CN104326462B - A kind of production method preparing calcium dihydrogen phosphate by-product red bean special fertilizer - Google Patents
A kind of production method preparing calcium dihydrogen phosphate by-product red bean special fertilizer Download PDFInfo
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- CN104326462B CN104326462B CN201410478074.6A CN201410478074A CN104326462B CN 104326462 B CN104326462 B CN 104326462B CN 201410478074 A CN201410478074 A CN 201410478074A CN 104326462 B CN104326462 B CN 104326462B
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Abstract
The present invention relates to chemical technology field, a kind of production method preparing calcium dihydrogen phosphate by-product red bean special fertilizer, it is changed by the coefficients such as the temperature of calcium dihydrogen phosphate 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 calcium dihydrogen phosphate, the absorptivity of this red bean special fertilizer produced is good, in filtrate, add formaldehyde simultaneously make a kind of controlled-releasing compounding fertilizer, this red bean special fertilizer produced disclosure satisfy that the nutritional need in each period in growth cycle, substantially increase red bean 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 calcium dihydrogen phosphate by-product red bean special fertilizer
Method.
Background technology
Red bean (formal name used at school: Vigna angularis) is legume, has another name called red bean, red bean, is annual upright or winding
Herbaceous plant, summer at florescence, really phase 9～October, seed is edible and medicinal, is usually used in cooking congee, sweetened bean paste processed, people in daily life
" red bean " mentioned refer to its fruit.Red bean is tight with grain, look purple, red person is preferred, and the tonneau power of liquor food is strong, and detumescence is logical
Breast effect is very imitated, but for a long time food then to make us black and thin knot dry.Sowing after the Summer Solstice, about the high chi of bean seedlings stem, its branches and leaves are as cowpea
Branches and leaves, to fall flowering, less than spending of cowpea, color in silver brown, have peculiar smell.The pod of knot is about two or three cun.Compare GREEN PEAS
Slightly larger, the micro-leukorrhea of color of the leather is red, just harvesting during half blue or green half Huang.Ormosia high protein, low-fat high nutrition based food, Er Qiehan
There are the nutrients such as protein, carbohydrate, fat, dietary fiber, Cobastab group, vitamin E, potassium, calcium, iron, phosphorus, zinc.Red bean has rich
Rich irony, can make popularity look ruddy, it is also possible to enrich blood, stimulate circulation, strengthen muscle power, build up resistance.At present, red
Beans are often used in planting process based on nitrogen, phosphorus, the mixing fertilizer of potassium, and its absorptivity ratio is relatively low.
Calcium dihydrogen phosphate, is colourless three inclined tab shapes, granular or crystalline powder, is widely used in aquiculture animal and livestock and poultry
The feed addictive of cultivated animals, as leavening agent, dough conditioner, buffer, nutritional supplement, emulsifying agent, stabilizer etc.
Quality improver.It mainly makes and includes that thermal phosphoric acid and phosphoric acid by wet process produce calcium dihydrogen phosphate, 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, wet process phosphoric acid for preparing phosphorus
The basic step of acid dihydride calcium 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 solubility is the highest, at 20 DEG C in phosphoamide
Time, its solubility is that 85g/100ml (refers to " phosphate fertilizer and composite 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
Doing waste water to discharge, both wasted resource, and can cause again the waste of resource, the dipotassium hydrogen phosphate product purity being simultaneously manufactured is the highest.
During Wet-process Phosphoric Acid Production calcium dihydrogen phosphate, the purity of calcium dihydrogen phosphate 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 maize special fertilizer and the absorbing state of maize are ground
Study carefully, effectively inquire into out from the filtrate of Wet-process Phosphoric Acid Production calcium dihydrogen phosphate, produce maize special fertilizer, solve phosphoric acid by wet process raw
Produce the problems such as active ingredient cannot utilize in the filtrate of calcium dihydrogen phosphate, 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 calcium dihydrogen phosphate by-product red bean special fertilizer
Method, by unique process production design, improve the purity of calcium dihydrogen phosphate, 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 red bean producing out the growth of applicable red bean is special
Fertile.
The present invention is achieved by the following technical programs.
A kind of production method preparing calcium dihydrogen phosphate by-product red bean special fertilizer, comprises the following steps
(1) phosphoric acid of wet-method is used to be (1.3～1.6) with phosphoamide according to mol ratio: 1 mixes, and with the speed that heats up
Degree is that 5 DEG C/min is warming up to 160 DEG C from 95 DEG C, stirring reaction 4～5h, isolated intermediate；
(2) by intermediate, CaCO3Stirring reaction in phosphoric acid solution put into by solid simultaneously, after reaction terminates, uses phosphoric acid solution
Adjust the pH value of solution to 3.2, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and the slip of nitrogenous, phosphorus, potassium is placed in cooler crystallizer
Cool to 30 DEG C, carry out crystallize filtration treatment, make filtrate in cooler crystallizer circulation crystallization process, it is thus achieved that filter cake be phosphoric acid
Calcium dihydrogen product, the component content in detection filtrate；
(3) add potassium hydroxide solution and phosphoric acid solution filtrate, adjust nitrogen, phosphorus, potassium content and pH value in filtrate, work as filter
PH value in liquid is 3.5～4.0, nitrogen component content be 20～25%, phosphorus composition content be 10～15%, potassium component content be 12
～when 18%, stop adding potassium hydroxide solution and phosphoric acid solution；
(4) solution of step (3) adds formalin, during big 6～8 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, keep constant when reaching 120 DEG C, keep 1 when pressure and temperature all arrive peak
～2h, obtain suspension emulsion A,
(5) the most again in suspension emulsion A add trace element, obtain suspension emulsion B, described trace element be iron,
One or more in boron, arsenic, manganese, copper, cobalt, molybdenum, then red bean special fertilizer is made in recrystallization, granulation and drying.
Described potassium hydroxide solution concentration is 20～25%.
The concentration of described phosphoric acid solution is 20～25%.
The concentration of described formalin is 30～35%, and the mol ratio of formaldehyde and phosphoamide is (0.5～1.5):
4。
Described 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 atmospheric pressure, obtain crystal, dry finally by granulation and obtain red bean special fertilizer.
The described Chemical Mixed Fertilizer that red bean special fertilizer is compound state, wherein the content of nitrogen component be 18-21%, phosphorus composition content
It is 11-14% for 10-12%, potassium component content.
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 and there is coordinate bond between C atom and O atom, and containsWithCan
Controlled Release Fertilizer.
In the present invention, by urea 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, it will
Close with phosphoric acid, and then carry out ionic polymerization under the temperature environment when urea phosphate coordinate bond dialysis so thatIon generates with phosphoric acidIntermediate-ion, makes in solution containing a large amount of simultaneously
Dihydrogen phosphate, make in solution containing substantial amounts of dihydrogen phosphate simultaneously, when adding calcium carbonate compound, biphosphate
Root generates calcium dihydrogen phosphate with calcium carbonate reaction, is not separated out by decrease temperature crystalline；It is subsequently adding potassium hydroxide solution, works as potassium ion
During content excess, it will react with the ammonium radical ion in intermediate-ion, further make intermediate-ion chelate intoIntermediate-ion, and with positive charge, so when solution participates in other electronegative from
Nutritional labeling when son or compound, it will form compound salt with this ion, in the abundantest product.
Meanwhile, urea is in the case of acidity, and phosphoamide can react with formalin, generates urea aldehyde series of productsOrThe most longer
Chemical chain,In the case of acidity, reaction can be continued with phosphoamide and formaldehyde to generate OrDeng urea aldehyde series of products after fertilising, through the effect of microorganism
Under, N, the C element being easily absorbed by plants can be discharged, the chain length of its urea aldehyde is the longest, and chain needs the time ruptured the longest, produces fertilizer efficiency
Time can discharge after a certain time, can reach the effect of sustained release generally,
The release fertilizer efficiency time be 0～40 day,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 calcium dihydrogen phosphate, phosphoamide mutually synthermal
Under solubility relatively large, isolated phosphoamide crystal is rich in NH4·H2PO4In other crystal, entered cooling simultaneously and separated out
Possibly together with substantial amounts of phosphoamide, H in filtrate after phosphoamide crystal2PO4 -、HPO4 2-、PO4 3-Utilize Deng not operatively, the present invention
The temperature of wet process phosphoric acid for preparing calcium dihydrogen phosphate is regulated 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 calcium dihydrogen phosphate 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 change
When conjunction 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, forming coordinate bond, this intermediate-ion can be formed with centering element compound chelating
Multielement intermediate-ion, and then can continue to the compound electronegative with other or ion formation chelate, improve double salt
Middle constituent content, and then the nutrient content in the double salt that this ion exists can be adjusted, meanwhile, this chelate can carry out again water
Solve and by crop, and then effectively for a long time can provide fertilizer efficiency for crop, meanwhile, in conjunction with element in the solution that this ion is existed
The mensuration of content, and then adjust each constituent content when double salt is formed, dry and obtain compound state double salt composite fertilizer, its absorptivity pole
Good, reduce red bean planting cost and improve red bean quality；
2. phosphoamide composition containing part in filtrate, adds formalin, in acid condition and certain pressure intensity and temperature
Under degree, generateOrDeng
Urea aldehyde series composite fertilizer, can make this red bean special fertilizer reach the effect of realizing controlled-release；
3. by effective uptake of n-p-k element is examined by the constituent content in red bean special fertilizer and red bean
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 composite 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, hydrogen ion is combined with urea 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 react generation Ca with acid2+, by fall
Temperature crystallization, generates Ca (H2PO4)2, in filtrate, then add potassium hydroxide solution, when potassium ion excess, dihydrogen phosphate
Form calcium dihydrogen phosphate 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 composite 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, hydrogen ion is by CaCO3In Ca become calcium ion, dihydrogen phosphate and calcium from
Son reaction generates calcium dihydrogen phosphate, 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, urea and formaldehyde are in the case of acidity, can produce and react:
Reaction equation five
Reaction equation six
Generate urea aldehyde series of productsOr
The most longer chemical chain,In the case of acidity, reaction can be continued with phosphoamide and formaldehyde to generate OrDeng urea aldehyde series of products after fertilising, through the effect of microorganism
Under, N, the C element being easily absorbed by plants can be discharged, the chain length of its urea aldehyde is the longest, and chain needs the time ruptured the longest, produces fertilizer efficiency
Time can discharge after a certain time, can reach the effect of sustained release generally,
The release fertilizer efficiency time be 0～40 day,Release fertilizer efficiency
Time is 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, the aqueous solution is acidity, starts point time melted
Solve and release carbon dioxide and ammonia.
Embodiment one
A kind of production method preparing calcium dihydrogen phosphate by-product red bean special fertilizer that the present invention provides, comprises the following steps:
(1) be that 1.3:1 mix with phosphoamide according to mol ratio with the phosphoric acid of wet-method, and with programming rate be 5 DEG C/
Min is warming up to 160 DEG C from 95 DEG C, stirring reaction 5h, isolated intermediate；
(2) by intermediate, CaCO3Stirring reaction in phosphoric acid solution put into by solid simultaneously, after reaction terminates, uses phosphoric acid solution
Adjust the pH value of solution to 3.2, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and the slip of nitrogenous, phosphorus, potassium is placed in cooler crystallizer
Cool to 30 DEG C, carry out crystallize filtration treatment, make filtrate in cooler crystallizer circulation crystallization process, it is thus achieved that filter cake be phosphoric acid
Calcium dihydrogen product, the component content in detection filtrate；
(3) add, filtrate, the potassium hydroxide solution and the phosphoric acid solution of 20% that concentration is 25%, adjust nitrogen in filtrate, phosphorus,
Potassium content and pH value, when in filtrate, pH value is 4.0, the content of nitrogen component is 25%, phosphorus composition content is 10%, potassium component content
When being 18%, stop adding potassium hydroxide solution and phosphoric acid solution；
(4) in the solution of step (3) add formalin, the concentration of described formalin is 35%, and formaldehyde with
The mol ratio of phosphoamide is 1.5:4, during big 6 atmospheric pressure of solution Quick-pressing, increases pressure, when reaching with the speed of 30Pa/min
Keep constant during to 10 atmospheric pressure, when being rapidly heated to 80 DEG C, with the ramp of 5 DEG C/min, keep when reaching 120 DEG C
Constant, keep 2h when pressure and temperature all arrive peak, obtain suspension emulsion A；
(5) the most again in suspension emulsion A add trace element, obtain suspension emulsion B, described trace element be iron,
One or more in boron, arsenic, manganese, copper, cobalt, molybdenum, then red bean special fertilizer is made in recrystallization, granulation and drying.
Entering detection, the purity of calcium dihydrogen phosphate is more than 98%, and the red bean special fertilizer obtained containsThe potassium phosphate composite fertilizer of root and Chemical Mixed Fertilizer, wherein the content of nitrogen component be 21%, phosphorus become
Point content is 10%, potassium component content is 14%.
Embodiment two
A kind of production method preparing calcium dihydrogen phosphate by-product red bean special fertilizer that the present invention provides, comprises the following steps
(1) phosphoric acid using wet-method is that 1.6:1 mixes with phosphoamide according to mol ratio, and with programming rate be 5 DEG C/
Min is warming up to 160 DEG C from 95 DEG C, stirring reaction 4h, isolated intermediate；
(2) by intermediate, CaCO3Stirring reaction in phosphoric acid solution put into by solid simultaneously, after reaction terminates, uses phosphoric acid solution
Adjust the pH value of solution to 3.2, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and the slip of nitrogenous, phosphorus, potassium is placed in cooler crystallizer
Cool to 35 DEG C, carry out crystallize filtration treatment, make filtrate in cooler crystallizer circulation crystallization process, it is thus achieved that filter cake be phosphoric acid
Calcium dihydrogen product, the component content in detection filtrate；
(3) add the phosphoric acid solution of the potassium hydroxide solution 25% that concentration is 20% filtrate, adjust nitrogen, phosphorus, potassium in filtrate
Content and pH value, when in filtrate, pH value is 3.5, the content of nitrogen component is 20%, phosphorus composition content is 15%, potassium component content is
When 12%, stop adding potassium hydroxide solution and phosphoric acid solution；
(4) in the solution of step (3) add formalin, the concentration of described formalin is 30%, and formaldehyde with
The mol ratio of phosphoamide is 0.5:4, during big 8 atmospheric pressure of solution Quick-pressing, increases pressure, when reaching with the speed of 20Pa/min
Keep constant during to 12 atmospheric pressure, when being rapidly heated to 100 DEG C, with the ramp of 5 DEG C/min, protect when reaching 120 DEG C
Hold constant, keep 2h when pressure and temperature all arrive peak, obtain suspension emulsion A,
(5) the most again in suspension emulsion A add trace element, obtain suspension emulsion B, described trace element be iron,
One or more in boron, arsenic, manganese, copper, cobalt, molybdenum, then red bean special fertilizer is made in recrystallization, granulation and drying.
Entering detection, the purity of calcium dihydrogen phosphate is more than 98%, and the red bean special fertilizer obtained containsThe potassium phosphate composite fertilizer of root and Chemical Mixed Fertilizer, wherein the content of nitrogen component be 18%, phosphorus
Component content is 12%, potassium component content is 11%.
Embodiment three
A kind of production method preparing calcium dihydrogen phosphate by-product red bean special fertilizer that the present invention provides, comprises the following steps
(1) phosphoric acid using wet-method is that 1.5:1 mixes with phosphoamide according to mol ratio, and with programming rate be 5 DEG C/
Min is warming up to 160 DEG C from 95 DEG C, stirring reaction 4h, isolated intermediate；
(2) by intermediate, CaCO3Stirring reaction in phosphoric acid solution put into by solid simultaneously, after reaction terminates, uses phosphoric acid solution
Adjust the pH value of solution to 3.2, it is thus achieved that nitrogenous, the slip of phosphorus, potassium, and the slip of nitrogenous, phosphorus, potassium is placed in cooler crystallizer
Cool to 33 DEG C, carry out crystallize filtration treatment, make filtrate in cooler crystallizer circulation crystallization process, it is thus achieved that filter cake be phosphoric acid
Calcium dihydrogen product, the component content in detection filtrate；
(3) add, filtrate, potassium hydroxide solution and the phosphoric acid solution of 23% that concentration is 22%, adjust nitrogen in filtrate,
Phosphorus, potassium content and pH value, when in filtrate, pH value is 3.8, the content of nitrogen component is 23%, phosphorus composition content is 12%, potassium composition
When content is 15%, calcium component content is 4%, stop adding potassium hydroxide solution and phosphoric acid solution；
(4) in the solution of step (3) add formalin, the concentration of described formalin is 33%, and formaldehyde with
The mol ratio of phosphoamide is 1:4, during big 7 atmospheric pressure of solution Quick-pressing, increases pressure, when reaching with the speed of 25Pa/min
Keep constant during 10～12 atmospheric pressure, when being rapidly heated to 80～100 DEG C, with the ramp of 4 DEG C/min, when reaching 120
DEG C time keep constant, when pressure and temperature all arrive peak keep 1.5h, obtain suspension emulsion A,
(5) the most again in suspension emulsion A add trace element, obtain suspension emulsion B, described trace element be iron,
One or more in boron, arsenic, manganese, copper, cobalt, molybdenum, then red bean special fertilizer is made in recrystallization, granulation and drying.
Entering detection, the purity of calcium dihydrogen phosphate is more than 98%, and the red bean special fertilizer obtained containsThe potassium phosphate composite fertilizer of root and Chemical Mixed Fertilizer, wherein the content of nitrogen component be 20%, phosphorus become
Point content is 11%, potassium component content is 12%.
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
The most directly the red bean of result is applied fertilizer as fertilizer using the red bean special fertilizer that above-described embodiment makes, and make training
Red bean seedling is cultivated by nutrient solution, the yield of statistics red bean, after Solution culture method 30, detects N, P, K therein and divides content, with
And the growing way situation of red bean seedling.
Control group 1～3
Fertile as fertilizer using common N, P, K mixing, wherein N, P, K component content in this mixing fertilizer is respectively at embodiment
One is identical to N, P, K component content in embodiment three, and fertilising is planted in the production to red bean respectively, and makes nutrient solution to red bean
Seedling is cultivated, the yield of statistics red bean, after Solution culture method 30, detects N, P, K component content therein.
By being the contrast of experimental group and control group, the yield high 50 of the yield increased group of experimental group～80kg/ mu,
In cultivating seedling, N, P, K residual condition in the nutrient solution in experimental group is 30%, 31%, 27% respectively simultaneously, the lowest
N, P, K residual content in nutrient solution in control group.
Claims (7)
1. prepare a production method for calcium dihydrogen phosphate by-product red bean special fertilizer, comprise the following steps:
(1) phosphoric acid of wet-method is used to be (1.3～1.6) with phosphoamide according to mol ratio: 1 mixes, and with programming rate for 5
DEG C/min is warming up to 160 DEG C from 95 DEG C, stirring reaction 4～5h, isolated intermediate；
(2) 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 nitrogenous, the slip of phosphorus, potassium, and the slip of nitrogenous, phosphorus, potassium is placed in cooler crystallizer cooling
To 30 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, the component content in detection filtrate；
(3) add potassium hydroxide solution and phosphoric acid solution filtrate, adjust nitrogen, phosphorus, potassium content and pH value in filtrate, when in filtrate
PH value be 3.5～4.0, nitrogen component content be 20～25%, phosphorus composition content be 10～15%, potassium component content be 12～
When 18%, stop adding potassium hydroxide solution and phosphoric acid solution；
(4) solution of step (3) adds formalin, during solution Quick-pressing to 6～8 atmospheric pressure, with 20～30Pa/
The speed of min increases pressure, keeps constant when reaching 10～12 atmospheric pressure, when being rapidly heated to 80～100 DEG C, with 2～5
DEG C/ramp of min, keep constant when reaching 120 DEG C, keep 1～2h when pressure and temperature all arrive peak,
To suspension emulsion A；
(5) the most again in suspension emulsion A add trace element, obtain suspension emulsion B, described trace element be iron, boron,
One or more in arsenic, manganese, copper, cobalt, molybdenum, then red bean special fertilizer is made in recrystallization, granulation and drying.
Prepare the production method of calcium dihydrogen phosphate by-product red bean special fertilizer the most as claimed in claim 1, it is characterised in that: described
Potassium hydroxide solution concentration be 20～25%.
Prepare the production method of calcium dihydrogen phosphate by-product red bean special fertilizer the most as claimed in claim 1, it is characterised in that: described
The concentration of phosphoric acid solution 20～25%.
Prepare the production method of calcium dihydrogen phosphate by-product red bean special 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 formaldehyde and phosphoamide is (0.5～1.5): 4.
Prepare the production method of calcium dihydrogen phosphate by-product red bean special 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 crystalline substance
Body, dries finally by granulation and obtains red bean special fertilizer.
Prepare the production method of calcium dihydrogen phosphate by-product red bean special fertilizer the most as claimed in claim 1, it is characterised in that: described
The Chemical Mixed Fertilizer that red bean special fertilizer is compound state, wherein the content of nitrogen component be 18-21%, phosphorus composition content be 10-12%, potassium
Component content is 11-14%.
Prepare the production method of calcium dihydrogen phosphate by-product red bean special fertilizer the most as claimed in claim 6, 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
And the dotted line between oxygen atom represents and there is coordinate bond between C atom and O atom, and containWithCan
Controlled Release Fertilizer.
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|---|---|---|---|---|
| GB1191635A (en) * | 1966-07-27 | 1970-05-13 | Marchon Products Ltd | Improvements in the manufacture of Orthophosphates |
| CN1343186A (en) * | 1999-03-18 | 2002-04-03 | Oms投资公司 | Processes for preparing granular composite fertilizer compositions and products produced thereby |
| CN103787293A (en) * | 2014-01-24 | 2014-05-14 | 贵阳中化开磷化肥有限公司 | Method for preparing sodium dihydrogen phosphate by utilizing phosphoric acid by wet process |
| 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 CN201410478074.6A patent/CN104326462B/en not_active Expired - Fee Related
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 |
| CN1343186A (en) * | 1999-03-18 | 2002-04-03 | Oms投资公司 | Processes for preparing granular composite fertilizer compositions and products produced thereby |
| CN103787293A (en) * | 2014-01-24 | 2014-05-14 | 贵阳中化开磷化肥有限公司 | Method for preparing sodium dihydrogen phosphate by utilizing phosphoric acid by wet process |
| 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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| CN104326462A (en) | 2015-02-04 |
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