CN104326455B - A kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer - Google Patents
A kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew 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 Chinese yew 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 Chinese yew special fertilizer produced is good, and this Chinese yew special fertilizer simultaneously produced disclosure satisfy that the nutritional need in each period in the growth of taxol cycle, is efficient Chemical Mixed Fertilizer.
Description
Technical field
The present invention relates to chemical technology field, particularly relate to a kind of life preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer
Product 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.
Chinese yew, also known as Japanese yew, Chi Baisong.It it is the rare plants for anticancer being on the brink of extinction generally acknowledged in the world.It it is the Quaternary Period
One of lonely left ancient seeds in glacier.Nearly 2,500,000 years are the most grown.Wild red is only deposited at present in the tool report whole world
About beans China fir 25,000,000 strain.Slow long biological evolution and gene genetic impart the internal structure that these species are unique, taxol
(TAXOL), taxol be exactly one of the extract of this plant, in state-owned 4 kind of 1 mutation, i.e. China Chinese yew, taxus chinensis in northeast,
Taxusyunnanensis, southerm yew, Xizang Taxus chinensis etc., be distributed in northeast, south China and southwest.Sichuan is mainly distributed on cyclopentadienyl
County, Heisui River, Maerkang, Wenchuan, Luding, Kangding, Xichang, can manage, the area such as Miyi.The wild taxus resource of China is excessively cut
Cutting down and day by day increase the weight of, wild taxus resource has suffered serious destruction, so needing substantial amounts of artificial cultivation, applies fertilizer Chinese yew
In technology, often when plantation, use common farm manure, add nitrogen, phosphorus, potash fertilizer the most every year, the growing way of its Chinese yew
Slowly, and soil compaction is serious.
According to another report:
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 Chinese yew, cause the growing way of Chinese yew to subtract
Delay or rest.
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 Chinese yew special fertilizer and the absorbing state of Chinese yew are ground
Study carefully, effectively inquire into out from the filtrate of Wet-process Phosphoric Acid Production potassium dihydrogen phosphate, produce Chinese yew special fertilizer, solve phosphoric acid by wet process
The purity producing potassium dihydrogen phosphate is the highest, and in filtrate, active ingredient such as cannot utilize at the problem, and the absorptivity of this special fertilizer is good simultaneously
With the effect of realizing controlled-release, at home in fertilizer production, have no report.
Summary of the invention
For above technical problem, the invention provides a kind of production preparing potassium dihydrogen phosphate by-product Chinese yew 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 di(2-ethylhexyl)phosphate simultaneously
The active ingredient of hydrogen potassium, produces out the Chinese yew special fertilizer of applicable growth of taxol.
The present invention is achieved by the following technical solutions:
A kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer that the present invention provides, mainly includes following
Step:
1) using phosphoric acid to mix with phosphoamide, and be that 6 DEG C/min is warming up to 160 DEG C from 80 DEG C with programming rate, stirring is anti-
Answer 4-5h, isolated intermediate；Using this intermediate to mix with alkaline potassium salt again, regulation pH value is 8.5-9.0, and reaction terminates
After, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and the slip of nitrogenous, phosphorus, potassium is placed in cooler crystallizer cools to 35～40 DEG C, enter
Row crystallization filtration treatment, make filtrate in cooler crystallizer circulation crystallization process, it is thus achieved that filter cake be potassium dihydrogen phosphate product, inspection
Survey the component content in filtrate；
2) in filtrate, add formalin, with calcium hydroxide, potassium hydroxide and phosphoric acid solution regulate solution pH value and
Nitrogen, phosphorus, potassium, the content of calcium component, put into mixed liquor in retort, pressure increases to 8～10 atmospheric pressure, is rapidly heated
During to 85 DEG C, with the ramp of 5～6 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, increases pressure, simultaneously temperature from 85 DEG C with the speed of 1～2 DEG C/min
Rate heats up, and when temperature reaches 95 DEG C, keeps 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, adjusts
The scope of joint pH to 7.0～7.4, adds a small amount of zinc sulfate, copper sulphate, manganese sulfate, ammonium molybdate, ferrous sulfate, chelated iron, boron
One at least in sand, 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 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 16-19%, phosphorus composition content be 3-7%, potassium becomes
When point 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) the compound state composite fertilizer that separates out just finished product is fabricated to a diameter of
The particle 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 red
Beans China fir special fertilizer.
The mol ratio that described phosphoric acid mixes with phosphoamide is (1.2-1.5): 1.
The mol ratio that described intermediate mixes with alkaline potassium salt is 1:(1.1-1.4).
The mol ratio of the phosphoamide contained in described formaldehyde and solution is (0.8～0.9): 1.
Described step 2) calcium hydroxide concentration is 35～40%, the concentration of potassium hydroxide is 30～35%, phosphoric acid solution
Concentration be 20～25%.
Described step 2) the regulation pH value of solution and nitrogen, phosphorus, potassium, calcium component content particularly as follows: pH value 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
It is 12～18%.
Described step 3) increase pressure particularly as follows: be quickly ramped up to 2 atmospheric pressure time, with the speed of 50～100Pa/min
Rate increases atmospheric pressure, keeps constant when reaching 3 atmospheric pressure.
Described step 4) sulfuric acid concentration be 5～15%.
Described Chinese yew special fertilizer is the Chemical Mixed Fertilizer of compound state.
The Chemical Mixed Fertilizer of described compound state containsThe potassium phosphate composite fertilizer of root, and
A small amount ofWithThe compound state composite fertilizer of urea aldehyde.
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.WithWhenIon is in phosphoric acid environment,
Will be 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 generation potassium dihydrogen phosphate, and phase
Continue and reach saturated；When potassium content excess, it will react with the ammonium radical ion in intermediate-ion, further make middle from
Son chelates intoIntermediate-ion, and with positive charge, and then when solution participates in other
When electronegative ion or compound, it will form compound salt with this ion, the nutrition in the abundantest product becomes
Point.
Meanwhile, phosphoamide at pH under 8.5～9.0 alkaline case, when carrying out liter gentle pressurized treatments, meeting and formalin
Reaction, generatesDeng urea aldehyde series of products,It is difficult to preserve under alkaline case Deng urea aldehyde series of products, therefore
This needs the pH value with sulfuric acid solution regulation solution when 7.0～7.4, separates out the time preserved longer.Simultaneously Deng 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.
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 at C and O
Between formed coordinate bond, this intermediate-ion can with centering element compound chelating formed multielement intermediate-ion, Jin Erneng
Enough continuation forms chelate with other electronegative compounds or ion, improves constituent content in double salt, and then can adjust
Nutrient content in the double salt that this ion whole exists, meanwhile, this chelate can be hydrolyzed again and by crop, and then can have
The long-term of effect provides fertilizer efficiency for crop, meanwhile, in conjunction with the mensuration of constituent content in the solution that there is this ion, and then adjusts multiple
Each constituent content when salt is formed, dries and obtains compound state double salt composite fertilizer, and its absorptivity is fabulous, reduces planting yew
This and improve Chinese yew 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 red
Beans China fir 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 Chinese yew early stage nutrition further；
4. this Chinese yew 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 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, when a liter gentleness is pressurizeed, can send out
Give birth to row react:
Reaction equation five
Reaction equation six
GenerateDeng urea aldehyde series of products,In urea aldehyde
Series of products are difficult to preserve under alkaline case, so needing the pH value with sulfuric acid solution regulation solution when 7.0～7.4, analyse
Go out the time preserved longer.SimultaneouslyExist Deng urea aldehyde series of products
After fertilising, under the effect of microorganism, can discharge N, the C element being easily absorbed by plants, the chain length of its urea aldehyde is the longest,
Chain needs the time ruptured the longest, and 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
The present embodiment provide a kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer, mainly include with
Lower 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, after reaction terminates, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and is put by the slip of nitrogenous, phosphorus, potassium
In cooler crystallizer, cool to 35～40 DEG C, carry out crystallizing filtration treatment, make filtrate at circulation crystallization in cooler crystallizer
Reason, it is thus achieved that filter cake be potassium dihydrogen phosphate product, detection filtrate in component content；
2) in filtrate, add formalin, according to being that 0.8:1 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, wherein calcium hydroxide concentration is 40%, potassium hydroxide dense
Degree is 30%, and the concentration of phosphoric acid solution is 20%, when detect the pH value of solution 9.0, the content of nitrogen component be 18-25%,
When phosphorus composition content is 4-8%, potassium component content is 12-16%, calcium component content is when being 12～18%, is put into instead by mixed liquor
Answer in tank, pressure increased to 8～10 atmospheric pressure, be rapidly heated 85 DEG C time, with the ramp of 5～6 DEG C/min, arrive
During to 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, adjusts
The scope of joint pH to 7.0, described sulfuric acid concentration is 15%, is subsequently adding a small amount of zinc sulfate, copper sulphate, manganese sulfate, molybdic acid
One at least in ammonium, ferrous sulfate, chelated iron, borax, 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 ofThe potassium phosphate of root, and a small amount ofWith
Deng the compound state composite fertilizer just finished product of urea aldehyde, when the content of the nitrogen component in compound state composite fertilizer just finished product be 16%, phosphorus becomes
When point content is 7%, 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) the compound state composite fertilizer that separates out just finished product is fabricated to a diameter of
The particle 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 red
Beans China fir special fertilizer, this special fertilizer is the Chemical Mixed Fertilizer of compound state.
Embodiment two
The present embodiment provide a kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer, mainly include with
Lower 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, after reaction terminates, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and is put by the slip of nitrogenous, phosphorus, potassium
In cooler crystallizer, cool to 35～40 DEG C, carry out crystallizing filtration treatment, make filtrate at circulation crystallization in cooler crystallizer
Reason, it is thus achieved that filter cake be potassium dihydrogen phosphate product, detection filtrate in component content；
2) in filtrate, add formalin, according to being that 0.9:1 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, wherein calcium hydroxide concentration is 35%, potassium hydroxide dense
Degree 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 be 18-25%,
When phosphorus composition content is 4-8%, potassium component content is 12-16%, calcium component content is when being 12～18%, is put into instead by mixed liquor
Answer in tank, pressure increased to 8～10 atmospheric pressure, be rapidly heated 85 DEG C time, with the ramp of 5～6 DEG C/min, arrive
During to 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, adjusts
The scope of joint pH to 7.4, described sulfuric acid concentration is 5%, is subsequently adding a small amount of zinc sulfate, copper sulphate, manganese sulfate, molybdic acid
One at least in ammonium, ferrous sulfate, chelated iron, borax, 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 ofThe potassium phosphate of root, and a small amount ofWith
Deng the compound state composite fertilizer just finished product of urea aldehyde, when the content of the nitrogen component in compound state composite fertilizer just finished product be 19%, phosphorus becomes
When point content is 3%, 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) the compound state composite fertilizer that separates out just finished product is fabricated to a diameter of
The particle 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 red
Beans China fir special fertilizer, this special fertilizer is the Chemical Mixed Fertilizer of compound state.
Embodiment three
The present embodiment provide a kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer, mainly include with
Lower 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 8.7, after reaction terminates, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and is put by the slip of nitrogenous, phosphorus, potassium
In cooler crystallizer, cool to 35～40 DEG C, carry out crystallizing filtration treatment, make filtrate at circulation crystallization in cooler crystallizer
Reason, 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 that 0.85:1 mixes with the mol ratio of the phosphoamide contained in solution,
Regulate the pH value of solution with calcium hydroxide, potassium hydroxide and phosphoric acid solution, wherein calcium hydroxide concentration is 37%, and potassium hydroxide is dense
Degree is 33%, and the concentration of phosphoric acid solution is 22%, when detect the pH value of solution 8.8, the content of nitrogen component be 18-25%,
When phosphorus composition content is 4-8%, potassium component content is 12-16%, calcium component content is when being 12～18%, is put into instead by mixed liquor
Answer in tank, pressure increased to 8～10 atmospheric pressure, be rapidly heated 85 DEG C time, with the ramp of 5～6 DEG C/min, arrive
During to 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, adjusts
The scope of joint pH to 7.2, described sulfuric acid concentration is 10%, is subsequently adding a small amount of zinc sulfate, copper sulphate, manganese sulfate, molybdic acid
One at least in ammonium, ferrous sulfate, chelated iron, borax, 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 ofThe potassium phosphate of root, and a small amount ofWithDeng
The compound state composite fertilizer just finished product of urea aldehyde, when the content of the nitrogen component in compound state composite fertilizer just finished product be 18%, phosphorus composition
When content is 5%, 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) the compound state composite fertilizer that separates out just finished product is fabricated to a diameter of
The particle 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 red
Beans China fir special fertilizer, this 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, Chinese yew carried out soilless culture, cultivate
After 30 days, in detection nutrient solution, the content of N, P, K, Ca composition, observes its growing way, named A1 simultaneously.
Experimental example two is to test example four
The Chinese yew special fertilizer being successful with embodiment one to embodiment tripartite's method, as fertilizer, makes nutrient solution, right
Chinese yew carries out soilless culture, cultivate 15 days, 30 days, after 50 days, the content of N, P, K, Ca composition in detection nutrient solution respectively, with
Time observe 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 Chinese yew 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 Chinese yew 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 Chinese yew 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 Chinese yew special fertilizer that the present invention produces
In N, P, K, Ca composition only remain 30～40% and do not absorbed, illustrate that the Chinese yew special fertilizer that the present invention produces has absorption
The feature that rate is good.
Meanwhile, this experimental example also observes Chinese yew the 15th day, the 30th day, the growing way situation of the 50th day, is specially and uses
Above-mentioned experimental example cultivates 50 strain Chinese yew respectively, observes its growing way situation, such as table 4:
Table 4: Chinese yew was the 15th day, the 30th day, the growing way situation of the 50th day
As can be seen from Table 4, in a short time, the fertile Chinese yew special fertilizer produced with the present invention of common mixing is without much districts
Not, when cultivating 30 days, there is malnutritive, leaf Huang phenomenon without the Chinese yew that earth culture is supported in common mixed fertilizer, and the present invention produces
The Chinese yew cultivated of Chinese yew special fertilizer grow fine, its sprouting growing way is very fast, without yellow leaf phenomenon, during by the 50th day, commonly
Stopping growing occurs in the fertile Chinese yew supported without earth culture of mixing, and the most yellow leaf phenomenon is serious, and the Chinese yew that the present invention produces is special
The fertile growth of taxol cultivated is relatively slow, but without yellow leaf phenomenon.Illustrate that the Chinese yew special fertilizer that the present invention produces has realizing controlled-release
Effect.
Claims (9)
1. prepare a production method for potassium dihydrogen phosphate by-product Chinese yew special fertilizer, mainly comprise the steps that
1) use phosphoric acid to mix with phosphoamide, and be that 6 DEG C/min is warming up to 160 DEG C from 80 DEG C with programming rate, stirring reaction 4-
5h, isolated intermediate；Using this intermediate to mix with alkaline potassium salt again, regulation pH value is 8.5-9.0, after reaction terminates,
Obtain nitrogenous, the slip of phosphorus, potassium, and the slip of nitrogenous, phosphorus, potassium is placed in cooler crystallizer cools to 35～40 DEG C, carry out
Crystallization filtration treatment, make filtrate in cooler crystallizer circulation crystallization process, it is thus achieved that filter cake be potassium dihydrogen phosphate product, detection
Component content in filtrate；
2) in filtrate, add formalin, with calcium hydroxide, potassium hydroxide and phosphoric acid solution regulate the pH value of solution and nitrogen,
Phosphorus, potassium, the content of calcium component, put into mixed liquor in retort, pressure increases to 8～10 atmospheric pressure, is rapidly heated
When 85 DEG C, with the ramp of 5～6 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, increases pressure, simultaneously temperature from 85 DEG C with the speed liter of 1～2 DEG C/min
Temperature, when temperature reaches 95 DEG C, keeps 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, regulates pH
To the scope of 7.0～7.4, add in a small amount of zinc sulfate, copper sulphate, manganese sulfate, ammonium molybdate, ferrous sulfate, chelated iron, borax
One at least, 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 at the beginning of compound state composite fertilizer
Finished product, when the content of the nitrogen component in compound state composite fertilizer just finished product be 16-19%, phosphorus composition content be 3-7%, potassium composition contains
Amount for 11-14% time, calcium component content be 10-15% time, stop crystallization；
6) granulation is dried, in this step, first by step 5) the compound state composite fertilizer that separates out just finished product be fabricated to a diameter of 0.2～
The particle of 0.4cm, be subsequently placed in temperature be 45～50 DEG C, flow velocity be 3～4m/s ammonia environment in dry, make Chinese yew special
With fertilizer.
A kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer, its feature exists
In: the mol ratio that described phosphoric acid mixes with phosphoamide is (1.2-1.5): 1.
A kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer, its feature exists
In: the mol ratio that described intermediate mixes with alkaline potassium salt is 1:(1.1-1.4).
A kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer, its feature exists
In: the mol ratio of the phosphoamide contained in described formaldehyde and solution is (0.8～0.9): 1.
A kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer, its feature exists
In described step 2) calcium hydroxide concentration is 35～40%, the concentration of potassium hydroxide is 30～35%, the concentration of phosphoric acid solution
It is 20～25%.
A kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer, its feature exists
In described step 2) pH value of regulation solution and nitrogen, phosphorus, potassium, calcium component content particularly as follows: pH value is 8.5～9.0, nitrogen
When the content of composition is 18-25%, phosphorus composition content is 4-8%, potassium component content is 12-16%, calcium component content be 12～
18%.
A kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer, its feature exists
In described step 4) sulfuric acid concentration be 5～15%.
A kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer, its feature exists
In: described Chinese yew special fertilizer is the Chemical Mixed Fertilizer of compound state.
9. want a kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer as described in 9 such as right, it is characterised in that:
The Chemical Mixed Fertilizer of described compound state containsThe potassium phosphate composite fertilizer of root, and a small amount ofThe compound state composite fertilizer of urea aldehyde.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1191635A (en) * | 1966-07-27 | 1970-05-13 | Marchon Products Ltd | Improvements in the manufacture of Orthophosphates |
| CN1060648A (en) * | 1990-10-08 | 1992-04-29 | 邢新华 | Polybasic fertilizer |
| CN1583681A (en) * | 2004-05-24 | 2005-02-23 | 陈天骏 | Agricultural composite manure and preparing method thereof |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6254655B1 (en) * | 1999-03-18 | 2001-07-03 | Oms Investments, Inc. | Processes for preparing granular composite fertilizer compositions and products produced thereby |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1191635A (en) * | 1966-07-27 | 1970-05-13 | Marchon Products Ltd | Improvements in the manufacture of Orthophosphates |
| CN1060648A (en) * | 1990-10-08 | 1992-04-29 | 邢新华 | Polybasic fertilizer |
| CN1583681A (en) * | 2004-05-24 | 2005-02-23 | 陈天骏 | Agricultural composite manure and preparing method thereof |
| 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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