CN104310361B - A kind of production method preparing biphosphate calcium oxide by-product tree peony special fertilizer - Google Patents
A kind of production method preparing biphosphate calcium oxide by-product tree peony special fertilizer Download PDFInfo
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Abstract
The present invention relates to chemical technology field, a kind of production method preparing potassium dihydrogen phosphate by-product tree peony special fertilizer, it is changed by the coefficients such as the temperature of potassium dihydrogen phosphate being prepared by phosphoric acid by wet process, improve the purity of potassium dihydrogen phosphate product, the Chemical Mixed Fertilizer containing N, P, K compound state can be produced simultaneously, and in filtrate, add a kind of controlled-releasing compounding fertilizer of formaldehyde making.The method is possible not only to improve the purity of potassium dihydrogen phosphate, and the absorptivity of this tree peony special fertilizer produced is good, and this tree peony special fertilizer simultaneously produced disclosure satisfy that the nutritional need in each period in tree peony growth cycle, is efficient Chemical Mixed Fertilizer.
Description
Technical field
The present invention relates to chemical technology field, particularly relate to a kind of production preparing potassium dihydrogen phosphate by-product tree peony special fertilizer
Method.
Background technology
Potassium dihydrogen phosphate, is widely used in the work of the almost all types such as all types of industrial crops, grain, melon fruits and vegetables
Thing, has notable increasing both production and income, the amount of changing optimizes many excellent effects such as quality, resistant to lodging, disease and insect resistance, preventing and treating early ageing, and
There is the malnourished effect overcoming the plant growth later stage aging absorbability of root system to decline and to cause, belong to novel high density phosphorus
Potassium Was Used compound fertilizer, is efficient phosphorus potassium complex fertilizer agriculturally.Current domestic a lot of fertilizer producers are all producing di(2-ethylhexyl)phosphate
Hydrogen K composite fertilizer, its production method mainly have neutralisation, extraction, ion-exchange, double decomposition, direct method, crystallisation and
Electrolysis etc., wherein double decomposition includes that thermal phosphoric acid and phosphoric acid by wet process produce potassium dihydrogen phosphate, and thermal phosphoric acid cost is relatively big,
Should not be as being widely popularized, therefore, Wet-process Phosphoric Acid Production potassium dihydrogen phosphate product becomes main method, wet process phosphoric acid for preparing phosphorus
The basic step of acid is as follows:
Reaction equation one:
CO(NH2)2+H3PO4=CO (NH2)2.H3PO4
Reaction equation two
CO(NH2)2.H3PO4+ KOH=KH2PO4+H2O+CO(NH2)2
Reacting at 40～80 DEG C in whole reaction, there is not any change in substantial amounts of phosphoamide after the completion of reaction, with
Time due to phosphoamide solubility the highest, when 20 DEG C, its solubility is that 85g/100ml (refers to " phosphate fertilizer and composite fertilizer " volume 20
6th phase solubility of chemical fertilizer and Compound fertilizer production technology), the rising of the solubility with temperature of phosphoamide simultaneously and increase
Greatly, so the phosphoamide contained in filtrate by cooling crystal separate out after, in filtrate possibly together with a large amount of undecomposed phosphoamides,
K+、H2PO4 -、HPO4 2-、PO4 3-If directly doing waste water and discharge, both having wasted resource, the waste of resource, meanwhile, analysis can be caused again
The purity of the dipotassium hydrogen phosphate crystal gone out is the highest.
Tree peony (Paeonia suffruticosa Andr.) is the xylophyta of Paeoniaceae Paeonia sect. Moutan, is original
Traditional famous flower in China.It is wide in variety, and flower is very large, colourful, elegant and poised.Have " aromatic ", " in spending it
King " title.Annual 4～bloom May, a big look gorgeous, magnificent incomparably, the rich elegance of appearance, the fragrance of flowers assails one's nose, very popular.
But, the tree peony nature florescence is short and excessively concentrates, while leaving numerous regretting to the domestic and foreign tourists come because of respect for the fame,
Also the industrialized development of tree peony is constrained.Along with the progress of technology, tree peony four seasons open technique has broken through, but, there is also
Spend little, less, pattern the most just, view and admire the problems such as quality is low.Therefore, tree peony Restraining culture quality is improved, for meeting visitor's anniversary
The long-cherished wish admired the beauty of flowers, significant.
Conventional tree peony fertilizing method is: with chicken manure, oil meal or bone meal fertilizer, or chemical fertilizer, such as patent
Number being the patent of invention " a kind of tree peony Restraining culture method " of CN201310011469.0, its fertilising is: every two days to blade face spray
Executing a mass concentration is the potassium dihydrogen phosphate of 0.1%, and every five days is the phosphinylidyne of 0.1% to mass concentration of foliage-spray
Amine, the vertical flower bud phase, mass concentration of pouring is the compound solution of 0.2% weekly.Patent No. CN201210039212.1
Patent of invention " a kind of nutritional compound fertilizer for dicentra spectabilis and preparation method thereof ", its composite fertilizer material be thunder godvine, the root bark of shaggy-fruited dittany,
Trifoliate jewelvine, tobacco leaf, Radix Isatidis, phosphoamide, ammonium nitrate, potassium dihydrogen phosphate, potassium sulfate, calcium nitrate, magnesium sulfate, borax, zinc sulfate, sulphur
Acid ferrous iron, methyl Tobe, copper sulphate etc., it is fertile, according to another report that it is exactly the mixing simply mixed by various fertilizer:
Phosphoamide, the plant absorption utilization rate of carbon ammonium be: 20% one 46%；
The plant absorption utilization rate of phosphate fertilizer (two ammoniums, an ammonium, coarse whiting) is: 10% one 25%；
The plant absorption utilization rate of common potash fertilizer is: 45% one 60%.
Unabsorbed mixing fertilizer, easily causes soil compaction, mixing simultaneously fertile release and lose too fast, the later stage is because of rain
Water soaking or fertilizer self decompose, and cause the nutrition in soil cannot supply the needs of tree peony, cause the growing way of tree peony to slow down or
Person is rested.
During Wet-process Phosphoric Acid Production potassium dihydrogen phosphate, the purity of potassium dihydrogen phosphate is the highest, possibly together with greatly in filtrate
Measure undecomposed phosphoamide, K+、H2PO4 -、HPO4 2-、PO4 3-Deng material, the researcher of the present invention is from substantial amounts of prior art literature
And exploration for many years and research, and the tradition component content of tree peony special fertilizer and the absorbing state of tree peony are studied,
Effectively inquire into out from the filtrate of Wet-process Phosphoric Acid Production potassium dihydrogen phosphate, produce tree peony special fertilizer, solve Wet-process Phosphoric Acid Production phosphorus
The purity of acid dihydride potassium is the highest, and in filtrate, active ingredient such as cannot utilize at the problem, and the absorptivity of this special fertilizer is good and controlled simultaneously
The effect released, at home in fertilizer production, has no report.
Summary of the invention
For above technical problem, the invention provides a kind of producer preparing potassium dihydrogen phosphate by-product tree peony special fertilizer
Method, by unique process production design, improves the purity of potassium dihydrogen phosphate, makes full use of wet process phosphoric acid for preparing biphosphate simultaneously
The active ingredient of potassium, produces out the tree peony special fertilizer of applicable tree peony growth.
The present invention is achieved by the following technical solutions:
A kind of production method preparing potassium dihydrogen phosphate by-product tree peony special fertilizer that the present invention provides, mainly includes following step
Rapid:
1) use phosphoric acid to be (1.2-1.5) with phosphoamide according to mol ratio: 1 mixes, and with programming rate be 6 DEG C/min from
80 DEG C are warming up to 160 DEG C, stirring reaction 4-5h, isolated intermediate；Use again this intermediate and alkaline potassium salt according to mole
Ratio is 1:(1.1-1.4) mixing, regulation pH value is 8.5-9.0, after reaction terminates, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and will contain
Nitrogen, phosphorus, the slip of potassium are placed in cooler crystallizer and cool to 35～40 DEG C, carry out crystallizing filtration treatment, make filtrate at cooling knot
In brilliant device, circulation crystallization processes, it is thus achieved that filter cake be potassium dihydrogen phosphate product, the component content in detection filtrate；
2) in filtrate, formalin is added, according to being (0.4～0.6) with the mol ratio of phosphoamide that contains in solution: 1
Mixing, regulates the pH value of solution with calcium hydroxide, potassium hydroxide and phosphoric acid solution, when the pH value detected in solution 8.5～
When the content of 9.0 nitrogen components is 20-25%, phosphorus composition content is 2-6%, potassium component content is 10-14%, calcium component content be
When 3～7%, mixed liquor is put in retort, pressure is increased to 8～10 atmospheric pressure, be rapidly heated 85 DEG C time, with 5
～the ramp of 6 DEG C/min, when reaching 120 DEG C, keep 2～3h；
3) by step 2) solution that obtains is divided into two parts,
The solution fast cooling taking a deal to 60 DEG C and is depressurized under normal pressure stand, named solution A,
The solution taking a deal is put in a retort, when atmospheric pressure is quickly ramped up to 2 atmospheric pressure, with 50～100Pa/
The speed of min increases atmospheric pressure, simultaneously temperature from 85 DEG C with the ramp of 1～2 DEG C/min, when reaching 3 atmospheric pressure, temperature
When reaching 95 DEG C, keep 0.5～1h, named solution B；
4) by step 3) solution A that obtains, it is cooled to 60～65 DEG C after B mixing, and add a certain amount of H2SO4Solution,
The scope of regulation pH to 7.0～7.4, adds a small amount of magnesium sulfate, borax, zinc sulfate, ferrous sulfate, thiophanate methyl, sulfuric acid
At least one of copper, stands 0.5～1h, obtains solution C；
5) by step 4) in the solution C that obtains be cooled to 20～25 DEG C, carry out crystallizing filtration treatment, obtain substantial amounts of
The potassium phosphate of root, and a small amount ofDeng the change of urea aldehyde
He Tai composite fertilizer just finished product, and describedWithMol ratio is 1:(3
～5), when the content of the nitrogen component in compound state composite fertilizer just finished product be 17-20%, phosphorus composition content be 1-4%, potassium composition contains
Amount for 8-10% time, calcium component content be 2～5% time stop crystallization；
6) granulation is dried, in this step, first by step 5) mixture that separates out is fabricated to a diameter of 0.2～0.4cm
Particle, be subsequently placed in temperature be 45～50 DEG C, flow velocity be 3～4m/s ammonia environment in dry, make tree peony special fertilizer.
Further, step 2) in the calcium hydroxide concentration that adds be 20～25%, the concentration of described potassium hydroxide is
25～30%, the concentration of described phosphoric acid solution is 20～25%.
Further, described step 4) sulfuric acid concentration be 5～15%.
Further, described tree peony special fertilizer is the Chemical Mixed Fertilizer of compound state.
In the present invention, by phosphoamide and phosphoric acid at 80 DEG C, and in the environment of being warming up to 160 DEG C with the speed of 5 DEG C/min
Reaction, generates urea phosphate, and being stepped up along with temperature, and then makes the coordinate bond dialysis between urea phosphate form two kinds
Ion like material, be exactly i.e.WhenIon is in phosphoric acid environment
In, it will close with phosphoric acid, and then carry out ionic polymerization under the temperature environment when urea phosphate coordinate bond dialysis so thatIon generates with phosphoric acidIntermediate-ion, makes to contain in solution simultaneously
Substantial amounts of dihydrogen phosphate, when adding potassium ion compound, dihydrogen phosphate and potassium ion react generation potassium dihydrogen phosphate, and
In succession reach saturated；When potassium content excess, it will react with the ammonium radical ion in intermediate-ion, further make centre
Ion chelating becomesIntermediate-ion, and with positive charge, and then when solution participates in it
Nutrition when his electronegative ion or compound, it will form compound salt with this ion, in the abundantest product
Composition.
Meanwhile, phosphoamide, can react with formalin at pH under 8.5～9.0 alkaline case, generatesDeng urea aldehyde series of products,
It is difficult to preserve under alkaline case Deng urea aldehyde series of products, so needing the pH value with sulfuric acid solution regulation solution 7.0～7.4
Time, separate out the time preserved longer.SimultaneouslyDeng urea aldehyde series
Product, after fertilising, under the effect of microorganism, can discharge N, the C element being easily absorbed by plants, the chain of its urea aldehyde
The longest, chain needs the time ruptured the longest, and the time producing fertilizer efficiency can discharge after a certain time, can reach sustained release
Effect.
The beneficial effects of the present invention is:
Compared with prior art, there is following characteristics in the present invention:
1. rich in carbon amide solution in the filtrate of conventional wet lay phosphoric acid potassium dihydrogen phosphate making, phosphoamide mutually synthermal
Under solubility relatively large, isolated phosphoamide crystal is rich in KH2PO4In other crystal, entered cooling simultaneously and separated out phosphinylidyne
Possibly together with substantial amounts of phosphoamide, K in filtrate after amine crystal+、H2PO4 -、HPO4 2-、PO4 3-Utilizing Deng not operatively, the present invention will
The temperature of phosphoric acid by wet process potassium dihydrogen phosphate making regulates to 80～160 DEG C, and heats up from 80 DEG C to 160 DEG C with the speed of 5 DEG C/min
In the environment of react, not only make the potassium dihydrogen phosphate product purity of precipitation reach more than 98%, filtrate also generateCation, to filtrate crystallisation separate out generate compound state Chemical Mixed Fertilizer go out finished product time, protect
Demonstrate,prove compound state Chemical Mixed Fertilizer to go out in finished productIntermediate-ion and dihydrogen phosphate, and C Yu O it
Between form coordinate bond, this intermediate-ion can form multielement intermediate-ion with centering element compound chelating, and then can
Continue to form chelate with other electronegative compounds or ion, improve constituent content in double salt, and then can adjust
Nutrient content in the double salt that this ion exists, meanwhile, this chelate can be hydrolyzed again and by crop, and then can be effective
Long-term for crop provide fertilizer efficiency, meanwhile, ins conjunction with the mensuration of constituent content in the solution that this ion is existed, so adjustment double salt
Each constituent content during formation, dries and obtains compound state double salt composite fertilizer, and its absorptivity is fabulous, reduce tree peony planting cost and
Improve tree peony quality；
2. phosphoamide composition containing part in filtrate, adds formalin, in alkalescence condition and certain pressure intensity and temperature
Under degree, generateDeng urea aldehyde series composite fertilizer, this can be made male
Red special fertilizer reaches the effect of realizing controlled-release；
3., during granulating and drying, be passed through the ammonia that flow velocity is certain, can absorbed nitrogen element further, after fertilising
Can quickly be absorbed by plants, ensure that the supply of tree peony early stage nutrition further；
4. this tree peony special fertilizer has the advantages that absorptivity is good, realizing controlled-release formula is good, uses the plantation of this tree peony special fertilizer male
Pellet, not only many in bud quantity, bud is big, and seed is full.
Detailed description of the invention
Below in conjunction with specific embodiment, the concrete technical scheme of the present invention is described in detail.
Principle illustrates:
The present invention carries out research and discussion by the mechanism reacting phosphoric acid and phosphoamide, and combines prior art literature
Solution arrives, and phosphoric acid and phosphoamide react generation urea phosphate, and its molecular formula is: CO (NH2)2.H3PO4, in the environment of higher temperature,
Chemical bond meeting dialysis between H and O in phosphoric acid, hydrogen ion is combined with phosphoamide and forms the ionic state containing positive charge so that
Urea phosphate forms the ion double salt that a kind of positive and negative charge attracts mutually, its mechanism structural response following expression: CO (NH2)2.H3PO4
→(H2PO4)-.(H2NCONH3)+
Further, urea phosphate ion double salt phosphoric acid exist in the environment of, (H therein2NCONH3)+Cation and phosphorus
Acid is close, forms the intermediate-ion of C → O coordinate bond, is (CO5PN2H8)+, and then make in urea phosphate intermediate containing a large amount of
(H2PO4)-(CO5PN2H8)+Ion, when adding excessive and appropriate potassium ion, dihydrogen phosphate is formed with potassium ion
Potassium dihydrogen phosphate crystal is precipitated, unnecessary potassium ion and (CO5PN2H8)+Ionic reaction, and displace part NH4 +So that molten
Containing (CO in liquid5PNH4K)+Double salt ion, and analyzed and control the content of N in solution, P, K element by detection, in heating
It is dried and can be prepared by containing N, P, the compound state composite fertilizer of K element.
Its concrete reaction principle will carry out further instruction by following reaction structure formula and reaction mechanism:
Reaction equation one:
CO(NH2)2+H3PO4→CO(NH2)2.H3PO4
Reaction equation two:
Reaction equation three:
Wherein, the dotted line between carbon atom and oxygen atom represents and there is coordinate bond between C atom and O atom.
Reaction equation four:
Wherein, the dotted line between carbon atom and oxygen atom represents and there is coordinate bond between C atom and O atom.
In the present invention, phosphoamide and formaldehyde are under being 8.5～9.0 alkaline case in pH value, are 8～10 air by pressure
Pressure, temperature be 85～120 DEG C can produce reaction:
Reaction equation five
Reaction equation six
GenerateDeng urea aldehyde series of products,It is difficult to preserve under alkaline case Deng urea aldehyde series of products,
So needing the pH value with sulfuric acid solution regulation solution when 7.0～7.4, separate out the time preserved longer.SimultaneouslyDeng urea aldehyde series of products after fertilising, through microorganism
Effect under, N, the C element being easily absorbed by plants can be discharged, the chain length of its urea aldehyde is the longest, and chain needs the time of fracture more
Long, the time producing fertilizer efficiency can discharge after a certain time, can reach the effect of sustained release.
Noun illustrates:
Urea phosphate (Urea phosphate, UP), No. CAS is 4861-19-2, and molecular formula is CH7N2O5P, is represented by CO
(NH2)2·H3PO4:
Being a kind of fine chemical product being widely used in the fields such as animal husbandry, industry, agricultural, its solid is white crystals
Or crystalline powder, soluble in water and alcohol, insoluble in ethers, toluene and carbon tetrachloride, the aqueous solution is acidity, starts point time melted
Solve and release carbon dioxide and ammonia.
Embodiment one
A kind of production method preparing potassium dihydrogen phosphate by-product tree peony special fertilizer that the present embodiment provides, mainly includes following
Step:
1) using phosphoric acid is that 1.2:1 mixes with phosphoamide according to mol ratio, and is that 6 DEG C/min rises from 80 DEG C with programming rate
Temperature is to 160 DEG C, and 4-5h, isolated intermediate are reacted in stirring；Using this intermediate and alkaline potassium salt again is 1 according to mol ratio:
1.4 mixing, regulation pH value is 8.5-9.0, after reaction terminates, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and by nitrogenous, phosphorus, the material of potassium
Slurry is placed in cooler crystallizer and cools to 35～40 DEG C, carries out crystallizing filtration treatment, makes filtrate circulate knot in cooler crystallizer
Brilliant process, it is thus achieved that filter cake be potassium dihydrogen phosphate product, the component content in detection filtrate；
2) in filtrate, add formalin, according to being that 0.4:1 mixes with the mol ratio of the phosphoamide contained in solution, use
Calcium hydroxide, potassium hydroxide and the pH value of phosphoric acid solution regulation solution, described calcium hydroxide concentration is 25%, described hydrogen-oxygen
The concentration changing potassium is 25%, and the concentration of described phosphoric acid solution is 25%, when the pH value detected in solution is at 8.5～9.0 nitrogen
When the content of composition is 20-25%, phosphorus composition content is 2-6%, potassium component content is 10-14%, calcium component content be 3～
When 7%, mixed liquor is put in retort, pressure is increased to 8～10 atmospheric pressure, be rapidly heated 85 DEG C time, with 5～6
DEG C/ramp of min, when reaching 120 DEG C, keep 2～3h；
3) by step 2) solution that obtains is divided into two parts,
The solution fast cooling taking a deal to 60 DEG C and is depressurized under normal pressure stand, named solution A,
The solution taking a deal is put in a retort, when atmospheric pressure is quickly ramped up to 2 atmospheric pressure, with 50～100Pa/
The speed of min increases atmospheric pressure, simultaneously temperature from 85 DEG C with the ramp of 1～2 DEG C/min, when reaching 3 atmospheric pressure, temperature
When reaching 95 DEG C, keep 0.5～1h, named solution B；
4) by step 3) solution A that obtains, it is cooled to 60～65 DEG C after B mixing, and add a certain amount of H2SO4Solution,
The scope of regulation pH to 7.0～7.4, sulfuric acid concentration is 5%, adds a small amount of magnesium sulfate, borax, zinc sulfate, ferrous sulfate, first
Base thiophanate, copper sulphate at least one, stand 0.5～1h, obtain solution C；
5) by step 4) in the solution C that obtains be cooled to 20～25 DEG C, carry out crystallizing filtration treatment, obtain compound state and be combined
Fertile just finished product, when the content of the nitrogen component in compound state composite fertilizer just finished product be 20%, phosphorus composition content be 1%, potassium composition contains
When amount is 10%, calcium component content stop crystallization when being 2%；
6) granulation is dried, in this step, first by step 5) mixture that separates out is fabricated to a diameter of 0.2～0.4cm
Particle, be subsequently placed in temperature be 45～50 DEG C, flow velocity be 3～4m/s ammonia environment in dry, make tree peony special fertilizer, this is male
Red special fertilizer is the Chemical Mixed Fertilizer of compound state.
The Chemical Mixed Fertilizer of this compound state include containingThe potassium phosphate of root, as
And contain Deng the Chemical Mixed Fertilizer of realizing controlled-release and describedWithMol ratio is 1:(3～5).
Embodiment two
A kind of production method preparing potassium dihydrogen phosphate by-product tree peony special fertilizer that the present embodiment provides, mainly includes following
Step:
1) using phosphoric acid is that 1.5:1 mixes with phosphoamide according to mol ratio, and is that 6 DEG C/min rises from 80 DEG C with programming rate
Temperature is to 160 DEG C, and 4-5h, isolated intermediate are reacted in stirring；Using this intermediate and alkaline potassium salt again is 1 according to mol ratio:
1.1 mixing, regulation pH value is 8.5-9.0, after reaction terminates, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and by nitrogenous, phosphorus, the material of potassium
Slurry is placed in cooler crystallizer and cools to 35～40 DEG C, carries out crystallizing filtration treatment, makes filtrate circulate knot in cooler crystallizer
Brilliant process, it is thus achieved that filter cake be potassium dihydrogen phosphate product, the component content in detection filtrate；
2) in filtrate, add formalin, according to being that 0.6:1 mixes with the mol ratio of the phosphoamide contained in solution, use
Calcium hydroxide, potassium hydroxide and the pH value of phosphoric acid solution regulation solution, described calcium hydroxide concentration is 20%, described hydrogen-oxygen
The concentration changing potassium is 30%, and the concentration of described phosphoric acid solution is 20%, when the pH value detected in solution is at 8.5～9.0 nitrogen
When the content of composition is 20-25%, phosphorus composition content is 2-6%, potassium component content is 10-14%, calcium component content be 3～
When 7%, mixed liquor is put in retort, pressure is increased to 8～10 atmospheric pressure, be rapidly heated 85 DEG C time, with 5～6
DEG C/ramp of min, when reaching 120 DEG C, keep 2～3h；
3) by step 2) solution that obtains is divided into two parts,
The solution fast cooling taking a deal to 60 DEG C and is depressurized under normal pressure stand, named solution A,
The solution taking a deal is put in a retort, when atmospheric pressure is quickly ramped up to 2 atmospheric pressure, with 50～100Pa/
The speed of min increases atmospheric pressure, simultaneously temperature from 85 DEG C with the ramp of 1～2 DEG C/min, when reaching 3 atmospheric pressure, temperature
When reaching 95 DEG C, keep 0.5～1h, named solution B；
4) by step 3) solution A that obtains, it is cooled to 60～65 DEG C after B mixing, and add a certain amount of H2SO4Solution,
The scope of regulation pH to 7.0～7.4, sulfuric acid concentration is 15%, add a small amount of magnesium sulfate, borax, zinc sulfate, ferrous sulfate,
Thiophanate methyl, copper sulphate at least one, stand 0.5～1h, obtain solution C；
5) by step 4) in the solution C that obtains be cooled to 20～25 DEG C, carry out crystallizing filtration treatment, obtain compound state and be combined
Fertile just finished product, when the content of the nitrogen component in compound state composite fertilizer just finished product be 17%, phosphorus composition content be 4%, potassium composition contains
When amount is 8%, calcium component content stop crystallization when being 5%；
6) granulation is dried, in this step, first by step 5) mixture that separates out is fabricated to a diameter of 0.2～0.4cm
Particle, be subsequently placed in temperature be 45～50 DEG C, flow velocity be 3～4m/s ammonia environment in dry, make tree peony special fertilizer, this is male
Red special fertilizer is the Chemical Mixed Fertilizer of compound state.
The Chemical Mixed Fertilizer of this compound state include containingThe potassium phosphate of root, as
And contain Deng the Chemical Mixed Fertilizer of realizing controlled-release and describedWithMol ratio is 1:(3～5).
Embodiment three
A kind of production method preparing potassium dihydrogen phosphate by-product tree peony special fertilizer that the present embodiment provides, mainly includes following
Step:
1) using phosphoric acid is that 1.3:1 mixes with phosphoamide according to mol ratio, and is that 6 DEG C/min rises from 80 DEG C with programming rate
Temperature is to 160 DEG C, and 4-5h, isolated intermediate are reacted in stirring；Using this intermediate and alkaline potassium salt again is 1 according to mol ratio:
1.3 mixing, regulation pH value is 8.5-9.0, after reaction terminates, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and by nitrogenous, phosphorus, the material of potassium
Slurry is placed in cooler crystallizer and cools to 35～40 DEG C, carries out crystallizing filtration treatment, makes filtrate circulate knot in cooler crystallizer
Brilliant process, it is thus achieved that filter cake be potassium dihydrogen phosphate product, the component content in detection filtrate；
2) in filtrate, add formalin, according to being that 0.5:1 mixes with the mol ratio of the phosphoamide contained in solution, use
Calcium hydroxide, potassium hydroxide and the pH value of phosphoric acid solution regulation solution, described calcium hydroxide concentration is 22%, described hydrogen-oxygen
The concentration changing potassium is 27%, and the concentration of described phosphoric acid solution is 23%, when the pH value detected in solution is at 8.5～9.0 nitrogen
When the content of composition is 20-25%, phosphorus composition content is 2-6%, potassium component content is 10-14%, calcium component content be 3～
When 7%, mixed liquor is put in retort, pressure is increased to 8～10 atmospheric pressure, be rapidly heated 85 DEG C time, with 5～6
DEG C/ramp of min, when reaching 120 DEG C, keep 2～3h；
3) by step 2) solution that obtains is divided into two parts,
The solution fast cooling taking a deal to 60 DEG C and is depressurized under normal pressure stand, named solution A,
The solution taking a deal is put in a retort, when atmospheric pressure is quickly ramped up to 2 atmospheric pressure, with 50～100Pa/
The speed of min increases atmospheric pressure, simultaneously temperature from 85 DEG C with the ramp of 1～2 DEG C/min, when reaching 3 atmospheric pressure, temperature
When reaching 95 DEG C, keep 0.5～1h, named solution B；
4) by step 3) solution A that obtains, it is cooled to 60～65 DEG C after B mixing, and add a certain amount of H2SO4Solution,
The scope of regulation pH to 7.0～7.4, sulfuric acid concentration is 10%, add a small amount of magnesium sulfate, borax, zinc sulfate, ferrous sulfate,
Thiophanate methyl, copper sulphate at least one, stand 0.5～1h, obtain solution C；
5) by step 4) in the solution C that obtains be cooled to 20～25 DEG C, carry out crystallizing filtration treatment, obtain compound state and be combined
Fertile just finished product, when the content of the nitrogen component in compound state composite fertilizer just finished product be 18%, phosphorus composition content be 3%, potassium composition contains
When amount is 9%, calcium component content stop crystallization when being 4%；
6) granulation is dried, in this step, first by step 5) mixture that separates out is fabricated to a diameter of 0.2～0.4cm
Particle, be subsequently placed in temperature be 45～50 DEG C, flow velocity be 3～4m/s ammonia environment in dry, make tree peony special fertilizer, this is male
Red special fertilizer is the Chemical Mixed Fertilizer of compound state.
The Chemical Mixed Fertilizer of this compound state include containingThe potassium phosphate of root, as
And contain Deng the Chemical Mixed Fertilizer of realizing controlled-release and describedWithMol ratio is 1:(3～5).
In order to preferably prove the beneficial effect that the present invention reaches, the present embodiment also provides for following experimental example, specific as follows:
Experimental example one
Fertile as fertilizer with common N, P, K, Ca mixing, wherein the content of nitrogen component be 18%, phosphorus composition content be
3%, when potassium component content is 9%, calcium component content be 4%, make nutrient solution, tree peony carried out soilless culture, cultivate 30 days
After, in detection nutrient solution, the content of N, P, K, Ca composition, observes its growing way, named A1 simultaneously.
Experimental example two
The tree peony special fertilizer being successful with embodiment one to embodiment tripartite's method, as fertilizer, makes nutrient solution, to male
Pellet carries out soilless culture, cultivate 15 days, 30 days, after 50 days, the content of N, P, K, Ca composition in detection nutrient solution, sees simultaneously respectively
Examine its growing way, be respectively designated as A2, A3, A4.
The concentration of the nutrient solution in above experimental example is suitable, and for prior art, this experimental example seldom elaborates, above reality
Test example with 20 strain tree peonies for testing result such as table 1, table 2 and table 3:
Table 1: the content of N, P, K, Ca composition after cultivating 15 days
Table 2: the content of N, P, K, Ca composition after cultivating 30 days
Table 3: the content of N, P, K, Ca composition after cultivating 50 days
From table 1～3 it can be seen that with common composite fertilizer compared with the tree peony special fertilizer that the present invention produces, cultivate the 15th
During it detection, the absorbing state difference of its N, P, K, Ca is little, but during to detection in the 30th day, the tree peony that the present invention produces is special
The content of N, P, K, Ca in fertile solution is significantly lower than common special fertilizer, and during to detection in the 50th day, common composite fertilizer cultivates
N, P, K, Ca component residue in liquid has 60～80% not absorb, and the present invention produce tree peony special fertilizer nutrient solution in N,
P, K, Ca composition only remains 30～40% and is not absorbed, and illustrates that the tree peony special fertilizer that the present invention produces has the spy that absorptivity is good
Point.
Also provide for following experimental example simultaneously:
Experimental example four
Fertile as fertilizer with common N, P, K, Ca mixing, wherein the content of nitrogen component be 18%, phosphorus composition content be
3%, when potassium component content is 9%, calcium component content be 4%, the tree peony that grown 3 years is applied fertilizer, fertilization time
In January, this experimental example is chosen 20 tree peonies of 3 years grown fine and is tested, and observes its bud quantity, named A2.
Experimental example five is to experimental example seven
The tree peony special fertilizer produced with above-described embodiment one to embodiment three, executes the tree peony that grown 3 years
Fertilizer, fertilization time is in January, and this experimental example is chosen 20 tree peonies of 3 years grown fine and tested, and observes its number of flowers
Amount, named B2, C2, D2.
Its statistics is as follows:
Table 4: tree peony bud quantity
| Numbering | Bud quantity (individual) |
| A2 | 8.5 |
| B2 | 11.4 |
| C2 | 12.6 |
| D2 | 12.3 |
As can be seen from the above table, the tree peony special fertilizer using preparation method of the present invention to produce, tree peony is applied fertilizer, its
Bud quantity ratio many 3～5 of common mixed fertilizer, illustrates the good absorbing effect of this tree peony special fertilizer.
Claims (4)
1. prepare a production method for potassium dihydrogen phosphate by-product tree peony special fertilizer, mainly comprise the steps that
1) phosphoric acid is used to be (1.2-1.5) with phosphoamide according to mol ratio: 1 mixes, and is that 6 DEG C/min is from 80 DEG C with programming rate
It is warming up to 160 DEG C, stirring reaction 4-5h, isolated intermediate；This intermediate is used with alkaline potassium salt according to mol ratio to be again
1:(1.1-1.4) mixing, regulation pH value is 8.5-9.0, react terminate after, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and by nitrogenous,
Phosphorus, the slip of potassium are placed in cooler crystallizer and cool to 35～40 DEG C, carry out crystallizing filtration treatment, make filtrate at cooler crystallizer
Middle circulation crystallization process, it is thus achieved that filter cake be potassium dihydrogen phosphate product, detection filtrate in component content；
2) in filtrate, formalin is added, according to being (0.4～0.6) with the mol ratio of phosphoamide that contains in solution: 1 mixes
Close, regulate the pH value of solution with calcium hydroxide, potassium hydroxide and phosphoric acid solution, when the pH value detected in solution 8.5～
9.0, when the content of nitrogen component is 20-25%, phosphorus composition content is 2-6%, potassium component content is 10-14%, calcium component content
When being 3～7%, mixed liquor is put in retort, pressure is increased to 8～10 atmospheric pressure, be rapidly heated 85 DEG C time, with
The ramp of 5～6 DEG C/min, when reaching 120 DEG C, keeps 2～3h；
3) by step 2) solution that obtains is divided into two parts,
The solution fast cooling taking a deal to 60 DEG C and is depressurized under normal pressure stand, named solution A,
The solution taking a deal is put in a retort, when atmospheric pressure is quickly ramped up to 2 atmospheric pressure, with 50～100Pa/min
Speed increases atmospheric pressure, and temperature is from 85 DEG C with the ramp of 1～2 DEG C/min simultaneously, reaches when reaching 3 atmospheric pressure, temperature
When 95 DEG C, keep 0.5～1h, named solution B；
4) by step 3) solution A that obtains, it is cooled to 60～65 DEG C after B mixing, and add a certain amount of H2SO4Solution, regulation
The scope of pH to 7.0～7.4, the magnesium sulfate of addition, borax, zinc sulfate, ferrous sulfate, thiophanate methyl, copper sulphate are at least
One, stands 0.5～1h, obtains solution C；
5) by step 4) in the solution C that obtains be cooled to 20～25 DEG C, carry out crystallizing filtration treatment, obtain
The potassium phosphate of root, andWithUrea aldehyde compound state be combined
Fertile just finished product, and describedWithMol ratio is 1:(3～5), when
The content of the nitrogen component in compound state composite fertilizer just finished product is 17-20%, phosphorus composition content is 1-4%, potassium component content is 8-
When 10%, calcium component content stop crystallization when being 2～5%；
6) granulation is dried, in this step, first by step 5) mixture that separates out is fabricated to the particle of a diameter of 0.2～0.4cm,
Be subsequently placed in temperature be 45～50 DEG C, flow velocity be 3～4m/s ammonia environment in dry, make tree peony special fertilizer.
A kind of production method preparing potassium dihydrogen phosphate by-product tree peony special fertilizer, it is characterised in that:
Step 2) in add calcium hydroxide concentration be 20～25%, the concentration of described potassium hydroxide is 25～30%, described phosphorus
The concentration of acid solution is 20～25%.
A kind of production method preparing potassium dihydrogen phosphate by-product tree peony special fertilizer, it is characterised in that:
Described step 4) sulfuric acid concentration be 5～15%.
A kind of production method preparing potassium dihydrogen phosphate by-product tree peony special fertilizer, it is characterised in that:
Described tree peony special fertilizer is the Chemical Mixed Fertilizer of compound state.
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