CN104326463B - A kind of production method preparing dalcium biphosphate by-product paddy rice-dedicated fertilizer - Google Patents
A kind of production method preparing dalcium biphosphate by-product paddy rice-dedicated fertilizer Download PDFInfo
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Abstract
The present invention relates to chemical technology field, a kind of production method preparing dalcium biphosphate by-product paddy rice-dedicated fertilizer, it is changed by the coefficients such as the temperature of dalcium biphosphate being prepared by phosphoric acid by wet process, improve the purity of biphosphate calcium product, can produce containing N simultaneously, P, the Chemical Mixed Fertilizer of K compound state, it is possible not only to improve the purity of dalcium biphosphate, the absorbance of this paddy rice-dedicated fertilizer produced is good, in filtrate, add formaldehyde simultaneously make a kind of controlled-releasing compounding fertilizer, this paddy rice-dedicated fertilizer produced disclosure satisfy that the nutritional need in each period in growth cycle, substantially increase rice yield, it it is efficient Chemical Mixed Fertilizer.
Description
Technical field
The present invention relates to chemical technology field, particularly relate to a kind of production preparing dalcium biphosphate by-product paddy rice-dedicated fertilizer
Method.
Background technology
The tied grain of rice of Oryza sativa L. claims rice or rice after shelling.Nearly half population in the world, all with rice for food.Eighties of last century is late
Phase, View of World Rice annual production average out to about 400,000,000,000 kilograms, cultivated area about 1.45 hundred million hectares.Produced rice
95% is eaten by the mankind.The cereal crops that Oryza sativa L. Ye Shi China is main, the improvement of rice quality is with the raising of yield increasingly
Receive publicity.
The growing process of Oryza sativa L. be divided into before, during and after three periods, early stage refers to from transplanting to the termination of point evil, namely water
The vegetative growth phase of rice, now to promote effective point of foxtail millet and to strive for that many fringes are as target；Refer to that Rice Growing has been enter into mid-term raw
Generative growth phase (pollen formation period), now attack big fringe as target with strong stalk, but fertilising can not be too much；Later stage refers to that Oryza sativa L. enters
People was eared to ripe period, and now to attack, grain is many, grain is satisfied, and should keep not take off fertilizer, again can not be remaining green when it is due to become yellow and ripe late-maturing, owing to making
There are some irrational factors during with, the plant recovery of nutrient not only resulting in fertilizer reduces, and makes to include soil ring
Serious destruction has been suffered in interior ecological environment in border.The use of agrochemical occupies very important in China's Rice Production
Status, confirms according to the substantial amounts of result of the test of China, N, P, K ratio of the current chemical fertilizer of China and soil nutrient supply situation and work
Thing is not in tune to the Absorption of nutrient, present Fertilizer Market mainly based on scattered fertilizer variety the most molten, instant, fast,
Exacerbate the waste of fertilizer and the loss of nutrient, must could meet the crop whole period of development by repeatedly topdressing on producing
Demand to nutrient, this not only takes a lot of work, increase fertilising cost, and topdress, top application fertilizer nutrient loss amount big, hence it is evident that reduce fertilizer
Effect, it is difficult to play the yield increasing effect of fertilizer.
China is populous, and average cultivated area is extremely limited, protects existing arable land, modified utilization dyskinetic soil meaning
Justice is great；The most how to prepare a kind of nutrient substance to enrich, nutrient release is coordinated persistently, and fertilizer nutrient utilization ratio is high,
Single fertilization is without topdressing or topdressing less, and can improve soil property, and the Special fertilizer for paddy rice increasing soil fertility becomes mesh
The front technical issues that need to address.
Dalcium biphosphate, dalcium biphosphate, inorganic compound, is colourless three inclined tab shapes, granular or crystalline powder, extensively
For aquatic animal and the feed additive of livestock and poultry cultivation animal, as bulking agent, dough conditioner, buffer agent, nutrition
The quality improvers such as enriching substance, emulsifying agent, stabilizer.It mainly makes and includes that thermal phosphoric acid and phosphoric acid by wet process produce biphosphate
Calcium, and thermal phosphoric acid cost is relatively big, should not be as being widely popularized, therefore, Wet-process Phosphoric Acid Production biphosphate calcium product becomes
Main method, the basic step of wet process phosphoric acid for preparing dalcium biphosphate is as follows:
Reaction equation one:
CO(NH2)2+H3PO4=CO (NH2)2.H3PO4
Reaction equation two
CO(NH2)2.H3PO4+CaCO3=Ca (H2PO4)2+CO(NH2)2+H2O+CO2
After whole reaction terminates, for there is any change, simultaneously because phosphoamide dissolubility is the highest, at 20 DEG C in phosphoamide
Time, its dissolubility is that 85g/100ml (refers to " phosphate fertilizer and compound fertilizer " volume 20 the 6th phase solubility of chemical fertilizer and compound
Fertile production technology), the rising of the solubility with temperature of phosphoamide simultaneously and increase, so the phosphoamide contained in filtrate is passing through
After cooling crystal separates out, possibly together with a large amount of undecomposed phosphoamides, NH in filtrate4 +、H2PO4 -、HPO4 2-、PO4 3-If directly done
Waste water is discharged, and had both wasted resource, and can cause again the waste of resource, and the dipotassium hydrogen phosphate product purity being simultaneously manufactured is the highest.
During Wet-process Phosphoric Acid Production dalcium biphosphate, the purity of dalcium biphosphate is the highest, possibly together with greatly in filtrate
Measure undecomposed phosphoamide, NH4 +、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 tradition component content of paddy rice-dedicated fertilizer and the absorbing state of Oryza sativa L. are ground
Study carefully, effectively inquire into out from the filtrate of Wet-process Phosphoric Acid Production dalcium biphosphate, produce paddy rice-dedicated fertilizer, solve phosphoric acid by wet process raw
Produce the problems such as effective ingredient cannot utilize in the filtrate of dalcium biphosphate, at home in fertilizer production, have no report.
Summary of the invention
For solving above-mentioned technical problem, the invention provides a kind of production preparing dalcium biphosphate by-product paddy rice-dedicated fertilizer
Method, by unique process production design, improve the purity of dalcium biphosphate, make full use of wet process phosphoric acid for preparing phosphoric acid simultaneously
Phosphoamide, NH in the filtrate of calcium dihydrogen4 +、H2PO4 -、HPO4 2-、PO4 3-Deng material, the Oryza sativa L. producing out applicable paddy growth is special
Fertile.
The present invention is achieved by the following technical programs.
The invention provides a kind of production method preparing dalcium biphosphate by-product paddy rice-dedicated fertilizer, use phosphoric acid and phosphinylidyne
Amine is (1.3-1.6) according to mol ratio: 1 mixing, and is that 5 DEG C/min is warming up to 160 DEG C from 95 DEG C with programming rate, stirring reaction
4-5h, isolated intermediate；By intermediate, CaCO3Stirring reaction in phosphoric acid solution put into by solid simultaneously, after reaction terminates,
Adjust the pH value of solution to 3.2 with phosphoric acid solution, it is thus achieved that slip, and slip is placed in cooler crystallizer cools to 30-35 DEG C,
Carry out crystallize filtration treatment, make filtrate in cooler crystallizer circulation crystallization process, it is thus achieved that filter cake be biphosphate calcium product,
Component content in detection filtrate；At filtrate hydro-oxidation potassium and phosphoric acid solution, when the pH of solution is 3.5-4.0, and nitrogen component contains
When amount is 20-25%, phosphorus composition content is 4-10%, potassium component content is 10-15%, stops adding potassium hydroxide and phosphoric acid is molten
Liquid；In filtrate, add formalin, and carry out pressurizeing and hyperthermic treatment, obtain suspension emulsion A, the most again to suspension emulsion A
Middle interpolation trace element, obtains suspension emulsion B, and then paddy rice-dedicated fertilizer is made in recrystallization, pelletize and drying.
Described potassium hydroxide solution concentration is 10-15%.
The concentration of described phosphoric acid solution is 10-15%.
The concentration of described formalin is 30-35%, and the mol ratio of the phosphoamide contained in formaldehyde and solution is
(0.5-1.5): 4.
Described pressurization and the design parameter of hyperthermic treatment be: during big 6-8 the atmospheric pressure of solution Quick-pressing, with 20-
The speed of 30Pa/min increases pressure, keeps 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, keeps constant when reaching 120 DEG C, keeps 1-2h when pressure and temperature all arrive peak.
Described trace element is one or more in ferrum, boron, arsenic, manganese, copper, cobalt, molybdenum.
Suspension emulsion B carries out crystallisation step and is down to 30-35 DEG C for cooling pressurized treatment, temperature, and pressure increases to 6-8 air
Pressure, obtains crystal, dries finally by pelletize and obtains paddy rice-dedicated fertilizer.
Described paddy rice-dedicated fertilizer is the Chemical Mixed Fertilizer of compound state, wherein the content of nitrogen component be 18-21%, phosphorus composition content
It is 8-13% for 4-7%, potassium component content.
The Chemical Mixed Fertilizer of described compound state contains in its composition containing following N P and K compound state structural formula:Wherein, the dotted line between carbon atom and oxygen atom represents that between C atom and O atom, existence is joined
Position key, and containWith
Realizing controlled-release fertile.
In the present invention, by carbamide and phosphoric acid at 95 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,
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 to contain in solution simultaneously
Substantial amounts of dihydrogen phosphate, when adding calcium carbonate compound, dihydrogen phosphate and calcium carbonate reaction generate dalcium biphosphate, no
Separated out by decrease temperature crystalline；It is subsequently adding potassium hydroxide solution, when potassium content excess, it will with the ammonium in intermediate-ion
Radical ion reacts, and further makes intermediate-ion chelate intoIntermediate-ion, and with positive electricity
Lotus, and then when solution participates in other electronegative ions or compound, it will form compound salt with this ion, enter one
Nutritional labeling in the abundant product of step.
Meanwhile, meanwhile, carbamide is at pH in the case of the acidity of 3.5-4.0, and phosphoamide can react with formalin, generates urea aldehyde
Series of productsOrEven
Longer chemical chain,In the case of acidity, reaction can be continued with phosphoamide and formaldehyde to generateSimultaneously
Continue to react with phosphoamide and formaldehyde in the case of acidity,OrDeng 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 slow release generally,The release fertilizer efficiency time be 0-40 days,
The release fertilizer efficiency time be 40-80 days.
The beneficial effects of the present invention is: compared with prior art, there is following characteristics in the present invention:
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 dalcium biphosphate, phosphoamide mutually synthermal
Under dissolubility relatively large, isolated phosphoamide crystal rich in other crystal such as NH4 H2PO4, simultaneously entering cooling analysis
Go out in the filtrate after phosphoamide crystal possibly together with substantial amounts of phosphoamide, H2PO4 -、HPO4 2-、PO4 3-Utilize Deng not operatively, this
The bright temperature by wet process phosphoric acid for preparing dalcium biphosphate regulates to 80-160 DEG C, and heats up from 95 DEG C to 160 with the speed of 5 DEG C/min
React in the environment of DEG C, not only make the dalcium biphosphate product purity of precipitation reach more than 98%, to filtrate adds Strong oxdiative
After potassium solution, filtrate also generatesCation, to filtrate crystallisation separate out generate chemical combination
When state Chemical Mixed Fertilizer goes out finished product, it is ensured that compound state Chemical Mixed Fertilizer goes out in finished productIntermediate-ion and
Dihydrogen phosphate, and between C and O, form coordinate bond, this intermediate-ion can be formed many with centering element compound chelating
Element intermediate-ion, and then can continue to the compound electronegative with other or ion formation chelate, improve in double salt
Constituent content, and then the nutrient content in the double salt that this ion exists can be adjusted, meanwhile, this chelate can be hydrolyzed again
And by crop, and then effectively can provide fertilizer efficiency for crop for a long time, contain in conjunction with element in the solution that this ion is existed meanwhile
The mensuration of amount, and then adjust each constituent content when double salt is formed, dry and obtain compound state double salt compound fertilizer, its absorbance pole
Good, reduce Rice Cropping cost and improve paddy quality；
2. phosphoamide composition containing part in filtrate, adds formalin, in acid condition and certain pressure intensity and temperature
Under degree, generateOr
Deng urea aldehyde series compound fertilizer, this paddy rice-dedicated fertilizer can be made to reach the effect of realizing controlled-release；
3. by effective absorbtivity of n-p-k element is examined by the constituent content in paddy rice-dedicated fertilizer and Oryza sativa L.
Cls analysis, and the constituent content in production process is adjusted and arranges in pairs or groups so that being combined of the compound state prepared
The fertile demand that can meet crop to greatest extent, and reduce in composite heat transfer because of element mismatch, the cost caused
Too high, further avoid too much element to put among soil, cause the solidification of compound fertilizer to pollute environment.
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, hydrion is combined with carbamide and forms the ionic state containing positive charge so that phosphorus
Acid urea 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 calcium carbonate in solution, calcium carbonate can generate Ca with acid reaction2+, by fall
Temperature crystallization, generates Ca (H2PO4)2, in filtrate, then add potassium hydroxide solution, when potassium ion excess, dihydrogen phosphate
Form dalcium biphosphate crystal with potassium ion to be precipitated, unnecessary potassium ion and (CO5PN2H8)+Ionic reaction, and displace portion
Divide NH4 +So that containing (CO in solution5PNH4K)+Double salt ion, and analyzed by detection and control N in solution, P, K element
Content, can be prepared by containing N, P, the compound state compound fertilizer of K element at heat drying.
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.
When with CaCO3In phosphoric acid during mixing, hydrion is by CaCO3In Ca become calcium ion, dihydrogen phosphate and calcium from
Son reaction generates dalcium biphosphate, and in succession reaches saturated；When separating out Ca (H2PO3)2After crystal, containing substantial amounts of in filtrateRoot, to adding potassium hydroxide solution, when potassium content excess, it will in in filtrate
Between ammonium radical ion reaction in ion.
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, carbamide and formaldehyde are in the case of being 3.5-4.0 acidity at pH value, can produce and react:
Reaction equation five
Reaction equation six
Generate urea aldehyde series of productsOr
The most longer chemical chain,OrDeng
Urea aldehyde series of products, after fertilising, under the effect of microorganism, can discharge N, the C element being easily absorbed by plants, its
The chain length of urea aldehyde is the longest, and chain needs the time ruptured the longest, and the time producing fertilizer efficiency can discharge after a certain time, permissible
Reach the effect of slow release generally,The release fertilizer efficiency time be 0-40 days,The release fertilizer efficiency time be 40-80 days.
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, aqueous solution is acidity, starts point time melted
Solve and release carbon dioxide and ammonia.
Embodiment one
Present embodiments provide a kind of production method preparing dalcium biphosphate by-product paddy rice-dedicated fertilizer, mainly include following
Step:
1) using phosphoric acid is that 1.3:1 mixes with phosphoamide according to mol ratio, and is that 5 DEG C/min rises from 95 DEG C with programming rate
Temperature is to 160 DEG C, and 4h, isolated intermediate are reacted in stirring；
2) by intermediate, CaCO3Stirring reaction in the phosphoric acid solution that concentration is 10% put into by solid simultaneously, and reaction terminates
After, adjust the pH value of solution to 3.2 with phosphoric acid solution that concentration is 10%, 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 30 DEG C, carry out crystallizing filtration treatment, make filtrate follow in cooler crystallizer
Ring crystallization treatment, it is thus achieved that filter cake be biphosphate calcium product, detection filtrate in component content；
3) add concentration filtrate and be 10% potassium hydroxide and concentration is 10% phosphoric acid solution, when the pH of solution is 3.5, nitrogen
When component content is 20%, phosphorus composition content is 4%, potassium component content is 10%, stop adding potassium hydroxide and phosphoric acid solution；
4) adding concentration in filtrate is the formalin of 30%, and the phosphoamide contained in formaldehyde and solution mole
Than being 0.5:4, carrying out pressurizeing and hyperthermic treatment, obtain suspension emulsion A, described pressurization and the design parameter of hyperthermic treatment be:
During big 6-8 the atmospheric pressure of solution Quick-pressing, increase pressure with the speed of 20-30Pa/min, protect when reaching 10 atmospheric pressure
Hold constant, when being rapidly heated to 80 DEG C, with the ramp of 2 DEG C/min, keep constant when reaching 120 DEG C, when pressure and temperature
Degree keeps 1-2h when all arriving peak.
5) in suspension emulsion A, one or more trace element in ferrum, boron, arsenic, manganese, copper, cobalt, molybdenum are added the most again,
Obtain suspension emulsion B,
6) suspension emulsion B carrying out crystallisation step and is down to 30 DEG C for cooling pressurized treatment, temperature, pressure increases to 6 air
Pressure, obtains crystal, dries finally by pelletize and obtains paddy rice-dedicated fertilizer.
The paddy rice-dedicated fertilizer obtained is the Chemical Mixed Fertilizer of compound state, wherein the content of nitrogen component be 18%, phosphorus composition content be
4%, potassium component content is 8%；The Chemical Mixed Fertilizer of this compound state contains in its composition containing following N P and K compound state structural formula:Wherein, the dotted line between carbon atom and oxygen atom represents existence coordination between C atom and O atom
Key, and containWith
Realizing controlled-release fertile.
Embodiment two
Present embodiments provide a kind of production method preparing dalcium biphosphate by-product paddy rice-dedicated fertilizer, mainly include following
Step:
1) using phosphoric acid is that 1.6:1 mixes with phosphoamide according to mol ratio, and is that 5 DEG C/min rises from 95 DEG C with programming rate
Temperature is to 160 DEG C, and 5h, isolated intermediate are reacted in stirring；
2) by intermediate, CaCO3Stirring reaction in the phosphoric acid solution that concentration is 15% put into by solid simultaneously, and reaction terminates
After, adjust the pH value of solution to 3.2 with phosphoric acid solution that concentration is 15%, 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 DEG C, carry out crystallizing filtration treatment, make filtrate follow in cooler crystallizer
Ring crystallization treatment, it is thus achieved that filter cake be biphosphate calcium product, detection filtrate in component content；
3) add concentration filtrate and be 15% potassium hydroxide and concentration is 15% phosphoric acid solution, when the pH of solution is 4.0, nitrogen
When component content is 25%, phosphorus composition content is 10%, potassium component content is 15%, stops adding potassium hydroxide and phosphoric acid is molten
Liquid；
4) adding concentration in filtrate is the formalin of 35%, and the phosphoamide contained in formaldehyde and solution mole
Than being 1.5:4, carrying out pressurizeing and hyperthermic treatment, obtain suspension emulsion A, described pressurization and the design parameter of hyperthermic treatment be:
During big 8 atmospheric pressure of solution Quick-pressing, increase pressure with the speed of 20-30Pa/min, keep when reaching 12 atmospheric pressure
Constant, when being rapidly heated to 100 DEG C, with the ramp of 5 DEG C/min, keep constant when reaching 120 DEG C, when pressure and temperature
1-2h is kept when all arriving peak.
5) in suspension emulsion A, one or more trace element in ferrum, boron, arsenic, manganese, copper, cobalt, molybdenum are added the most again,
Obtain suspension emulsion B,
6) suspension emulsion B carrying out crystallisation step and is down to 35 DEG C for cooling pressurized treatment, temperature, pressure increases to 8 air
Pressure, obtains crystal, dries finally by pelletize and obtains paddy rice-dedicated fertilizer.
The paddy rice-dedicated fertilizer obtained is the Chemical Mixed Fertilizer of compound state, wherein the content of nitrogen component be 21%, phosphorus composition content be
7%, potassium component content is 13%；The Chemical Mixed Fertilizer of this compound state contains in its composition containing following N P and K compound state structural formula:Wherein, the dotted line between carbon atom and oxygen atom represents existence between C atom and O atom
Coordinate bond, and containWith
Realizing controlled-release fertile.
Embodiment three
Present embodiments provide a kind of production method preparing dalcium biphosphate by-product paddy rice-dedicated fertilizer, mainly include following
Step:
1) using phosphoric acid is that 1.5:1 mixes with phosphoamide according to mol ratio, and is that 5 DEG C/min rises from 95 DEG C with programming rate
Temperature is to 160 DEG C, and 4.5h, isolated intermediate are reacted in stirring；
2) by intermediate, CaCO3Stirring reaction in the phosphoric acid solution that concentration is 13% put into by solid simultaneously, and reaction terminates
After, adjust the pH value of solution to 3.2 with phosphoric acid solution that concentration is 13%, 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 33 DEG C, carry out crystallizing filtration treatment, make filtrate follow in cooler crystallizer
Ring crystallization treatment, it is thus achieved that filter cake be biphosphate calcium product, detection filtrate in component content；
3) add concentration filtrate and be 13% potassium hydroxide and concentration is 13% phosphoric acid solution, when the pH of solution is 3.7, nitrogen
When component content is 23%, phosphorus composition content is 8%, potassium component content is 13%, stop adding potassium hydroxide and phosphoric acid solution；
4) adding concentration in filtrate is the formalin of 33%, and the phosphoamide contained in formaldehyde and solution mole
Than being 1:4, carrying out pressurizeing and hyperthermic treatment, obtain suspension emulsion A, described pressurization and the design parameter of hyperthermic treatment be: molten
During big 7 atmospheric pressure of liquid Quick-pressing, increase pressure with the speed of 25Pa/min, keep constant when reaching 11 atmospheric pressure,
When being rapidly heated to 90 DEG C, with the ramp of 4 DEG C/min, keep constant when reaching 120 DEG C, when pressure and temperature all arrive
1-2h is kept during peak.
5) in suspension emulsion A, one or more trace element in ferrum, boron, arsenic, manganese, copper, cobalt, molybdenum are added the most again,
Obtain suspension emulsion B,
6) suspension emulsion B carrying out crystallisation step and is down to 33 DEG C for cooling pressurized treatment, temperature, pressure increases to 7 air
Pressure, obtains crystal, dries finally by pelletize and obtains paddy rice-dedicated fertilizer.
The paddy rice-dedicated fertilizer obtained is the Chemical Mixed Fertilizer of compound state, wherein the content of nitrogen component be 20%, phosphorus composition content be
6%, potassium component content is 10%；The Chemical Mixed Fertilizer of this compound state contains in its composition containing following N P and K compound state structural formula:Wherein, the dotted line between carbon atom and oxygen atom represents that between C atom and O atom, existence is joined
Position key, and containWithCan
Controlled Release Fertilizer.
In order to well prove the beneficial effect of patent of the present invention, the present invention also provides for following experimental example:
Experimental group 1-3
Using the paddy rice-dedicated fertilizer of above-described embodiment making as the most direct fertilization of rice to result of fertilizer, and make training
Rice seedling is cultivated by nutrient solution, and the yield of statistics Oryza sativa L., Solution culture method, after 15 days, detects N, P, K composition therein and contains
Amount, and the growing way situation of rice seedling.
Matched group 1-3
Fertile as fertilizer using common N, P, K, Ca mixing, wherein N, P, K component content in this mixing fertilizer is respectively at reality
Executing example one identical to N, P, K component content in embodiment three, fertilising is planted in the production to Oryza sativa L. respectively, and makes culture fluid pair
Rice seedling is cultivated, and the yield of statistics Oryza sativa L., Solution culture method, after 15 days, detects N, P, K component content therein.
By being the contrast of experimental group and matched group, the yield height 100-200kg/ mu of the yield increased group of experimental group,
In cultivating seedling, N, P, K residual condition in the nutritional solution in experimental group is 39%, 31%, 27% respectively simultaneously, far away
Less than N, P, K residual content in the nutritional solution in matched group.
Claims (9)
1. preparing a production method for dalcium biphosphate by-product paddy rice-dedicated fertilizer, employing phosphoric acid with phosphoamide according to mol ratio is
(1.3-1.6): 1 mixing, and it is that 5 DEG C/min is warming up to 160 DEG C from 95 DEG C with programming rate, stirring reaction 4-5h, isolated
Intermediate；By intermediate, CaCO3Stirring reaction in phosphoric acid solution put into by solid simultaneously, after reaction terminates, adjusts with phosphoric acid solution
The pH value of solution is to 3.2, it is thus achieved that slip, and slip is placed in cooler crystallizer and cools to 30-35 DEG C, carries out crystallizing at filtration
Reason, make filtrate in cooler crystallizer circulation crystallization process, it is thus achieved that filter cake be biphosphate calcium product, detection filtrate in one-tenth
Divide content；At filtrate hydro-oxidation potassium and phosphoric acid solution, when the pH of solution is 3.5-4.0, and nitrogen component content is 20-25%, phosphorus
When component content is 4-10%, potassium component content is 10-15%, stop adding potassium hydroxide and phosphoric acid solution；Add in filtrate
Enter formalin, and carry out pressurizeing and hyperthermic treatment, obtain suspension emulsion A, in suspension emulsion A, add trace unit the most again
Element, obtains suspension emulsion B, and then paddy rice-dedicated fertilizer is made in recrystallization, pelletize and drying.
Prepare the production method of dalcium biphosphate by-product paddy rice-dedicated fertilizer the most as claimed in claim 1, it is characterised in that: described
Potassium hydroxide solution concentration be 10-15%.
Prepare the production method of dalcium biphosphate by-product paddy rice-dedicated fertilizer the most as claimed in claim 1, it is characterised in that: described
The concentration of phosphoric acid solution be 10-15%.
Prepare the production method of dalcium biphosphate by-product paddy rice-dedicated fertilizer the most as claimed in claim 1, it is characterised in that: described
The concentration of formalin be 30-35%, and the mol ratio of the phosphoamide contained in formaldehyde and solution is (0.5-1.5): 4.
Prepare the production method of dalcium biphosphate by-product paddy rice-dedicated fertilizer the most as claimed in claim 1, it is characterised in that: described
Pressurization and the design parameter of hyperthermic treatment be: during big 6-8 the atmospheric pressure of solution Quick-pressing, with the speed of 20-30Pa/min
Increase pressure, keep when reaching 10-12 atmospheric pressure constant, when being rapidly heated to 80-100 DEG C, with the speed of 2-5 DEG C/min
Heat up, keep constant when reaching 120 DEG C, keep 1-2h when pressure and temperature all arrive peak.
Prepare the production method of dalcium biphosphate by-product paddy rice-dedicated fertilizer the most as claimed in claim 1, it is characterised in that: described
Trace element be one or more in ferrum, boron, arsenic, manganese, copper, cobalt, molybdenum.
Prepare the production method of dalcium biphosphate by-product paddy rice-dedicated fertilizer the most as claimed in claim 1, it is characterised in that: suspend
Emulsion B carries out crystallisation step and is down to 30-35 DEG C for cooling pressurized treatment, temperature, and pressure increases to 6-8 atmospheric pressure, obtains crystal,
Dry finally by pelletize and obtain paddy rice-dedicated fertilizer.
Prepare the production method of dalcium biphosphate by-product paddy rice-dedicated fertilizer the most as claimed in claim 1, it is characterised in that: described
The Chemical Mixed Fertilizer that paddy rice-dedicated fertilizer is compound state, wherein the content of nitrogen component be 18-21%, phosphorus composition content be 4-7%, potassium become
Dividing content is 8-13%.
Prepare the production method of dalcium biphosphate by-product paddy rice-dedicated fertilizer the most as claimed in claim 8, it is characterised in that: described
The Chemical Mixed Fertilizer of compound state contain in its composition containing following N P and K compound state structural formula:
Wherein, the dotted line between carbon atom and oxygen atom represents and there is coordinate bond between C atom and O atom, and containsWithCan
Controlled Release Fertilizer.
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| CN201410478265.2A CN104326463B (en) | 2014-09-19 | 2014-09-19 | A kind of production method preparing dalcium biphosphate by-product paddy rice-dedicated fertilizer |
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Citations (5)
| 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 |
| CN1343186A (en) * | 1999-03-18 | 2002-04-03 | Oms投资公司 | Processes for preparing granular composite fertilizer compositions and products produced thereby |
| CN1583681A (en) * | 2004-05-24 | 2005-02-23 | 陈天骏 | Agricultural composite manure and preparing method thereof |
| CN104003363A (en) * | 2014-05-20 | 2014-08-27 | 贵阳中化开磷化肥有限公司 | Production method of calcium dihydrogen phosphate |
-
2014
- 2014-09-19 CN CN201410478265.2A patent/CN104326463B/en not_active Expired - Fee Related
Patent Citations (5)
| 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 |
| CN1343186A (en) * | 1999-03-18 | 2002-04-03 | Oms投资公司 | Processes for preparing granular composite fertilizer compositions and products produced thereby |
| CN1583681A (en) * | 2004-05-24 | 2005-02-23 | 陈天骏 | Agricultural composite manure and preparing method thereof |
| CN104003363A (en) * | 2014-05-20 | 2014-08-27 | 贵阳中化开磷化肥有限公司 | Production method of calcium dihydrogen phosphate |
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Effective date of registration: 20160715 Address after: No. 237 Jinyang City Kailin Lake District Road 550009 Guizhou city of Guiyang Province Applicant after: GUIZHOU KAILIN GROUP Co.,Ltd. Applicant after: GUIZHOU KEXIN METALLURGICAL Co.,Ltd. Applicant after: Guizhou University Address before: Xifeng County in Guizhou Province, Guiyang city town 551109 Applicant before: GUIYANG SINOCHEM KAILIN FERTILIZER Co.,Ltd. Applicant before: GUIZHOU KEXIN METALLURGICAL Co.,Ltd. Applicant before: Guizhou University |
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