CN104310345B - Method for preparing potassium dihydrogen phosphate and preparing special fertilizer for hawthorn fruits as byproduct - Google Patents
Method for preparing potassium dihydrogen phosphate and preparing special fertilizer for hawthorn fruits as byproduct Download PDFInfo
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- CN104310345B CN104310345B CN201410477863.8A CN201410477863A CN104310345B CN 104310345 B CN104310345 B CN 104310345B CN 201410477863 A CN201410477863 A CN 201410477863A CN 104310345 B CN104310345 B CN 104310345B
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Abstract
The invention relates to the technical field of chemical industry, and especially relates to a method for preparing potassium dihydrogen phosphate and preparing a special fertilizer for hawthorn fruits as a byproduct. The temperature and other coefficients of the preparation technology of potassium dihydrogen phosphate from phosphoric acid through a wet process are changed, so the purity of the potassium dihydrogen phosphate product is improved, and the N, P and K compounded fertilizer is produced. The method improves the purity of potassium dihydrogen phosphate, and the produced special fertilizer for hawthorn fruits has high absorptivity; and formaldehyde is added to a filtrate to prepare the controlled release compound fertilizer. The produced special fertilizer for hawthorn fruits can meet the nutrition needs of hawthorn fruits in all stages of the growth period of hawthorn fruits, greatly increases the output of hawthorn fruits, and is an efficient compound fertilizer.
Description
Technical field
The present invention relates to chemical technology field, more particularly, to a kind of production of potassium dihydrogen phosphate preparation by-product hawthorn 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, many excellent effects such as the amount of changing optimizes quality, resistant to lodging, disease and insect resistance, preventing and treating senilism, and
There is the malnourished effect overcoming the aging absorbability of plant growth later stage root system to decline and leading to, belong to novel high density phosphorus
Potassium Was Used compound fertilizer, is efficient phosphorus potassium complex fertilizer agriculturally.Domestic at present 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, crystallization process and
Electrolysis etc., wherein double decomposition include thermal phosphoric acid and phosphoric acid by wet process preparing potassium dihydrogen phosphate, and thermal phosphoric acid cost is larger,
Should not be used as being widely popularized, therefore, Wet-process Phosphoric Acid Production potassium dihydrogen phosphate product becomes main method, phosphoric acid by wet process 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
Carry out at a temperature of 60～80 DEG C of whole reaction, after reaction terminates, phosphoamide is that any change occurs, simultaneously by
Very high in phosphoamide solubility, when 20 DEG C, its dissolubility (refers to for 85g/100ml《Phosphate fertilizer and compound fertilizer》Volume 20 the 6th
Phase solubility of chemical fertilizer and Compound fertilizer production technology), the rising of the solubility with temperature of phosphoamide simultaneously and increase, therefore
The phosphoamide containing in this filtrate, after separating out by crystal of lowering the temperature, also contains undecomposed phosphoamide, K in a large number in filtrate+、
H2PO4 ~、HPO4 2～、PO4 3～If directly doing waste water and discharging, both waste of resource, can cause the waste of resource again, be simultaneously manufactured
Dipotassium hydrogen phosphate product purity is not high.
Thornbuss is deciduous tree, and leaf is bordering on avette, has pinniform drastic crack, floral white.Fruit is spherical, peony, has little
Speckle, sour in the mouth, can eat, also can be used as medicine.Its this strong adaptability, is in mountain ridge unfertile land, and growth promoter also than other fruit trees is
Good.Fructus Crataegi slice contain multivitamin, Crataegolic acid, tartaric acid, citric acid, malic acid etc., also contain flavonoid, lactone, saccharide, egg
The mineral such as white matter, fat and calcium, phosphorus, ferrum, contained lipolytic enzyme can promote the digestion of fat food.Promote gastric secretion and
Increase the functions such as gastric enzyme element.The traditional Chinese medical science thinks, Fructus Crataegi has that removing food stagnancyization is stagnant, convergence and dysentery, activating blood circulation to dissipate blood stasis the effects such as.
At present, people, when applying fertilizer to thornbuss, are typically chased after to thornbuss using raw materials such as chemical fertilizer, phosphoamide, human excrement
Fertilizer, such as a kind of patent of invention " fructus crataegi pinnatifidae organic fertilizer special and its preparation side of Patent No. CN201410000616.9
Method ", a kind of patent of invention " compound method of big silk tops thornbuss base manure " of Patent No. CN201210166792.0, the patent No.
Patent of invention " a kind of Preparation method for yield-increasing fertilizer for hawthorn trees " for CN201110154561.3 etc..Although effect is good, change
In fertilizer, phosphoamide, contained nutrition much can not meet the nutritional need of thornbuss, easily causes thornbuss because lacking nutrition
Growth is slow, the haw berry born is little, lightweight, and premunition is poor, and color is poor, and various pest and disease damages easily occur.
According to another report, the absorbance of compound fertilizer is as follows：
Phosphoamide, the plant absorption utilization rate of carbon ammonium are：20% one 46%；
The plant absorption utilization rate of phosphate fertilizer (diammonium, an ammonium, triple superphosphate) is：10% one 25%；
Commonly the plant absorption utilization rate of potash fertilizer is：45% one 60%.
During Wet-process Phosphoric Acid Production potassium dihydrogen phosphate, the purity of potassium dihydrogen phosphate is not high, also contains big 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 literary composition
Offer and exploration for many years and research, and the absorbing state of the component content to traditional hawthorn special fertilizer and Fructus Crataegi is ground
Study carefully, effectively inquire into out and produce hawthorn special fertilizer from the filtrate of Wet-process Phosphoric Acid Production potassium dihydrogen phosphate, solve phosphoric acid by wet process life
Produce the problems such as in the filtrate of potassium dihydrogen phosphate, effective ingredient cannot utilize, at home in fertilizer production, have no report.
Content of the invention
For solving above-mentioned technical problem, the invention provides a kind of production of potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer
Method, by unique process production design, improve the purity of potassium dihydrogen phosphate, make full use of phosphoric acid by wet process phosphoric acid simultaneously
Phosphoamide, K in the filtrate of potassium dihydrogen+、H2PO4 ~、HPO4 2～、PO4 3～Deng material, the Fructus Crataegi producing out suitable Fructus Crataegi growth is special
Fertile.
The present invention is achieved by the following technical programs.
A kind of production method of potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer that the present invention provides, using phosphoric acid and phosphinylidyne
Amine is (1.2～1.6) according to mol ratio：1 mixing, and it is warming up to 160 DEG C for 5 DEG C/min from 80 DEG C with programming rate, stirring is anti-
Answer 4～5h, separate and obtain intermediate；This intermediate and alkaline potassium salt is adopted to be 1 according to mol ratio again：(1.1～1.3) mix,
After reaction terminates, obtain the nitrogenous, slip of phosphorus, potassium, and the slip of nitrogenous, phosphorus, potassium is placed in cooler crystallizer cools to 40
～45 DEG C, carry out crystallizing filtration treatment, make filtrate circulation crystallization process in cooler crystallizer, the filter cake of acquisition is biphosphate
Potassium product, the component content in detection filtrate；In filtrate plus alkalescence potassium and phosphoric acid, when the pH of solution is 8.5～9.0, nitrogen component
Content is 25～30%, phosphorus composition content is 7～12%, potassium composition content is 15～20%, adds formalin in filtrate,
And pressurizeed and hyperthermic treatment, obtain suspension emulsion A, then add the calcium, moderate-element such as magnesium, micro- again in suspension emulsion A
Secondary element and amino acidses chelate, obtain suspension emulsion B, then again decrease temperature crystalline step obtain compound state Chemical Mixed Fertilizer thick
Product, when wherein nitrogen component content be 20～25%, phosphorus composition content be to stop knot when 6～9%, potassium composition content is 13～18%
Crystalline substance, then makes hawthorn special fertilizer by pelletize and drying.
Alkalescence potassium is potassium oxide solid or potassium hydroxide solid or potassium hydroxide solution, when for potassium hydroxide solution, dense
Spend for 30～35%.
The concentration of described phosphoric acid solution is 17～20%.
The concentration of described formalin is that the mol ratio of the phosphoamide containing in 35～40%, and formaldehyde and solution is
(0.5～1.5)：4.
The design parameter of described pressurization and hyperthermic treatment is：Quick-pressing, to 6～8 atmospheric pressure, is rapidly heated to 80
～100 DEG C, keep 0.5～1h, then solution aliquot be divided into two parts,
The solution taking a deal continues to keep 3 atmospheric pressure and 80 DEG C of constant, holding 0.5～1h, obtains suspension emulsion a,
Take a component solution Quick-pressing big 6～8 atmospheric pressure when, pressure is increased with the speed of 20～40Pa/min,
Keep constant when reaching 10～12 atmospheric pressure, when being rapidly heated to 80～100 DEG C, with the ramp of 2～5 DEG C/min,
Keep constant when reaching 100 DEG C, keep 1～2h when pressure and temperature all reach peak, obtain suspension emulsion b,
Then suspension emulsion a and suspension emulsion b is mixed, obtain suspension emulsion A.
Described trace element is the trace element such as ferrum, boron, arsenic, manganese, copper, cobalt, molybdenum.
It is cooling pressurized treatment that suspension emulsion B carries out crystallisation step, and temperature is down to 30～35 DEG C, and pressure increases to 6～8 greatly
Air pressure, obtains crystal, obtains hawthorn special fertilizer finally by granulation drying.
Described drying be oven drying at low temperature, temperature at 35～40 DEG C, and to drying environment circulation be passed through flow velocity be 3～
The ammonia of 4m/s.
The Chemical Mixed Fertilizer of described compound state contains following N P and K compound state structural formula：
Wherein, the dotted line between carbon atom and oxygen atom represents there is coordinate bond between C atom and O atom.
The Chemical Mixed Fertilizer of described compound state also containsWith's
The Chemical Mixed Fertilizer of realizing controlled-release.
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 with temperature, and then makes coordinate bond dialysis between urea phosphate form two kinds
Ion like material, that is, be exactlyWhenIon is in phosphoric acid environment
In, it will close with phosphoric acid, and then carry out ionic polymerization under the temperature environment in urea phosphate coordinate bond dialysis so thatIon is generated with phosphoric acidIntermediate-ion, makes to contain greatly in solution simultaneously
The dihydrogen phosphate of amount, when adding potassium ion compound, dihydrogen phosphate and potassium ion react generation potassium dihydrogen phosphate, and phase
Continue and reach saturation；When potassium content is excessive, it will react with the ammonium ion in intermediate-ion, further make centre from
Son chelates intoIntermediate-ion, and carry positive charge, and then when participating in other in solution
When electronegative ion or compound, it will form compound salt with this ion, the nutrition further enriched in product becomes
Point.
Meanwhile, phosphoamide, in pH under 8.5～9.0 alkaline case, is pressurized and hyperthermic treatment, meeting and formaldehyde
Solution reaction, generatesEtc. ureaformaldehyde series of products, simultaneouslyEtc. ureaformaldehyde series of products after fertilising, through microorganism
Under effect, the N being easily absorbed by plants, C element can be discharged, the chain length of its ureaformaldehyde is longer, chain needs the time of fracture longer,
The time producing fertilizer efficiency can discharge after a certain time, can reach the effect of slow release.
The beneficial effects of the present invention is：Compared with prior art, there are following characteristics in the present invention：
1. in the filtrate of conventional wet lay phosphoric acid potassium dihydrogen phosphate making be rich in carbon amide solution, phosphoamide mutually synthermal
Under dissolubility relatively large, the phosphoamide crystal isolated is rich in KH2PO4In other crystal, entered cooling simultaneously and separated out phosphinylidyne
Also contain in filtrate after amine crystal substantial amounts of phosphoamide, K+、H2PO4 ~、HPO4 2～、PO4 3～Utilize Deng not operatively, the present invention
By the temperature adjustment of phosphoric acid by wet process potassium dihydrogen phosphate making to 80～160 DEG C, and heated up from 80 DEG C to 160 with the speed of 5 DEG C/min
React in the environment of DEG C, not only make the potassium dihydrogen phosphate product purity of precipitation reach more than 98%, also generate in filtrateCation, to filtrate crystallisation separate out generate compound state chemical mixed fertilizer go out finished product when, protect
Demonstrate,prove compound state chemical mixed fertilizer to go out in finished productIntermediate-ion and dihydrogen phosphate, and C and O it
Between form coordinate bond, this intermediate-ion can be chelated with centering element compound and form multielement intermediate-ion, and then can
Continue the compound negatively charged with other or ion forms chelate, 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 mensure of constituent content in the solution that this ion is existed, so adjustment double salt
Each element content during formation, dries and obtains compound state double salt compound fertilizer, and by avoiding the addition of chlorine element so that compound state
While the product quality of double salt compound fertilizer disclosure satisfy that the requirement of Fructus Crataegi nutritional labeling, it is to avoid the damage that fertilizer brings to Fructus Crataegi
Evil, reduces Fructus Crataegi planting cost and improves Fructus Crataegi quality；
2. the phosphoamide composition containing part in filtrate, adds formalin, in alkalescence condition and certain pressure intensity and temperature
Under degree, generateEtc. ureaformaldehyde series compound fertilizer, this mountain can be made
Short, bristly hair or beard special fertilizer reaches the effect of realizing controlled-release；
3. this hawthorn special fertilizer has the characteristics that absorbance is good, realizing controlled-release formula is good, and the yield of Fructus Crataegi is high.
Specific embodiment
With reference to specific embodiment, the concrete technical scheme of the present invention is described in detail.
Principle explanation：
The present invention carries out research and discussion by the mechanism that phosphoric acid and phosphoamide are reacted, and combines prior art literature
Solve, phosphoric acid and phosphoamide react generation urea phosphate, its molecular formula is：CO(NH2)2.H3PO4, in the environment of higher temperature,
Chemical bond between H and O in phosphoric acid can dialysis, hydrion and phosphoamide combine to form the ionic state containing positive charge so that
Urea phosphate forms the ion double salt that a kind of positive and negative charge phase attracts, its mechanism structural response following expression：CO(NH2)2.H3PO4
→(H2PO4)~.(H2NCONH3)+
Further, urea phosphate ion double salt phosphoric acid presence in the environment of, (H therein2NCONH3)+Cation and phosphorus
Acid is close, forms the intermediate-ion of C → O coordinate bond, as (CO5PN2H8)+, and then make to contain in a large number in urea phosphate intermediate
(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 it is molten
(CO is contained in liquid5PNH4K)+Double salt ion, and by testing and analyzing and controlling the content of N in solution, P, K element, in heating
Drying can be prepared by containing N, P, K element compound state composite fertilizer.
Its specific reaction principle will be by following reaction structure formula and reaction mechanism come further instruction：
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 there is coordinate bond between C atom and O atom.
Reaction equation four：
Wherein, the dotted line between carbon atom and oxygen atom represents there is coordinate bond between C atom and O atom.
In the present invention, phosphoamide and formaldehyde are being under 8.5～9.0 alkaline case in pH value, are pressurized and hyperthermic treatment, can produce
Life is once reacted：
Reaction equation five
Reaction equation six
GenerateEtc. ureaformaldehyde series of products, simultaneouslyEtc. ureaformaldehyde series of products after fertilising, through microorganism
Under effect, the N being easily absorbed by plants, C element can be discharged, the chain length of its ureaformaldehyde is longer, chain needs the time of fracture longer,
The time producing fertilizer efficiency can discharge after a certain time, can reach the effect of slow release.
Noun explanation：
Urea phosphate (Urea phosphate, UP), No. CAS is 4861～19～2, and molecular formula is CH7N2O5P, is represented by
CO(NH2)2·H3PO4：
It is 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, aqueous solution is in acidity, starts point during melting
Solution releases carbon dioxide and ammonia.
Embodiment one
A kind of production method of potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer, its step is as follows：
1) phosphoric acid and phosphoamide is adopted to be 1.2 according to mol ratio：1 mixing, and risen from 80 DEG C with programming rate for 5 DEG C/min
Temperature to 160 DEG C, stirring reaction 4～5h, separate obtain intermediate；This intermediate and alkaline potassium salt is adopted to be 1 according to mol ratio again：
1.3 mixing, after reaction terminates, obtain the nitrogenous, slip of phosphorus, potassium, and the slip of nitrogenous, phosphorus, potassium are placed in cooler crystallizer
Cool to 40～45 DEG C, carry out crystallizing filtration treatment, make filtrate circulation crystallization process in cooler crystallizer, the filter cake of acquisition is
Potassium dihydrogen phosphate product, the component content in detection filtrate, alkalescence potassium is potassium oxide solid or potassium hydroxide solid or hydroxide
Potassium solution, when for potassium hydroxide solution, concentration is 30%；
2) in filtrate plus alkalescence potassium and phosphoric acid, alkalescence potassium is potassium oxide solid or potassium hydroxide solid or potassium hydroxide is molten
Liquid, when for potassium hydroxide solution, concentration is 35%, the concentration of described phosphoric acid solution 17%, when the pH of solution is adjusted to
9.0, when nitrogen component content is 25%, phosphorus composition content is 12%, potassium composition content is 15%, add formaldehyde molten in filtrate
Liquid, the concentration of described formalin is 40%, and the mol ratio of the phosphoamide containing in formaldehyde and solution is 0.5：4, and
Pressurizeed and hyperthermic treatment, specific as follows：
Quick-pressing, to 6～8 atmospheric pressure, is rapidly heated to 80～100 DEG C, keeps 0.5～1h, then by solution decile
Amount it is divided into two parts, take the solution of a deal to continue to keep 3 atmospheric pressure and 80 DEG C of constant, holding 0.5～1h, obtain the breast that suspends
Liquid a；Take a component solution Quick-pressing big 6～8 atmospheric pressure when, pressure is increased with the speed of 20～40Pa/min, when reaching
Keep constant during to 10～12 atmospheric pressure, when being rapidly heated to 80～100 DEG C, with the ramp of 2～5 DEG C/min, when reaching
Keep constant during to 100 DEG C, keep 1～2h when pressure and temperature all reach peak, obtain suspension emulsion b.Then will hang
Floating emulsion a and suspension emulsion b mixing, obtain suspension emulsion A；
3) moderate-element, trace element and the amino acidses chelates such as calcium, magnesium, institute are added and then again in suspension emulsion A
The trace element stated is the trace element such as ferrum, boron, arsenic, manganese, copper, cobalt, molybdenum, obtains suspension emulsion B；
4) and then again temperature is down to 30～35 DEG C, and pressure increases to 6～8 atmospheric pressure, obtains the Chemical Mixed Fertilizer crude product of compound state,
When wherein nitrogen component content be 20%, phosphorus composition content be to stop crystallization when 9%, potassium composition content is 13%；
5) and then by pelletize and drying make hawthorn special fertilizer, wherein dry as oven drying at low temperature, temperature at 35～40 DEG C,
And the ammonia that flow velocity is 3～4m/s is passed through to drying environment circulation.
By originally letting slip the Chemical Mixed Fertilizer that the hawthorn special fertilizer made is compound state, wherein it is rich in
The nitrogen-phosphorus-potassium compound fertilizer of root and Realizing controlled-release Chemical Mixed Fertilizer.
Embodiment two
A kind of production method of potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer, its step is as follows：
1) phosphoric acid and phosphoamide is adopted to be 1.6 according to mol ratio：1 mixing, and risen from 80 DEG C with programming rate for 5 DEG C/min
Temperature to 160 DEG C, stirring reaction 4～5h, separate obtain intermediate；This intermediate and alkaline potassium salt is adopted to be 1 according to mol ratio again：
1.1 mixing, after reaction terminates, obtain the nitrogenous, slip of phosphorus, potassium, and the slip of nitrogenous, phosphorus, potassium are placed in cooler crystallizer
Cool to 40～45 DEG C, carry out crystallizing filtration treatment, make filtrate circulation crystallization process in cooler crystallizer, the filter cake of acquisition is
Potassium dihydrogen phosphate product, the component content in detection filtrate, alkalescence potassium is potassium oxide solid or potassium hydroxide solid or hydroxide
Potassium solution, when for potassium hydroxide solution, concentration is 35%；
2) in filtrate plus alkalescence potassium and phosphoric acid, alkalescence potassium is potassium oxide solid or potassium hydroxide solid or potassium hydroxide is molten
Liquid, when for potassium hydroxide solution, concentration is 30%, the concentration of described phosphoric acid solution 20%, when the pH of solution is adjusted to
8.5, when nitrogen component content is 30%, phosphorus composition content is 7%, potassium composition content is 20%, in filtrate, add formalin,
The concentration of described formalin is the mol ratio of the phosphoamide containing in 35%, and formaldehyde and solution is 1.5：4, and carry out
Pressurization and hyperthermic treatment, specific as follows：
Quick-pressing, to 6～8 atmospheric pressure, is rapidly heated to 80～100 DEG C, keeps 0.5～1h, then by solution decile
Amount it is divided into two parts, take the solution of a deal to continue to keep 3 atmospheric pressure and 80 DEG C of constant, holding 0.5～1h, obtain the breast that suspends
Liquid a；Take a component solution Quick-pressing big 6～8 atmospheric pressure when, pressure is increased with the speed of 20～40Pa/min, when reaching
Keep constant during to 10～12 atmospheric pressure, when being rapidly heated to 80～100 DEG C, with the ramp of 2～5 DEG C/min, when reaching
Keep constant during to 100 DEG C, keep 1～2h when pressure and temperature all reach peak, obtain suspension emulsion b.Then will hang
Floating emulsion a and suspension emulsion b mixing, obtain suspension emulsion A；
3) moderate-element, trace element and the amino acidses chelates such as calcium, magnesium, institute are added and then again in suspension emulsion A
The trace element stated is the trace element such as ferrum, boron, arsenic, manganese, copper, cobalt, molybdenum, obtains suspension emulsion B；
4) and then again temperature is down to 30～35 DEG C, and pressure increases to 6～8 atmospheric pressure, obtains the Chemical Mixed Fertilizer crude product of compound state,
When wherein nitrogen component content be 25%, phosphorus composition content be to stop crystallization when 6%, potassium composition content is 18%；
5) and then by pelletize and drying make hawthorn special fertilizer, wherein dry as oven drying at low temperature, temperature at 35～40 DEG C,
And the ammonia that flow velocity is 3～4m/s is passed through to drying environment circulation.
By originally letting slip the Chemical Mixed Fertilizer that the hawthorn special fertilizer made is compound state, wherein it is rich in
The nitrogen-phosphorus-potassium compound fertilizer of root and Realizing controlled-release Chemical Mixed Fertilizer.
Embodiment three
A kind of production method of potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer, its step is as follows：
1) phosphoric acid and phosphoamide is adopted to be 1 .4 according to mol ratio：1 mixing, and with programming rate for 5 DEG C/min from 80 DEG C
It is warming up to 160 DEG C, stirring reaction 4～5h, separate and obtain intermediate；Using this intermediate and alkaline potassium salt according to mol ratio it is again
1：1.2 mixing, after reaction terminates, obtain the nitrogenous, slip of phosphorus, potassium, and the slip of nitrogenous, phosphorus, potassium are placed in cooler crystallizer
In cool to 40～45 DEG C, carry out crystallizing filtration treatment, make filtrate circulation crystallization process in cooler crystallizer, the filter cake of acquisition
For potassium dihydrogen phosphate product, detect the component content in filtrate, alkalescence potassium is potassium oxide solid or potassium hydroxide solid or hydrogen-oxygen
Change potassium solution, when for potassium hydroxide solution, concentration is 33%；
2) in filtrate plus alkalescence potassium and phosphoric acid, alkalescence potassium is potassium oxide solid or potassium hydroxide solid or potassium hydroxide is molten
Liquid, when for potassium hydroxide solution, concentration is 34%, the concentration of described phosphoric acid solution 18%, when the pH of solution is adjusted to
8.8, when nitrogen component content is 27%, phosphorus composition content is 9%, potassium composition content is 18%, in filtrate, add formalin,
The concentration of described formalin is the mol ratio of the phosphoamide containing in 36%, and formaldehyde and solution is 1：4, and carry out adding
Pressure and hyperthermic treatment, specific as follows：
Quick-pressing, to 6～8 atmospheric pressure, is rapidly heated to 80～100 DEG C, keeps 0.5～1h, then by solution decile
Amount it is divided into two parts, take the solution of a deal to continue to keep 3 atmospheric pressure and 80 DEG C of constant, holding 0.5～1h, obtain the breast that suspends
Liquid a；Take a component solution Quick-pressing big 6～8 atmospheric pressure when, pressure is increased with the speed of 20～40Pa/min, when reaching
Keep constant during to 10～12 atmospheric pressure, when being rapidly heated to 80～100 DEG C, with the ramp of 2～5 DEG C/min, when reaching
Keep constant during to 100 DEG C, keep 1～2h when pressure and temperature all reach peak, obtain suspension emulsion b.Then will hang
Floating emulsion a and suspension emulsion b mixing, obtain suspension emulsion A；
3) moderate-element, trace element and the amino acidses chelates such as calcium, magnesium, institute are added and then again in suspension emulsion A
The trace element stated is the trace element such as ferrum, boron, arsenic, manganese, copper, cobalt, molybdenum, obtains suspension emulsion B；
4) and then again temperature is down to 30～35 DEG C, and pressure increases to 6～8 atmospheric pressure, obtains the Chemical Mixed Fertilizer crude product of compound state,
When wherein nitrogen component content be 24%, phosphorus composition content be to stop crystallization when 8%, potassium composition content is 16%；
5) and then by pelletize and drying make hawthorn special fertilizer, wherein dry as oven drying at low temperature, temperature at 35～40 DEG C,
And the ammonia that flow velocity is 3～4m/s is passed through to drying environment circulation.
By originally letting slip the Chemical Mixed Fertilizer that the hawthorn special fertilizer made is compound state, wherein it is rich in
The nitrogen-phosphorus-potassium compound fertilizer of root and Realizing controlled-release Chemical Mixed Fertilizer.
In order to preferably prove the beneficial effect that the present invention realizes, present invention also offers test example once：
Experimental example one
The fertilizer planted as Fructus Crataegi using general N-P-K mixed fertilizer, wherein nitrogen component content are that 20%, phosphorus composition content is
9%th, potassium composition content is 13%, makes culture fluid, cultivates hawthorn seedling, is named as A1.Plant thornbuss, life with this mixed fertilizer
Entitled A2.
Test example two
The fertilizer planted as Fructus Crataegi using general N-P-K mixed fertilizer, wherein nitrogen component content are that 25%, phosphorus composition content is
6%th, potassium composition content is 18%, makes culture fluid, cultivates hawthorn seedling, is named as B1.Plant thornbuss, life with this mixed fertilizer
Entitled B2.
Test example three
The fertilizer planted as Fructus Crataegi using general N-P-K mixed fertilizer, wherein nitrogen component content are that 24%, phosphorus composition content is
8%th, potassium composition content is 16%, makes culture fluid, cultivates hawthorn seedling, is named as C1.Plant thornbuss, life with this mixed fertilizer
Entitled C2.
Test example four arrives test example six
The hawthorn special fertilizer that an above-described embodiment one produces to embodiment three respectively makes culture fluid, cultivates hawthorn seedling,
It is respectively designated as D1, E1, F1.An above-described embodiment one arrives the hawthorn special fertilizer plantation thornbuss that embodiment three produces respectively, point
It is not named as D2, E2, F2.
Above-mentioned test example plants 20 hawthorn seedlings and 10 mu of thornbusses respectively, and statistical result following (1) is cultivated to seedling
After 30 days, N, P, K, Ca content in detection culture fluid, statistical table is as follows：
As can be seen from the above table, the hawthorn special fertilizer that the present embodiment provides, the absorbance of its N, P, K substantially mixes than common
Fertile is good.
(2) growing way situation of xylocinnamomum, its yield of 1 mu of thornbuss of random statistical are counted, statistical result is as follows：
As can be seen from the above table, the hawthorn special fertilizer being made using the present embodiment, its fertilizer efficiency time is long, and the yield of Fructus Crataegi
Than the high 500～600kg/ mu of yield using common mixed fertilizer.
Claims (9)
1. a kind of production method of potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer, using phosphoric acid with phosphoamide according to mol ratio be
(1.2～1.6)：1 mixing, and it is warming up to 160 DEG C for 5 DEG C/min from 80 DEG C with programming rate, stirring reaction 4～5h, separate
To intermediate；This intermediate and alkaline potassium salt is adopted to be 1 according to mol ratio again：(1.1～1.3) mix, after reaction terminates, obtain
The nitrogenous, slip of phosphorus, potassium, and the slip of nitrogenous, phosphorus, potassium is placed in cooler crystallizer cools to 40～45 DEG C, crystallized
Filtration treatment, makes filtrate circulation crystallization process in cooler crystallizer, the filter cake of acquisition is potassium dihydrogen phosphate product, detects filtrate
In component content；In filtrate plus alkalescence potassium and phosphoric acid, when the pH of solution is 8.5～9.0, nitrogen component content is 25～30%,
Phosphorus composition content is 7～12%, potassium composition content is 15～20%, adds formalin, and pressurizeed and rise in filtrate
Temperature is processed, and obtains suspension emulsion A, then adds calcium, magnesium moderate-element, trace element and amino acidses again in suspension emulsion A
Chelate, obtains suspension emulsion B, and then decrease temperature crystalline step obtains the Chemical Mixed Fertilizer crude product of compound state again, when wherein nitrogen component contains
Measure for 20～25%, phosphorus composition content be 6～9%, potassium composition content be 13～18% when stop crystallization, then pass through pelletize and
Hawthorn special fertilizer is made in drying.
2. potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer as claimed in claim 1 production method it is characterised in that：Alkalescence
Potassium is potassium oxide solid or potassium hydroxide solid or potassium hydroxide solution, and when for potassium hydroxide solution, concentration is 30～35%.
3. potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer as claimed in claim 1 production method it is characterised in that：Described
Phosphoric acid solution concentration 17～20%.
4. potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer as claimed in claim 1 production method it is characterised in that：Described
Formalin concentration be the mol ratio of the phosphoamide containing in 35～40%, and formaldehyde and solution be (0.5～1.5)：
4.
5. potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer as claimed in claim 1 production method it is characterised in that：Described
Pressurization and the design parameter of hyperthermic treatment be：Quick-pressing, to 6～8 atmospheric pressure, is rapidly heated to 80～100 DEG C, keeps
Then solution aliquot is divided into two parts by 0.5～1h,
The solution taking a deal continues to keep 3 atmospheric pressure and 80 DEG C of constant, holding 0.5～1h, obtains suspension emulsion a,
Take a component solution Quick-pressing big 6～8 atmospheric pressure when, pressure is increased with the speed of 20～40Pa/min, when reaching
Keep constant during to 10～12 atmospheric pressure, when being rapidly heated to 80～100 DEG C, with the ramp of 2～5 DEG C/min, when reaching
Keep constant during to 100 DEG C, keep 1～2h when pressure and temperature all reach peak, obtain suspension emulsion b,
Then suspension emulsion a and suspension emulsion b is mixed, obtain suspension emulsion A.
6. potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer as claimed in claim 1 production method it is characterised in that：Described
Trace element be ferrum, boron, arsenic, manganese, copper, cobalt, molybdenum trace element.
7. potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer as claimed in claim 1 production method it is characterised in that：Suspend
It is cooling pressurized treatment that emulsion B carries out crystallisation step, and temperature is down to 30～35 DEG C, and pressure increases to 6～8 atmospheric pressure, obtains crystalline substance
Body, obtains hawthorn special fertilizer finally by granulation drying.
8. potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer as claimed in claim 1 production method it is characterised in that：Described
The Chemical Mixed Fertilizer of compound state contain following N P and K compound state structural formula：Wherein, carbon atom
Dotted line and oxygen atom between represents there is coordinate bond between C atom and O atom.
9. potassium dihydrogen phosphate preparation by-product hawthorn special fertilizer as claimed in claim 1 production method it is characterised in that：Described
The Chemical Mixed Fertilizer of compound state also containWithRealizing controlled-release compound
Fertile.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410477863.8A CN104310345B (en) | 2014-09-19 | 2014-09-19 | Method for preparing potassium dihydrogen phosphate and preparing special fertilizer for hawthorn fruits as byproduct |
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| CN201410477863.8A CN104310345B (en) | 2014-09-19 | 2014-09-19 | Method for preparing potassium dihydrogen phosphate and preparing special fertilizer for hawthorn fruits as byproduct |
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| CN1060648A (en) * | 1990-10-08 | 1992-04-29 | 邢新华 | Polybasic fertilizer |
| US6254655B1 (en) * | 1999-03-18 | 2001-07-03 | Oms Investments, Inc. | Processes for preparing granular composite fertilizer compositions and products produced thereby |
| CN100478311C (en) * | 2008-02-26 | 2009-04-15 | 山东金正大生态工程股份有限公司 | Special control-release fertilizer for haw tree and preparation method thereof |
| EP2766301A4 (en) * | 2011-10-13 | 2015-06-24 | Ekobalans Fenix Ab | Dewatering of phosphate precipitates |
| CN103803518A (en) * | 2014-01-24 | 2014-05-21 | 贵阳中化开磷化肥有限公司 | Method for preparing monopotassium phosphate by using wet-process phosphoric acid |
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Address after: Xifeng County in Guizhou Province, Guiyang city town 551109 Patentee after: Guiyang Kailin Chemical Co. Ltd. Patentee after: Guizhou Ke Xinhua smelting company limited Patentee after: Guizhou University Address before: Xifeng County in Guizhou Province, Guiyang city town 551109 Patentee before: Zhonghuakai Phosphorous Chemical Fertilizer Co., Ltd., Guiyang Patentee before: Guizhou Ke Xinhua smelting company limited Patentee before: Guizhou University |
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