CN104326457B - A kind of production method preparing dikalium phosphate by-product clube tree special fertilizer - Google Patents
A kind of production method preparing dikalium phosphate by-product clube tree special fertilizer Download PDFInfo
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Abstract
The present invention relates to chemical technology field, a kind of production method preparing dikalium phosphate by-product clube tree special fertilizer, it is changed by the coefficients such as the temperature of dikalium phosphate being prepared by phosphoric acid by wet process, improve the purity of dikalium 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 dikalium phosphate, and the absorptivity of this clube tree special fertilizer produced is good, and this clube tree special fertilizer simultaneously produced disclosure satisfy that the nutritional need in each period in clube tree 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 dikalium phosphate by-product clube tree special fertilizer
Method.
Background technology
Dikalium phosphate, is widely used in the crop of the almost all types such as all types of industrial crops, grain, melon fruits and vegetables,
Have 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 has
The malnourished effect overcoming the plant growth later stage aging absorbability of root system to decline and to cause, belongs to novel high density phosphorus potassium two
Elements compounding fertilizer, is efficient phosphorus potassium complex fertilizer agriculturally.Current domestic a lot of fertilizer producers are all producing dikalium phosphate again
Hefei, its production method mainly has neutralisation, extraction, ion-exchange, double decomposition, direct method, crystallisation and electrolysis
Deng, wherein double decomposition includes that thermal phosphoric acid and phosphoric acid by wet process produce dikalium phosphate, and thermal phosphoric acid cost is relatively big, unsuitable conduct
Being widely popularized, therefore, Wet-process Phosphoric Acid Production dikalium phosphate product becomes main method, the basic step of wet process phosphoric acid for preparing phosphoric acid
Rapid 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 urea, simultaneously after the completion of reaction
Owing to urea solubility is the highest, when 20 DEG C, its solubility is that 85g/100ml (refers to " phosphate fertilizer and composite fertilizer " volume 20 the 6th
Phase solubility of chemical fertilizer and Compound fertilizer production technology), the rising of the solubility with temperature of urea simultaneously and increase, so
The urea contained in filtrate is after separating out by cooling crystal, possibly together with a large amount of undecomposed urea, K in filtrate+、H2PO4 -、
HPO4 2-、PO4 3-If directly doing waste water and discharge, both having wasted resource, the waste of resource, meanwhile, the phosphoric acid hydrogen of precipitation can be caused again
The purity of dipotassium crystal is the highest.
Plum blossom, has another name called plum, another name: spring plum, dry branch plum, smoked plum, dark plum, the rose family, apricot belong to dungarunga, dilute shrub, bark
Light gray or band are green, smooth；Sprig is green, Glabrous.Blade elliptical or oval shape, plum originates in south China, and existing three
No matter the cultivation history of more than thousand year, view and admire or fruit tree all has many kinds.Many type not only outdoor croppings, for viewing and admiring, also may be used
To plant as potted flower, make plum, with orchid, bamboo, chrysanthemum referred to as " four gentleman ".Also with pine, bamboo referred to as " three durable plants of winter: pine, bamboo and plum blossom ".Plum with it
Noble and unsullied, strong, modest character, gives the excitation resolving to rouse oneself.In severe cold, it is first that plum opens all sorts of flowers, the spring the most all over the world, its
Florescence winter-spring season, really the phase 5-6 month.In the plantation of plum blossom seedling, often use farm organic fertilizer as base manure, utilization N P and K
Mixing is fertile as supplementing fertilizer, and its growing way is relatively slow, in the fertilising of plum blossom Cheng Shu, typically executes in January December to next year
Fertilizer, mainly N-P-K mixed fertilizer, if it is very few to apply fertilizer, the bud of its plum blossom is less, and ornamental value is the highest, if applied fertilizer
Many, it is possible that burn tree phenomenon, simultaneously the biggest to the destructiveness of soil.
During the present invention is directed to Wet-process Phosphoric Acid Production dikalium phosphate, the purity of dikalium phosphate is the highest, in filtrate possibly together with
A large amount of undecomposed urea, 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 clube tree special fertilizer and the absorbing state of clube tree are ground
Study carefully, effectively inquire into out from the filtrate of Wet-process Phosphoric Acid Production dikalium phosphate, produce clube tree special fertilizer, solve phosphoric acid by wet process raw
The purity producing dikalium phosphate is the highest, and in filtrate, active ingredient such as cannot utilize at the problem, simultaneously the absorptivity of this special fertilizer good with can
The effect of controlled release, at home in fertilizer production, has no report.
Summary of the invention
For above technical problem, the invention provides a kind of producer preparing dikalium phosphate by-product clube tree special fertilizer
Method, by unique process production design, improves the purity of dikalium phosphate, makes full use of wet process phosphoric acid for preparing dikalium phosphate simultaneously
Active ingredient, produces out the clube tree special fertilizer of applicable clube tree growth.
The present invention is achieved by the following technical solutions:
A kind of production method preparing dikalium phosphate by-product clube tree special fertilizer that the present invention provides, it is characterised in that: adopt
Mix with urea with phosphoric acid, then by being warming up to 80～160 DEG C, after stirring certain time, isolated intermediate, then use
This intermediate reacts with potassium hydroxide solution, then isolates potassium dihydrogen phosphate by decrease temperature crystalline, and detects the one-tenth in filtrate
Divide content；It is subsequently adding calcium hydroxide, potassium hydroxide and the pH value of phosphoric acid solution regulation solution and the content of N, P, K, Ca composition,
It is simultaneously introduced formalin, carries out pressurizeing and hyperthermic treatment, after reaction a period of time, add the trace unit useful to clube tree
Element, obtains compound state composite fertilizer just finished product by decrease temperature crystalline, when content nitrogen component being detected be 16-19%, phosphorus composition contains
When amount is 11-14% for 3-7%, potassium component content, calcium component content is when being 10-15%, stops crystallization, after carrying out granulation, then
Through being dried to obtain clube tree special fertilizer under ammonia atmosphere.
Further, described a kind of production method preparing dikalium phosphate by-product clube tree special fertilizer, mainly include with
Lower step:
1) phosphoric acid is used to be (1.2-1.5) with urea according to mol ratio: 1 mixes, and is that 6 DEG C/min is from 80 with programming rate
DEG C it is warming up to 160 DEG C, stirring reaction 4-5h, isolated intermediate；Use this intermediate and potassium hydroxide solution according to rubbing again
Your 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
Slip nitrogenous, phosphorus, potassium is placed in cooler crystallizer and cools to 35～40 DEG C, carries out crystallizing filtration treatment, makes filtrate in cooling
In crystallizer circulation crystallization process, it is thus achieved that filter cake be dikalium phosphate product, detection filtrate in component content；
2) in filtrate, add formalin, according to solution in be (0.6～0.7) containing the mol ratio of urea: 1 is mixed
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 18-25%, phosphorus composition content is 4-8%, potassium component content is 12-16%, calcium component content
When being 12～18%, 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, keep 2～3h；
3) by step 2) solution that obtains puts in a retort, when atmospheric pressure is quickly ramped up to 4 atmospheric pressure, with 50～
The speed of 100Pa/min increases atmospheric pressure, simultaneously temperature from 85 DEG C with the ramp of 1～2 DEG C/min, when reaching 6 air
When pressure, temperature reach 95 DEG C, keep 0.5～1h；
4) by step 3) solution that obtains is cooled to 60～65 DEG C, and add a certain amount of H2SO4Solution, regulation pH arrives
The scope of 7.0～7.4, adds in a small amount of zinc sulfate, copper sulphate, manganese sulfate, ammonium molybdate, ferrous sulfate, chelated iron, borax
One at least, stands 0.5～1h；
5) by step 4) in the solution that obtains be cooled to 20～25 DEG C, carry out crystallizing filtration treatment, containedThe salt of root, and containWith
Compound state composite fertilizer just finished product, when be 16-19% when the content that nitrogen component be detected, phosphorus composition content be 3-7%, potassium composition
When content is 11-14%, calcium component content is when being 10-15%, stops 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 clube tree special fertilizer.
Step 2) in add calcium hydroxide concentration be 35～40%, the concentration of described phosphoric acid solution is 20～25%.
Described step 4) sulfuric acid concentration be 5～15%.
Described clube tree special fertilizer is the Chemical Mixed Fertilizer of compound state.
In the present invention, by urea and phosphoric acid at 80 DEG C and anti-in the environment of being warming up to 160 DEG C with the speed of 5 DEG C/min
Should, generate urea phosphate, and being stepped up along with temperature, and then make the coordinate bond dialysis between urea phosphate and formed two kinds from
Sub-shape material, be exactly i.e.WithWhenIon is in phosphoric acid environment, 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 in solution containing big simultaneously
The dihydrogen phosphate of amount, when adding potassium ion compound, dihydrogen phosphate and potassium ion react and generate dikalium phosphate, and in succession
Reach saturated；When potassium content excess, it will react with the ammonium radical ion in intermediate-ion, further make intermediate-ion
Chelate intoIntermediate-ion, and with positive charge, and then when solution participates in other bands
Nutritional labeling when negative ion or compound, it will form compound salt with this ion, in the abundantest product.
Meanwhile, urea, 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 of products in fertilising
After, under the effect of microorganism, 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
Time to be ruptured is the longest, and the time producing fertilizer efficiency can discharge after a certain time, can reach the effect of sustained release.
The beneficial effects of the present invention is:
Compared with prior art, there is following characteristics in the present invention:
1. rich in urea liquid in the filtrate of conventional wet lay phosphoric acid dikalium phosphate, at the same temperature molten of urea
Xie Du is relatively large, and isolated urea crystal is rich in KH2PO4In other crystal, after entering cooling precipitated urea crystal simultaneously
Possibly together with substantial amounts of urea, K in filtrate+、H2PO4 -、HPO4 2-、PO4 3-Utilizing Deng not operatively, the present invention is by wet process phosphoric acid for preparing phosphorus
The temperature of acid dipotassium regulates to 80～160 DEG C, and reacts in the environment of 80 DEG C to 160 DEG C, no with the speed intensification of 5 DEG C/min
The dikalium phosphate product purity only making precipitation reaches more than 98%, also generates in filtrateSun
Ion, when separating out the compound state Chemical Mixed Fertilizer generated and going out finished product, it is ensured that compound state Chemical Mixed Fertilizer goes out in finished product to filtrate crystallisationIntermediate-ion and dihydrogen phosphate, and between C and O, form coordinate bond, this intermediate-ion
Multielement intermediate-ion can be formed with centering element compound chelating, and then can continue to the compound electronegative with other
Or ion forms chelate, improve constituent content in double salt, and then the nutrient that can adjust in the double salt that this ion exists contains
Amount, meanwhile, this chelate can be hydrolyzed again and by crop, and then effectively for a long time can provide fertilizer efficiency for crop, meanwhile,
In conjunction with the mensuration of constituent content in the solution that there is this ion, and then adjusting each constituent content when double salt is formed, drying obtains
Compound state double salt composite fertilizer, its absorptivity is fabulous, reduces clube tree planting cost and improves clube tree quality；
2. urea components containing part in filtrate, adds formalin, in alkalescence condition and certain pressure intensity and temperature
Under, generateDeng urea aldehyde series composite fertilizer, this clube tree can be made 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 clube tree early stage nutrition further；
4. this clube tree special fertilizer has the advantages that absorptivity is good, realizing controlled-release formula is good.
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 by carrying out research and discussion to the mechanism of phosphoric acid Yu urea reaction, and combines prior art literature understanding
Arriving, phosphoric acid generates urea phosphate with urea reaction, and its molecular formula is: CO (NH2)2.H3PO4, in the environment of higher temperature, phosphoric acid
In H and O between chemical bond can dialysis, hydrogen ion is combined with urea formation contain positive charge ionic state so that urea phosphate
Form 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
Dikalium phosphate crystal is precipitated, unnecessary potassium ion and (CO5PN2H8)+Ionic reaction, and displace part NH4 +So that solution
In containing (CO5PNH4K)+Double salt ion, and analyzed and control the content of N in solution, P, K element by detection, dry in heating
Dry 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, urea and formaldehyde are under being 8.5～9.0 alkaline case in pH value, can produce and react:
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
Under effect, can discharge N, the C element being easily absorbed by plants, the chain length of its urea aldehyde is the longest, and chain needs the time ruptured the longest,
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 dikalium phosphate by-product clube tree special fertilizer that the present embodiment provides, mainly includes following
Step:
1) using phosphoric acid is that 1.2:1 mixes with urea according to mol ratio, and is that 6 DEG C/min is from 80 DEG C of intensifications with programming rate
To 160 DEG C, stirring reaction 4-5h, isolated intermediate；This intermediate is used with potassium hydroxide solution according to mol ratio to be again
1:1.4 mixes, and regulation pH value is 8.5, after reaction terminates, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and by nitrogenous, phosphorus, the slip of potassium
It is placed in cooler crystallizer and cools to 35～40 DEG C, carry out crystallizing filtration treatment, make filtrate circulation crystallization in cooler crystallizer
Process, it is thus achieved that filter cake be dikalium phosphate product, detection filtrate in component content；
2) in filtrate, add formalin, according to being that 0.6:1 mixes with the mol ratio containing urea in solution, use hydrogen-oxygen
Changing calcium, potassium hydroxide and the pH value of phosphoric acid solution regulation solution, wherein calcium hydroxide concentration is 40%, and the concentration of phosphoric acid solution is
20%, when detect the pH value of solution 9.0, the content of nitrogen component is 18-25%, phosphorus composition content is 4-8%, potassium composition contains
Amount for 12-16% time, calcium component content be 12～18% time, 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, keep 2～3h；
3) by step 2) solution that obtains puts in a retort, when atmospheric pressure is quickly ramped up to 4 atmospheric pressure, with 50～
The speed of 100Pa/min increases atmospheric pressure, simultaneously temperature from 85 DEG C with the ramp of 1～2 DEG C/min, when reaching 6 air
When pressure, temperature reach 95 DEG C, keep 0.5～1h；
4) by step 3) solution that obtains is cooled to 60～65 DEG C, and add a certain amount of H2SO4Solution, regulation pH arrives
The scope of 7.0, described sulfuric acid concentration is 15%, is subsequently adding a small amount of zinc sulfate, copper sulphate, manganese sulfate, ammonium molybdate, sulfuric acid
One at least in ferrous iron, chelated iron, borax, stands 0.5～1h；
5) by step 4) in the solution that obtains be cooled to 20～25 DEG C, carry out crystallizing filtration treatment, containedThe salt of root, and containWith
Compound state composite fertilizer just finished product, when the content of the nitrogen component in compound state composite fertilizer just finished product be 16%, phosphorus composition content be
7%, when potassium component content is 11%, calcium component content is when being 15%, stops 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 clube tree special fertilizer, should
Special fertilizer is the Chemical Mixed Fertilizer of compound state.
Embodiment two
A kind of production method preparing dikalium phosphate by-product clube tree special fertilizer that the present embodiment provides, mainly includes following
Step:
1) using phosphoric acid is that 1.5:1 mixes with urea according to mol ratio, and is that 6 DEG C/min is from 80 DEG C of intensifications with programming rate
To 160 DEG C, stirring reaction 4-5h, isolated intermediate；This intermediate is used with potassium hydroxide solution according to mol ratio to be again
1:1.1 mixes, and regulation pH value is 8.5, after reaction terminates, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and by nitrogenous, phosphorus, the slip of potassium
It is placed in cooler crystallizer and cools to 35～40 DEG C, carry out crystallizing filtration treatment, make filtrate circulation crystallization in cooler crystallizer
Process, it is thus achieved that filter cake be dikalium phosphate product, detection filtrate in component content；
2) in filtrate, add formalin, according to being that 0.7:1 mixes with the mol ratio containing urea in solution, use hydrogen-oxygen
Changing calcium, potassium hydroxide and the pH value of phosphoric acid solution regulation solution, wherein calcium hydroxide concentration is 35%, and the concentration of phosphoric acid solution is
25%, when detect the pH value of solution 9.0, the content of nitrogen component is 18-25%, phosphorus composition content is 4-8%, potassium composition contains
Amount for 12-16% time, calcium component content be 12～18% time, 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, keep 2～3h；
3) by step 2) solution that obtains puts in a retort, when atmospheric pressure is quickly ramped up to 4 atmospheric pressure, with 50～
The speed of 100Pa/min increases atmospheric pressure, simultaneously temperature from 85 DEG C with the ramp of 1～2 DEG C/min, when reaching 6 air
When pressure, temperature reach 95 DEG C, keep 0.5～1h；
4) by step 3) solution that obtains is cooled to 60～65 DEG C, and add a certain amount of H2SO4Solution, regulation pH arrives
The scope of 7.4, described sulfuric acid concentration is 5%, is subsequently adding a small amount of zinc sulfate, copper sulphate, manganese sulfate, ammonium molybdate, sulfuric acid
One at least in ferrous iron, chelated iron, borax, stands 0.5～1h；
5) by step 4) in the solution that obtains be cooled to 20～25 DEG C, carry out crystallizing filtration treatment, containedThe salt of root, and containWith
Compound state composite fertilizer just finished product, when the content of the nitrogen component in compound state composite fertilizer just finished product be 19%, phosphorus composition content be
3%, when potassium component content is 14%, calcium component content is when being 10%, stops 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 clube tree special fertilizer, should
Special fertilizer is the Chemical Mixed Fertilizer of compound state.
Embodiment three
A kind of production method preparing dikalium phosphate by-product clube tree special fertilizer that the present embodiment provides, mainly includes following
Step:
1) using phosphoric acid is that 1.3:1 mixes with urea according to mol ratio, and is that 6 DEG C/min is from 80 DEG C of intensifications with programming rate
To 160 DEG C, stirring reaction 4-5h, isolated intermediate；This intermediate is used with potassium hydroxide solution according to mol ratio to be again
1:1.3, mixing, regulation pH value is 8.7, after reaction terminates, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and by nitrogenous, phosphorus, the slip of potassium
It is placed in cooler crystallizer and cools to 35～40 DEG C, carry out crystallizing filtration treatment, make filtrate circulation crystallization in cooler crystallizer
Process, it is thus achieved that filter cake be dikalium phosphate product, detection filtrate in component content；
2) in filtrate, add formalin, according to being that 0.65:1 mixes with the mol ratio containing urea in solution, use hydrogen
Calcium oxide, potassium hydroxide and the pH value of phosphoric acid solution regulation solution, wherein calcium hydroxide concentration is 37%, the concentration of phosphoric acid solution
Be 22%, when detect the pH value of solution 8.8, the content of nitrogen component is 18-25%, phosphorus composition content is 4-8%, potassium composition
When content is 12-16%, calcium component content is when being 12～18%, is put into by mixed liquor in retort, pressure increases to 8～10
Individual atmospheric pressure, be rapidly heated 85 DEG C time, with the ramp of 5～6 DEG C/min, when reaching 120 DEG C, keep 2～3h；
3) by step 2) solution that obtains puts in a retort, when atmospheric pressure is quickly ramped up to 4 atmospheric pressure, with 50～
The speed of 100Pa/min increases atmospheric pressure, simultaneously temperature from 85 DEG C with the ramp of 1～2 DEG C/min, when reaching 6 air
When pressure, temperature reach 95 DEG C, keep 0.5～1h；
4) by step 3) solution that obtains is cooled to 60～65 DEG C, and add a certain amount of H2SO4Solution, regulation pH arrives
The scope of 7.2, described sulfuric acid concentration is 10%, is subsequently adding a small amount of zinc sulfate, copper sulphate, manganese sulfate, ammonium molybdate, sulfuric acid
One at least in ferrous iron, chelated iron, borax, stands 0.5～1h；
5) by step 4) in the solution that obtains be cooled to 20～25 DEG C, carry out crystallizing filtration treatment, containedThe salt of root, and containWith
Compound state composite fertilizer just finished product, when the content of the nitrogen component in compound state composite fertilizer just finished product be 18%, phosphorus composition content be
5%, when potassium component content is 13%, calcium component content is when being 13%, stops 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 clube tree special fertilizer, should
Special fertilizer is the Chemical Mixed Fertilizer of compound state.
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 16%, phosphorus composition content be
7%, when potassium component content is 11%, calcium component content be 15%, make nutrient solution, clube tree carried out soilless culture, cultivate
After 30 days, the content of N, P, K, Ca composition, named A1 in detection nutrient solution.
Experimental example two is to experimental example four
The clube tree special fertilizer being successful with embodiment one to embodiment tripartite's method, as fertilizer, makes nutrient solution, right
Clube tree carries out soilless culture, cultivate 15 days, 30 days, after 50 days, the content of N, P, K, Ca composition in detection nutrient solution, life respectively
Entitled 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 night of staying at the bed-side of a patient at night with 20 strain plum blossom seedling 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 clube tree special fertilizer that the present invention produces, cultivate the
During detection in 15 days, the absorbing state difference of its N, P, K, Ca is little, but during to detection in the 30th day, the clube tree that the present invention produces
The content of N, P, K, Ca in special fertilizer solution is significantly lower than common special fertilizer, during to detection in the 50th day, common composite fertilizer
N, P, K, Ca component residue in nutrient solution has 60～80% not absorb, and the nutrient solution of the clube tree special fertilizer that the present invention produces
In N, P, K, Ca composition only remain 30～40% and do not absorbed, illustrate that the clube tree special fertilizer that the present invention produces has absorption
The feature that rate is good.
Experimental example five
Fertile as fertilizer with common N, P, K, Ca mixing, wherein the content of nitrogen component be 16%, phosphorus composition content be
7%, when potassium component content is 11%, calcium component content be 15%, apply fertilizer in January December to next year, choose 20
Ripe clube tree is as subjects.When blooming spring, randomly draw the bud that 1 clube tree observes its clube tree big
Little, the quantity of young shoot, bud quantity；During July, observe the quantity of system 1 shell clube tree new life young shoot, named A2.
Test example six is to test example eight
The clube tree special fertilizer being successful with embodiment one to embodiment tripartite's method is as fertilizer, in December to next year
January applies fertilizer, and dose is identical with test example five, chooses 20 ripe clube trees as subjects.Open in spring
Hua Shi, randomly draws 1 clube tree and observes the bud size of its clube tree, the quantity of young shoot, bud quantity；During July, observe
Unite the quantity of 1 shell clube tree new life young shoot, named B2, C2, D2.
Wherein, using A2 for radix as reference, data and the contrast of A2 in B2, C2, D2, its statistics is as follows:
Table 4: the bud quantity of clube tree, bud size, young shoot quantity
As can be seen from the above table, the clube tree special fertilizer that the use present invention makes is as plum blossom fertilizer, at its bud in spring
More, bud is relatively big, and young shoot quantity is more, illustrates that the absorptivity of this clube tree special fertilizer is good；When the July, its newborn young shoot
It is 1.5～2 times of common mixed fertilizer, illustrates that the fertilizer efficiency retention time of this clube tree special fertilizer is longer, there is the effect of realizing controlled-release.
Claims (4)
1. prepare a production method for dikalium phosphate by-product clube tree special fertilizer, mainly comprise the steps that
1) phosphoric acid is used to be (1.2-1.5) with urea according to mol ratio: 1 mixes, 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；Use this intermediate and potassium hydroxide solution according to mol ratio again
For 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 dikalium phosphate product, detection filtrate in component content；
2) in filtrate, add formalin, be (0.6～0.7) according to the mol ratio containing urea in solution: 1 mixes, use
Calcium hydroxide, potassium hydroxide and the pH value of phosphoric acid solution regulation solution, when the pH value detected in solution is 8.5～9.0, nitrogen becomes
Point content be 18-25%, phosphorus composition content be 4-8%, potassium component content when being 12-16%, calcium component content be 12～
When 18%, 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 puts in a retort, when atmospheric pressure is quickly ramped up to 4 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 6 atmospheric pressure, temperature
When reaching 95 DEG C, keep 0.5～1h；
4) by step 3) solution that obtains is cooled to 60～65 DEG C, and add a certain amount of H2SO4Solution, regulation pH to 7.0～
The scope of 7.4, adds in a small amount of zinc sulfate, copper sulphate, manganese sulfate, ammonium molybdate, ferrous sulfate, chelated iron, borax at least
One, stand 0.5～1h；
5) by step 4) in the solution that obtains be cooled to 20～25 DEG C, carry out crystallizing filtration treatment, containedThe salt of root, and containWithChange
He Tai composite fertilizer just finished product, when content nitrogen component being detected be 16-19%, phosphorus composition content be 3-7%, potassium component content be
During 11-14%, calcium component content is when being 10-15%, stops crystallization；
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 clube tree special fertilizer.
A kind of production method preparing dikalium phosphate by-product clube tree special fertilizer, it is characterised in that:
Step 2) in add calcium hydroxide concentration be 35～40%, the concentration of described phosphoric acid solution is 20～25%.
A kind of production method preparing dikalium phosphate by-product clube tree special fertilizer, it is characterised in that:
Described step 4) sulfuric acid concentration be 5～15%.
A kind of production method preparing dikalium phosphate by-product clube tree special fertilizer, it is characterised in that:
Described clube tree special fertilizer is the Chemical Mixed Fertilizer of compound state.
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Effective date of registration: 20160720 Address after: 550000 Huaxi District, Guizhou, Guiyang Applicant after: Guizhou University Applicant after: Phosphorylcholine group limited-liability company is opened in Guizhou Applicant after: Guizhou Ke Xinhua smelting company limited Address before: 550000 Huaxi District, Guizhou, Guiyang Applicant before: Guizhou University Applicant before: Zhonghuakai Phosphorous Chemical Fertilizer Co., Ltd., Guiyang Applicant before: Guizhou Ke Xinhua smelting company limited |
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