-3.0 weight part and 1.0-5.0 weight part, the specific surface area of this microballoon is 60-100 m
2/ g, size distribution is between 10-120 μm, and aperture is 5-100nm, and pore volume is 1.0-3.5 cm
3/ g, porosity is 70-90%.
Chemical fertilizer described above is nitrogenous fertilizer, phosphate fertilizer, potash fertilizer and trace element fertilizer, and wherein nitrogenous fertilizer is at least one of urea, ammonium chloride, ammonium sulfate, ammonium nitrate, bicarbonate of ammonia; Phosphate fertilizer is at least one of calcium superphosphate, double superhosphate, monoammonium phosphate, diammonium phosphate; Potash fertilizer is at least one of Repone K, potassium sulfate, saltpetre, potassium phosphate,monobasic; Trace element fertilizer is at least one of magnesium sulfate, manganous sulfate, iron nitrate, zinc sulfate, copper sulfate; Described relative molecular weight of chitosan is 10000-200000, and deacetylation is 80-95%.
The preparation method of a kind of chitosan sustained-release fertilizer of the present invention microballoon, is characterized in that preparation method comprises the following steps:
(1) put in agitator by the chitosan solid of 10-20 weight part, add the acetum that massfraction is 3-5%, obtained massfraction is the chitosan-acetic acid solution of 1-5%; Add the chemical fertilizer of 60-80 weight part and the polyvinyl alcohol of 1.0-3.0 weight part again, to stir 2-5min under the speed of 500-1000r/min, dissolve the composite solution obtaining chitosan and chemical fertilizer completely;
(2) sodium alginate of 1.0-5.0 weight part is dissolved in water, is made into the sodium alginate soln that massfraction is 0.2-0.5%, stand-by;
(3) composite solution of chitosan and chemical fertilizer is put in microwave reactor, under 200-500 r/min stirring velocity, in the composite solution of chitosan and chemical fertilizer, add the KOH solution of 1.0mol/L, regulate the pH=4.5-6.5 of composite solution with pH meter;
(4) parameter of microwave reactor is set: temperature 50-80 DEG C, rotating speed 600-1000 r/min, with this understanding the ionomer agent solution of 0.4-0.8 g/L is slowly joined in the composite solution in step (3), the mass ratio of linking agent and chitosan is 1:3-8, continue to stir 15-30min, obtain the microspheres solution of chitosan and chemical fertilizer;
(5) by the chitosan for preparing and chemical fertilizer microspheres solution centrifuge 5min, rotating speed is 4000 r/min, removes supernatant liquid, isolates chitosan sustained-release fertilizer microballoon; Microballoon is placed in the sodium alginate soln of step (2), sonic oscillation 10min under normal temperature, centrifugation, by product dry 15-30min at 60-80 DEG C of temperature, obtains chitosan microball slow release fertilizer.
Ion crosslinking agent described in above-mentioned steps (4) is any one in trisodium phosphate, tripoly phosphate sodium STPP, sodium tetrapolyphosphate, Sodium hexametaphosphate 99.
The stirrer used in above-mentioned steps (1) is homogenizer, rotating speed >=400r/min, and blade of stirrer maximum linear velocity, can be even by slurry agitation in 1-3min within 15s.
Be equipped with magnetic stirring apparatus in the microwave reactor used in above-mentioned steps (3), stirring velocity continuously adjustabe also shows in real time, and temperature controlling range: 0-250 DEG C, can install Dropping feeder; Utilize microwave radiation to accelerate speed of reaction, microballoon productive rate is high, and reaction conditions is easy to control, and can control microballoon pattern preferably, and easy to operate.
The drying machine used in above-mentioned steps (5) is roller dryer, and dried material thermal source is warm air, and temperature range is 50-150 DEG C.
Outstanding feature of the present invention and beneficial effect are:
1, in the present invention using chitosan microball as the solid support material of slow release fertilizer, by chitin modified one-tenth polymer microsphere, its surface-area and adsorptive power can be increased, and the microballoon formed has crosslinking net microvoid structure, fertilizer solution is added in the process being cross-linked into microballoon, fertilizer molecule coheres, be wrapped in cross-linked network micropore, and nutrient, along with the degraded slow releasing of chitosan microball, reaches the object of sustained-release and controlled release.
2, the present invention is by the also coated one deck sodium alginate film in the chitosan microball of preparation surface, because chitosan is a kind of polycation polysaccharide, sodium alginate is a kind of polyanionic polysaccharide, there is electrostatic polyreaction between the two, form thin film at microsphere surface, hinder the diffusion of fertilizer nutrient in microballoon, reduce the swelling ratio of chitosan microball, reduce the release initial stage because of the swelling generation of chitosan microball fertilizer nutrient prominently to release, slow down the release rate of fertilizer nutrient.
3, the chitosan material in the present invention is a kind of biodegradable natural macromolecular material, wide material sources, and crust waste can be utilized to refine and process, produce market potentiality to be exploited is huge; Chitosan or a kind of soil improvement agent, be a kind of organic fertilizer of high-quality, can be absorbed by plants, for plant-growth provides nutrition after degraded in soil.
4, the present invention adopts ionic cross-linking to prepare chitosan sustained-release fertilizer microballoon, preparation method is simple, environment-protecting asepsis, do not need in preparation process with an organic solvent with harmful chemical cross-linking agent as glutaraldehyde, epoxy chloropropane etc., experiment condition is simply gentle, is applicable to industrial production.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of the chitosan sustained-release fertilizer microballoon of accompanying drawing 1. embodiment 3 preparation.
Embodiment
Below in conjunction with embodiment, the present invention is explained in detail, is not restricted to the present invention.When not departing from aforesaid method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or improvement, all should be included within protection scope of the present invention.
embodiment 1
(1) put in agitator by the chitosan solid of 10 weight parts, add the acetum that massfraction is 3%, obtained massfraction is the chitosan-acetic acid solution of 5%; Add the polyvinyl alcohol of the urea of 50 weight parts, the monoammonium phosphate of 10 weight parts, the saltpetre of 10 weight parts, the manganous sulfate of 6 weight parts and 1.0 weight parts again, to stir 2min under the speed of 1000r/min, dissolve the composite solution obtaining chitosan and chemical fertilizer completely;
(2) sodium alginate of 5.0 weight parts is dissolved in water, be made into massfraction be 0.5% sodium alginate soln stand-by;
(3) composite solution of chitosan and chemical fertilizer is put in microwave reactor, under 200r/min stirring velocity, in the composite solution of chitosan and chemical fertilizer, add the KOH solution of 1.0mol/L, regulate the pH=5.0 of composite solution with pH meter;
(4) parameter of microwave reactor is set: temperature 50 C, rotating speed 600r/min, with this understanding the sodium pyrophosphate solution of 0.4g/L is slowly joined in the composite solution in step (3), the mass ratio of trisodium phosphate and chitosan is 1:3, continue to stir 30min, obtain the microspheres solution of chitosan and chemical fertilizer;
(5) by the chitosan for preparing and chemical fertilizer microspheres solution centrifuge 5min, rotating speed is 4000 r/min, goes upper liquid, isolates chitosan sustained-release fertilizer microballoon; Microballoon is placed in the sodium alginate soln of step (2), sonic oscillation 10min under normal temperature, centrifugation, by product dry 30min at 60 DEG C of temperature, obtains chitosan microball slow release fertilizer.
By chemical fertilizer leaching experiment, the nutrients release of a kind of chitosan sustained-release fertilizer of the present invention microballoon is as following table:
embodiment 2
(1) put in agitator by the chitosan of 12 weight parts, add the acetum that massfraction is 3%, obtained massfraction is the chitosan-acetic acid solution of 5%; Add the polyvinyl alcohol of the ammonium chloride of 40 weight parts, the calcium superphosphate of 20 weight parts, the Repone K of 10 weight parts, the magnesium sulfate of 5 weight parts, the manganous sulfate of 5 weight parts and 1.0 weight parts again, to stir 2min under the speed of 1000r/min, dissolve the composite solution obtaining chitosan and chemical fertilizer completely;
(2) sodium alginate of 4.0 weight parts is dissolved in water, be made into massfraction be 0.2% sodium alginate soln stand-by;
(3) composite solution of chitosan and chemical fertilizer is put in microwave reactor, under 300r/min stirring velocity, in the composite solution of chitosan and chemical fertilizer, add the KOH solution of 1.0mol/L, regulate the pH=6.0 of composite solution with pH meter;
(4) parameter of microwave reactor is set: temperature 60 C, rotating speed 700 r/min, with this understanding the sodium tripolyphosphate solution of 0.5 g/L is slowly joined in the composite solution in step (3), the mass ratio of tripoly phosphate sodium STPP and chitosan is 1:4, continue to stir 25min, obtain the microspheres solution of chitosan and chemical fertilizer;
(5) by the chitosan for preparing and chemical fertilizer microspheres solution centrifuge 5min, rotating speed is 4000 r/min, goes upper liquid, isolates chitosan sustained-release fertilizer microballoon; Microballoon is placed in the sodium alginate soln of step (2), sonic oscillation 10min under normal temperature, centrifugation, by product dry 25min at 70 DEG C of temperature, obtains chitosan microball slow release fertilizer.
By chemical fertilizer leaching experiment, the nutrients release of a kind of chitosan sustained-release fertilizer of the present invention microballoon is as following table:
Time |
Fertilizer release rate |
Sustained-release micro-spheres dissolution rate |
7d |
6% |
3% |
1 month |
30% |
25% |
2 months |
65% |
48% |
3 months |
80% |
70% |
4 months |
100% |
89% |
embodiment 3
(1) put in agitator by the chitosan solid of 16 weight parts, add the acetum that massfraction is 4%, obtained massfraction is the chitosan-acetic acid solution of 4%; Add the polyvinyl alcohol of the ammonium sulfate of 40 weight parts, the double superhosphate of 10 weight parts, the potassium sulfate of 20 weight parts, the iron nitrate of 6 weight parts and 1.0 weight parts again, to stir 5min under the speed of 500r/min, dissolve the composite solution obtaining chitosan and chemical fertilizer completely;
(2) sodium alginate of 3.0 weight parts is dissolved in water, be made into massfraction be 0.3% sodium alginate soln stand-by;
(3) composite solution of chitosan and chemical fertilizer is put in microwave reactor, under 400r/min stirring velocity, in the composite solution of chitosan and chemical fertilizer, add the KOH solution of 1.0mol/L, regulate the pH=4.5 of composite solution with pH meter;
(4) parameter of microwave reactor is set: temperature 70 C, rotating speed 800 r/min, with this understanding the sodium tetrapolyphosphate solution of 0.6 g/L is slowly joined in the composite solution in step (3), the mass ratio of sodium tetrapolyphosphate and chitosan is 1:5, continue to stir 20min, obtain the microspheres solution of chitosan and chemical fertilizer;
(5) by the chitosan for preparing and chemical fertilizer microspheres solution centrifuge 5 min, rotating speed is 4000 r/min, goes upper liquid, isolates chitosan sustained-release fertilizer microballoon; Microballoon is placed in the sodium alginate soln of step (2), sonic oscillation 10min under normal temperature, centrifugation, by product dry 15min at 80 DEG C of temperature, obtains chitosan microball slow release fertilizer.
By chemical fertilizer leaching experiment, the nutrients release of a kind of chitosan sustained-release fertilizer of the present invention microballoon is as following table:
Time |
Fertilizer release rate |
Sustained-release micro-spheres dissolution rate |
7d |
3% |
1% |
1 month |
28% |
18% |
2 months |
46% |
35% |
3 months |
75% |
62% |
4 months |
100% |
85% |
embodiment 4
(1) put in agitator by the chitosan solid of 18 weight parts, add the acetum that massfraction is 4%, obtained massfraction is the chitosan-acetic acid solution of 5%; Add the polyvinyl alcohol of the ammonium nitrate of 40 weight parts, the monoammonium phosphate of 20 weight parts, the saltpetre of 10 weight parts, the zinc sulfate of 5 weight parts and 2.0 weight parts again, to stir 3min under the speed of 800r/min, dissolve the composite solution obtaining chitosan and chemical fertilizer completely;
(2) sodium alginate of 2.0 weight parts is dissolved in water, be made into massfraction be 0.5% sodium alginate soln stand-by;
(3) composite solution of chitosan and chemical fertilizer is put in microwave reactor, under 500r/min stirring velocity, in the composite solution of chitosan and chemical fertilizer, add the KOH solution of 1.0mol/L, regulate the pH=5.5 of composite solution with pH meter;
(4) parameter of microwave reactor is set: temperature 80 DEG C, rotating speed 900 r/min, with this understanding the sodium hexametaphosphate solution of 0.8 g/L is slowly joined in the composite solution in step (3), the mass ratio of Sodium hexametaphosphate 99 and chitosan is 1:3-8, continue to stir 15min, obtain the microspheres solution of chitosan and chemical fertilizer;
(5) by the chitosan for preparing and chemical fertilizer microspheres solution centrifuge 5min, rotating speed is 4000 r/min, goes upper liquid, isolates chitosan sustained-release fertilizer microballoon; Microballoon is placed in the sodium alginate soln of step (2), sonic oscillation 30min under normal temperature, centrifugation, by product dry 15min at 80 DEG C of temperature, obtains chitosan microball slow release fertilizer.
By chemical fertilizer leaching experiment, the nutrients release of a kind of chitosan sustained-release fertilizer of the present invention microballoon is as following table:
Time |
Fertilizer release rate |
Sustained-release micro-spheres dissolution rate |
7d |
2% |
1% |
1 month |
15% |
10% |
2 months |
45% |
40% |
3 months |
82% |
75% |
4 months |
100% |
92% |
embodiment 5
(1) put in agitator by the chitosan solid of 20 weight parts, add the acetum that massfraction is 3%, obtained massfraction is the chitosan-acetic acid solution of 5%; Add the polyvinyl alcohol of the bicarbonate of ammonia of 30 weight parts, the diammonium phosphate of 20 weight parts, the potassium phosphate,monobasic of 20 weight parts, the copper sulfate of 10 weight parts and 3.0 weight parts again, to stir 2min under the speed of 1000r/min, dissolve the composite solution obtaining chitosan and chemical fertilizer completely;
(2) sodium alginate of 2.0 weight parts is dissolved in water, be made into massfraction be 0.5% sodium alginate soln stand-by;
(3) composite solution of chitosan and chemical fertilizer is put in microwave reactor, under 500r/min stirring velocity, in the composite solution of chitosan and chemical fertilizer, add the KOH solution of 1.0mol/L, regulate the pH=5.5 of composite solution with pH meter;
(4) parameter of microwave reactor is set: temperature 80 DEG C, rotating speed 1000 r/min, with this understanding the sodium hexametaphosphate solution of 0.8 g/L is slowly joined in the composite solution in step (3), the mass ratio of Sodium hexametaphosphate 99 and chitosan is 1:3-8, continue to stir 15min, obtain the microspheres solution of chitosan and chemical fertilizer;
(5) by the chitosan for preparing and chemical fertilizer microspheres solution centrifuge 5min, rotating speed is 4000 r/min, goes upper liquid, isolates chitosan sustained-release fertilizer microballoon; Microballoon is placed in the sodium alginate soln of step (2), sonic oscillation 10min under normal temperature, centrifugation, by product dry 15min at 80 DEG C of temperature, obtains chitosan microball slow release fertilizer.
By chemical fertilizer leaching experiment, the nutrients release of a kind of chitosan sustained-release fertilizer of the present invention microballoon is as following table:
Time |
Fertilizer release rate |
Sustained-release micro-spheres dissolution rate |
7d |
2% |
1% |
1 month |
15% |
10% |
2 months |
45% |
40% |
3 months |
82% |
75% |
4 months |
100% |
92% |