CN104310358A - Method for preparing calcium dihydrogen phosphate and preparing special fertilizer for maize as byproduct - Google Patents
Method for preparing calcium dihydrogen phosphate and preparing special fertilizer for maize as byproduct Download PDFInfo
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- CN104310358A CN104310358A CN201410477819.7A CN201410477819A CN104310358A CN 104310358 A CN104310358 A CN 104310358A CN 201410477819 A CN201410477819 A CN 201410477819A CN 104310358 A CN104310358 A CN 104310358A
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Abstract
The invention relates to the technical field of chemical industry, and especially relates to a method for preparing calcium dihydrogen phosphate and preparing a special fertilizer for maize as a byproduct. The temperature and other coefficients of the preparation technology of calcium dihydrogen phosphate from phosphoric acid through a wet process are changed, so the purity of the calcium dihydrogen phosphate product is improved, and the N, P and K compounded fertilizer is produced. The method improves the purity of calcium dihydrogen phosphate, and the produced special fertilizer for maize has high absorptivity; and formaldehyde is added to a filtrate to prepare the controlled release compound fertilizer. The produced special fertilizer for maize can meet the nutrition needs of maize in all stages of the growth period of maize, greatly increases the output of maize, and is an efficient compound fertilizer.
Description
Technical field
The present invention relates to chemical technology field, particularly relate to a kind of production method preparing monocalcium phosphate by-product maize special fertilizer.
Background technology
Maize is the seed of gramineous herbaceous plant grain, and shell i.e. millet.Also known as white fine strain of millet grain, Xian grain, hard grain.Widely cultivate in northern China.To gather autumn mature fruit, dry peeling shell and use.Taste is sweet, salty, cool in nature.The beneficial taste of energy, support kidney qi, except dysphoria with smothery sensation, and diuresis.For taste abnormal heat, gastric disorder causing nausea vomiting or insufficiency of the spleen diarrhoea; Dysphoria with smothery sensation is quenched one's thirst, dry; Accumulation of heat in the urinary bladder, dysuria etc.
According to pertinent data display, the content of vitamin E in maize fat is higher, is of value to and promotes that human endocrine is movable; The L-glutamic acid contained in maize has brain strengthening function; Maize can take a tonic or nourishing food to build up one's health kidney qi, removes spleen pathogenic heat in the stomach, beneficial gas.Old person's bitter.Stomach energy can be controlled, quench one's thirst, diuresis, stopping leak dysentery, separate borax and wheat poison.Feeding habits of cooking congee warm up.Feed nascent children's, can cook congee by porphyrize, as milk, every day, a small amount of feeding, can help digest, logical tune stomach.At present, the mixing fertilizer of nitrogen, phosphorus, potassium mainly used by maize in planting process, and its specific absorption is lower.
Monocalcium phosphate, colourless three inclined tab shapes, granular or crystalline powder, be widely used in the fodder additives of aquatic animal and livestock and poultry cultivation animal, as quality improvers such as raising agent, dough conditioner, buffer reagent, accessory substance, emulsifying agent, stablizers.It mainly makes and comprises thermal phosphoric acid and phosphoric acid by wet process produces monocalcium phosphate, and thermal phosphoric acid cost is comparatively large, unsuitable as extensively promoting, therefore, Wet-process Phosphoric Acid Production biphosphate calcium product becomes main method, and the basic step of wet process phosphoric acid for preparing monocalcium phosphate is as follows:
Reaction formula one:
CO(NH
2)
2+H
3PO
4＝CO(NH
2)
2.H
3PO
4
Reaction formula two
CO(NH
2)
2.H
3PO
4+CaCO
3＝Ca(H
2PO
4)
2+CO(NH
2)
2+H
2O+CO
2
After whole reaction terminates, for there is any change in carboxamide, simultaneously because carboxamide solubleness is very high, 20 DEG C time, its solubleness is 85g/100ml (refer to " phosphate fertilizer and composite fertilizer " the 20th volume the 6th phase---solubility of chemical fertilizer and Compound fertilizer production technology), simultaneously the solubility with temperature of carboxamide rising and increase, so the carboxamide contained in filtrate is after separating out by cooling crystal, also containing a large amount of undecomposed carboxamide, NH in filtrate
4 +, H
2pO
4 ~, HPO
4 2 ~, PO
4 3 ~if directly do waste water and discharge, both wasted resource, and can cause again the waste of resource, the dipotassium hydrogen phosphate product purity made is not high simultaneously.
For in Wet-process Phosphoric Acid Production monocalcium phosphate process, the purity of monocalcium phosphate is not high, also containing a large amount of undecomposed carboxamide, NH in filtrate
4 +, H
2pO
4 ~, HPO
4 2 ~, PO
4 3 ~deng material, investigator of the present invention is from a large amount of prior art documents and Exploration & stu dy for many years, and traditional component content of maize special fertilizer and the absorbing state of maize are studied, effectively inquire into out and produce maize special fertilizer from the filtrate of Wet-process Phosphoric Acid Production monocalcium phosphate, solve the problems such as effective constituent cannot utilize in the filtrate of Wet-process Phosphoric Acid Production monocalcium phosphate, at home in fertiliser production, have no report.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of production method preparing monocalcium phosphate by-product maize special fertilizer, by the process production design of uniqueness, improve the purity of monocalcium phosphate, make full use of carboxamide, NH in the filtrate of wet process phosphoric acid for preparing monocalcium phosphate simultaneously
4 +, H
2pO
4 ~, HPO
4 2 ~, PO
4 3 ~deng material, produce out the maize special fertilizer of applicable maize growth.
The present invention is achieved by the following technical programs.
The invention provides a kind of production method preparing monocalcium phosphate by-product maize special fertilizer, phosphoric acid is adopted to be (1.3 ~ 1.6) with carboxamide according to mol ratio: 1 mixes, and be that 5 DEG C/min is warming up to 160 DEG C from 95 DEG C with heat-up rate, stirring reaction 4 ~ 5h, is separated and obtains intermediate; By intermediate, CaCO
3phosphoric acid solution stirring reaction put into by solid simultaneously, after reaction terminates, the pH value of solution is adjusted to 3.2 with phosphoric acid solution, obtain nitrogenous, phosphorus, potassium, calcium slip, and the slip of nitrogenous, phosphorus, potassium is placed in cooling crystallizer cools to 30 ~ 35 DEG C, carry out crystallization filtration treatment, make filtrate circulation crystallization process in cooling crystallizer, the filter cake obtained is biphosphate calcium product, detects the component content in filtrate; At filtrate hydro-oxidation potassium and phosphoric acid solution, when when the pH of solution is 3.5 ~ 4.0, nitrogen component content is 20 ~ 25%, phosphorus composition content is 6 ~ 11%, potassium component content is 13 ~ 17%, stop adding potassium hydroxide and phosphoric acid solution; In filtrate, add formaldehyde solution, and carry out pressurizeing and hyperthermic treatment, obtain suspension emulsion A, and then add trace element in suspension emulsion A, obtain suspension emulsion B, and then maize special fertilizer is made in crystallization, granulation and oven dry.
Described potassium hydroxide solution concentration is 10 ~ 15%.
The concentration of described phosphoric acid solution is 10 ~ 15%.
The concentration of described formaldehyde solution is 30 ~ 35%, and the mol ratio of the carboxamide contained in formaldehyde and solution is (0.5 ~ 1.5): 4.
Described pressurization and the design parameter of hyperthermic treatment are: during large 6 ~ 8 normal atmosphere of solution Quick-pressing, pressure is increased with the speed of 20 ~ 30Pa/min, remain unchanged when reaching 10 ~ 12 normal atmosphere, when being rapidly heated to 80 ~ 100 DEG C, with the ramp of 2 ~ 5 DEG C/min, remaining unchanged when reaching 120 DEG C, keeping 1 ~ 2h when pressure and temperature all arrive maximum.
Described trace element is one or more in iron, boron, arsenic, manganese, copper, cobalt, molybdenum.
Suspension emulsion B carries out crystallisation step for cooling pressurized treatment, and temperature is down to 30 ~ 35 DEG C, and pressure increases to 6 ~ 8 normal atmosphere, obtains crystal, dries obtain maize special fertilizer finally by granulation.
Described maize special fertilizer is the Chemical Mixed Fertilizer of chemical combination state, and wherein the content of nitrogen component is 18-21%, phosphorus composition content is 5-8%, potassium component content is 9-13%.
The Chemical Mixed Fertilizer of described chemical combination state contains in its composition and contains following N P and K chemical combination state structural formula:
wherein, the dotted line between carbon atom and Sauerstoffatom represents to there is coordinate bond between C atom and O atom, and contains
with
the Chemical Mixed Fertilizer of realizing controlled-release.
In the present invention, by carboxamide and phosphoric acid at 95 DEG C, and react be warming up to the environment of 160 DEG C with the speed of 5 DEG C/min under, generate Ureaphil, and along with the progressively rising of temperature, and then make the coordinate bond dialysis between Ureaphil and form two kinds of ion like materials, be namely exactly
with
when
ion is in phosphoric acid environment, will be close with phosphoric acid, and then carries out ionic polymerization under temperature environment when the dialysis of Ureaphil coordinate bond, makes
ion and phosphoric acid generate
intermediate-ion, make containing a large amount of dihydrogen phosphates in solution, make containing a large amount of dihydrogen phosphates in solution, when adding calcium carbonate compound, dihydrogen phosphate and calcium carbonate reaction generate monocalcium phosphate, are not separated out by decrease temperature crystalline simultaneously simultaneously; Then add potassium hydroxide solution, when potassium content is excessive, will reacts with the ammonium radical ion in intermediate-ion, further make intermediate-ion chelating become
intermediate-ion, and with positive charge, and then when participating in other electronegative ions or compound in solution, compound salt will be formed with this ion, further enriching the nutritive ingredient in product.
Meanwhile, carboxamide at pH, under certain pressure intensity and temperature, can react with formaldehyde solution, generate under 8.5 ~ 9.0 alkaline case
deng urea aldehyde series product,
not easily preserve under alkaline case Deng urea aldehyde series product, so need to use the pH value of sulphuric acid soln regulator solution 7.0 ~ 7.4 time, the time of separating out preservation is longer.Simultaneously
deng urea aldehyde series product after fertilising, under the effect of microorganism, the N, the C element that are easily absorbed by plants can be discharged, the chain length of its urea aldehyde is longer, chain needs the time of fracture longer, and the time producing fertilizer efficiency can discharge after a certain time, can reach the effect of slowly-releasing.
Beneficial effect of the present invention is: compared with prior art, and the present invention exists following characteristics:
Compared with prior art, there is following characteristics in the present invention:
1. in the filtrate of conventional wet lay phosphoric acid monocalcium phosphate, be rich in carbon amide solution, the solubleness at the same temperature of carboxamide is relatively large, and isolated carboxamide crystal is rich in NH
4h
2pO
4in other crystal, entered in the filtrate after cooling precipitation carboxamide crystal also containing a large amount of carboxamide, H simultaneously
2pO
4 -, HPO
4 2-, PO
4 3-utilize Deng not operatively, the temperature of wet process phosphoric acid for preparing monocalcium phosphate is adjusted to 80 ~ 160 DEG C by the present invention, and react from the environment of 95 DEG C to 160 DEG C with the intensification of the speed of 5 DEG C/min, the monocalcium phosphate product purity of precipitation is not only made to reach more than 98%, after adding Strong oxdiative potassium solution in filtrate, also generate in filtrate
positively charged ion, to filtrate crystallisation separate out generate chemical combination state Chemical Mixed Fertilizer go out finished product time, ensure that chemical combination state Chemical Mixed Fertilizer goes out in finished product
intermediate-ion and dihydrogen phosphate, and coordinate bond is formed between C and O, this intermediate-ion can form multielement intermediate-ion with centering element compound chelating, and then the compound electronegative with other can be continued or ion forms inner complex, improve constituent content in double salt, and then the nutrient content that can adjust in the double salt of this ion existence, simultaneously, this inner complex can be hydrolyzed again and by crop, and then fertilizer efficiency can be provided for crop effectively for a long time, simultaneously, in conjunction with the mensuration of constituent content in the solution existed this ion, and then each constituent content during formation of adjustment double salt, dry and obtain chemical combination state double salt composite fertilizer, its specific absorption is fabulous, reduce maize planting cost and improve maize quality,
2. the carboxamide composition containing part in filtrate, adds formaldehyde solution, under alkaline condition and certain pressure intensity and temperature, adds formaldehyde solution, under alkaline condition and certain pressure intensity and temperature, generates
deng urea aldehyde series composite fertilizer, this maize special fertilizer can be made to reach the effect of realizing controlled-release;
3. by the constituent content in maize special fertilizer and maize the effective absorbed dose to n-p-k element carry out detection analyze, and carry out regulating to the constituent content in production process and arrange in pairs or groups, make the composite fertilizer of the chemical combination state prepared can meet the demand of crop to greatest extent, and reduce in composite heat transfer because element mismatch, the high cost caused, further avoid too much element to drop among soil, cause solidifying of composite fertilizer and contaminate environment.
Embodiment
Below in conjunction with specific embodiment, concrete technical scheme of the present invention is described in detail.
Principle illustrates:
The present invention carries out research and discussion by the mechanism of reacting phosphoric acid and carboxamide, and arrives in conjunction with prior art literature, and phosphoric acid and carboxamide react and generate Ureaphil, and its molecular formula is: CO (NH
2)
2.H
3pO
4under the environment of comparatively high temps, the chemical bond meeting dialysis between H and O in phosphoric acid, hydrogen ion is combined the ionic state formed containing positive charge with carboxamide, the ion double salt making Ureaphil form a kind of positive and negative charge to attract mutually, its mechanism structural response following expression: CO (NH
2)
2.H
3pO
4→ (H
2pO
4)
-. (H
2nCONH
3)
+
Further, under the environment that Ureaphil ion double salt exists at phosphoric acid, (H wherein
2nCONH
3)
+positive ion and phosphoric acid close, form the intermediate-ion of C → O coordinate bond, be (CO
5pN
2h
8)
+, and then make in Ureaphil intermediate containing a large amount of (H
2pO
4)
-(CO
5pN
2h
8)
+ion, when adding calcium carbonate in solution, calcium carbonate can generate Ca with acid-respons
2+, by decrease temperature crystalline, generate Ca (H
2pO
4)
2, then in filtrate, add potassium hydroxide solution, when potassium ion is excessive, dihydrogen phosphate and potassium ion form monocalcium phosphate crystal and are precipitated, unnecessary potassium ion and (CO
5pN
2h
8)
+ionic reaction, and displace part NH
4 +, make in solution containing (CO
5pNH
4k)
+double salt ion, and analyze by detecting and control the content of N in solution, P, K element, the chemical combination state composite fertilizer containing N, P, K element can be obtained at heat drying.
Its concrete reaction principle will carry out further instruction by following reaction structure formula and reaction mechanism:
Reaction formula one:
CO(NH
2)
2+H
3PO
4→CO(NH
2)
2.H
3PO
4
Reaction formula two:
Reaction formula three:
Wherein, the dotted line between carbon atom and Sauerstoffatom represents to there is coordinate bond between C atom and O atom.
When with CaCO
3when mixing in phosphoric acid, hydrogen ion is by CaCO
3in Ca become calcium ion, dihydrogen phosphate and calcium ion react and generate monocalcium phosphate, and in succession reach capacity; As precipitation Ca (H
2pO
3)
2after crystal, containing a large amount of in filtrate
root, adds potassium hydroxide solution in filtrate, when potassium content is excessive, will react with the ammonium radical ion in intermediate-ion.
Reaction formula four:
Wherein, the dotted line between carbon atom and Sauerstoffatom represents to there is coordinate bond between C atom and O atom.
In the present invention, carboxamide and formaldehyde are under being 8.5 ~ 9.0 alkaline case in pH value, are 8 ~ 10 normal atmosphere by pressure, and temperature is 85 ~ 120 DEG C can produce reaction:
Reaction formula five
Reaction formula six
Generate
deng urea aldehyde series product, simultaneously
deng urea aldehyde series product after fertilising, under the effect of microorganism, the N, the C element that are easily absorbed by plants can be discharged, the chain length of its urea aldehyde is longer, chain needs the time of fracture longer, and the time producing fertilizer efficiency can discharge after a certain time, can reach the effect of slowly-releasing.
Noun illustrates:
Ureaphil (Ureaphosphate, UP), No. CAS is 4861 ~ 19 ~ 2, and molecular formula is CH
7n
2o
5p, can be expressed as CO (NH
2)
2h
3pO
4:
It is a kind of fine chemical product being widely used in the fields such as livestock industry, industry, agricultural, its solid is white crystals or crystalline powder, and soluble in water and alcohol is insoluble to ethers, toluene and tetracol phenixin, the aqueous solution, in acid, start during melting to decompose and releases carbonic acid gas and ammonia.
Embodiment one
A kind of production method preparing monocalcium phosphate by-product maize special fertilizer provided by the invention, comprises the following steps
4) adopt the phosphoric acid of wet-method to be that 1.3:1 mixes with carboxamide according to mol ratio, and be that 5 DEG C/min is warming up to 160 DEG C from 95 DEG C with heat-up rate, stirring reaction 5h, separation obtains intermediate;
5) separation obtains intermediate; By intermediate, CaCO
3phosphoric acid solution stirring reaction put into by solid simultaneously, reaction times is 2h, after reaction terminates, by the pH value of phosphoric acid solution adjustment solution to 3.2, obtain nitrogenous, phosphorus, potassium slip, and the slip of nitrogenous, phosphorus, potassium is placed in cooling crystallizer cools to 30 DEG C, carry out crystallization filtration treatment, make filtrate circulation crystallization process in cooling crystallizer, the filter cake of acquisition is biphosphate calcium product, detects the component content in filtrate;
6) adding concentration filtrate is the potassium hydroxide solution of 15% and the phosphoric acid solution of 10%, nitrogen, phosphorus, potassium, calcium contents and pH value in adjustment filtrate, when in filtrate when the pH of solution is 8.5, when nitrogen component content is 20%, phosphorus composition content is 6%, potassium component content is 13%, stop adding potassium hydroxide solution and phosphoric acid solution;
7) formaldehyde solution is added in the solution of step (3), the concentration of described formaldehyde solution is 30%, and the mol ratio of the carboxamide contained in formaldehyde and solution is 1.5:4, during large 6 normal atmosphere of solution Quick-pressing, pressure is increased with the speed of 30Pa/min, remain unchanged when reaching 10 normal atmosphere, when being rapidly heated to 80 DEG C, with the ramp of 5 DEG C/min, remain unchanged when reaching 120 DEG C, keep 2h when pressure and temperature all arrive maximum, obtain suspension emulsion A
8) add trace element and then in suspension emulsion A, obtain suspension emulsion B, described trace element is one or more in iron, boron, arsenic, manganese, copper, cobalt, molybdenum, and then maize special fertilizer is made in crystallization, granulation and oven dry.
Entered detection, the purity of monocalcium phosphate is more than 98%, and the maize special fertilizer obtained contains
the potassiumphosphate composite fertilizer of root and and containing
with
the Chemical Mixed Fertilizer of realizing controlled-release, wherein the content of nitrogen component is 18%, phosphorus composition content is 5%, potassium component content is 9%.
Embodiment two
A kind of production method preparing monocalcium phosphate by-product maize special fertilizer provided by the invention, comprises the following steps
(1) adopt the phosphoric acid of wet-method to be that 1.6:1 mixes with carboxamide according to mol ratio, and be that 5 DEG C/min is warming up to 160 DEG C from 95 DEG C with heat-up rate, stirring reaction 4h, separation obtains intermediate;
(2) separation obtains intermediate; By intermediate, CaCO
3phosphoric acid solution stirring reaction put into by solid simultaneously, reaction times is 2h, after reaction terminates, by the pH value of phosphoric acid solution adjustment solution to 3.2, obtain nitrogenous, phosphorus, potassium slip, and the slip of nitrogenous, phosphorus, potassium is placed in cooling crystallizer cools to 35 DEG C, carry out crystallization filtration treatment, make filtrate circulation crystallization process in cooling crystallizer, the filter cake of acquisition is biphosphate calcium product, detects the component content in filtrate;
(3) adding concentration filtrate is the potassium hydroxide solution of 11% and the phosphoric acid solution of 12%, nitrogen, phosphorus, potassium, calcium contents and pH value in adjustment filtrate, when in filtrate when the pH of solution is 9.0, when nitrogen component content is 25%, phosphorus composition content is 11%, potassium component content is 17%, stop adding potassium hydroxide solution and phosphoric acid solution;
(4) formaldehyde solution is added in the solution of step (3), the concentration of described formaldehyde solution is 30 ~ 35%, and the mol ratio of the carboxamide contained in formaldehyde and solution is 0.5:4, during large 8 normal atmosphere of solution Quick-pressing, pressure is increased with the speed of 20Pa/min, remain unchanged when reaching 12 normal atmosphere, when being rapidly heated to 100 DEG C, with the ramp of 5 DEG C/min, remain unchanged when reaching 120 DEG C, keep 2h when pressure and temperature all arrive maximum, obtain suspension emulsion A
(5) add trace element and then in suspension emulsion A, obtain suspension emulsion B, described trace element is one or more in iron, boron, arsenic, manganese, copper, cobalt, molybdenum, and then maize special fertilizer is made in crystallization, granulation and oven dry.
Entered detection, the purity of monocalcium phosphate is more than 98%, and the maize special fertilizer obtained contains
the potassiumphosphate composite fertilizer of root and and containing
with
the Chemical Mixed Fertilizer of realizing controlled-release, wherein the content of nitrogen component is 21%, phosphorus composition content is 8%, potassium component content is 13%.
Embodiment three
A kind of production method preparing monocalcium phosphate by-product maize special fertilizer provided by the invention, comprises the following steps
(1) adopt the phosphoric acid of wet-method to be that 1.5:1 mixes with carboxamide according to mol ratio, and be that 5 DEG C/min is warming up to 160 DEG C from 95 DEG C with heat-up rate, stirring reaction 4h, separation obtains intermediate;
(2) separation obtains intermediate; By intermediate, CaCO
3phosphoric acid solution stirring reaction put into by solid simultaneously, reaction times is 2h, after reaction terminates, the pH value of solution is adjusted to 3.2 with phosphoric acid solution, and then ammonia is passed in flourish solution, reaction times is 1.5h, after reaction terminates, obtain nitrogenous, phosphorus, potassium slip, and the slip of nitrogenous, phosphorus, potassium is placed in cooling crystallizer cools to 33 DEG C, carry out crystallization filtration treatment, make filtrate circulation crystallization process in cooling crystallizer, the filter cake obtained is biphosphate calcium product, detects the component content in filtrate;
(3) adding concentration filtrate is the potassium hydroxide solution of 10% and the phosphoric acid solution of 15%, nitrogen, phosphorus, potassium, calcium contents and pH value in adjustment filtrate, when in filtrate when the pH of solution is 8.8, when the content of nitrogen component is 23%, phosphorus composition content is 6%, potassium component content is 15%, stop adding potassium hydroxide solution and phosphoric acid solution;
(4) formaldehyde solution is added in the solution of step (3), the concentration of described formaldehyde solution is 30 ~ 35%, and the mol ratio of the carboxamide contained in formaldehyde and solution is 1.0:4, during large 7 normal atmosphere of solution Quick-pressing, pressure is increased with the speed of 25Pa/min, remain unchanged when reaching 10 ~ 12 normal atmosphere, when being rapidly heated to 80 ~ 100 DEG C, with the ramp of 4 DEG C/min, remain unchanged when reaching 120 DEG C, keep 1.5h when pressure and temperature all arrive maximum, obtain suspension emulsion A
(5) add trace element and then in suspension emulsion A, obtain suspension emulsion B, described trace element is one or more in iron, boron, arsenic, manganese, copper, cobalt, molybdenum, and then maize special fertilizer is made in crystallization, granulation and oven dry.
Entered detection, the purity of monocalcium phosphate is more than 98%, and the maize special fertilizer obtained contains
the potassiumphosphate composite fertilizer of root and and containing
with
the Chemical Mixed Fertilizer of realizing controlled-release, wherein the content of nitrogen component is 189%, phosphorus composition content is 7%, potassium component content is 11%.
In order to well prove the beneficial effect of patent of the present invention, the present invention also provides following experimental example:
Experimental group 1 ~ 3
Using above-described embodiment make maize special fertilizer as fertilizer respectively the direct maize to result apply fertilizer, with make nutrient solution maize seedling cultivated, the output of statistics maize, Solution culture method is after 15 days, detect N, P, K, Ca component content wherein, and the growing way situation of maize seedling.
Control group 1 ~ 3
Fertile in fertilizer using common N, P, K, Ca mixing, N, P, K, Ca component content wherein in this mixing fertilizer is identical to N, P, K, Ca component content in embodiment three respectively at embodiment one, respectively to the production plantation fertilising of maize, with make nutrient solution maize seedling cultivated, the output of statistics maize, Solution culture method, after 15 days, detects N, P, K, Ca component content wherein.
By being the contrast of experimental group and control group, high 100 ~ 200kg/ the mu of output of the yield increased group of experimental group, in seedling is cultivated, N, P, K, Ca residual condition in nutritive medium simultaneously in experimental group is 39%, 31%, 27%, 29% respectively, well below N, P, K, Ca residual content in the nutritive medium in control group.
Claims (9)
1. prepare the production method of monocalcium phosphate by-product maize special fertilizer for one kind, phosphoric acid is adopted to be (1.3 ~ 1.6) with carboxamide according to mol ratio: 1 mixes, and be that 5 DEG C/min is warming up to 160 DEG C from 95 DEG C with heat-up rate, stirring reaction 4 ~ 5h, is separated and obtains intermediate; By intermediate, CaCO
3phosphoric acid solution stirring reaction put into by solid simultaneously, after reaction terminates, the pH value of solution is adjusted to 3.2 with phosphoric acid solution, obtain nitrogenous, phosphorus, potassium, calcium slip, and the slip of nitrogenous, phosphorus, potassium is placed in cooling crystallizer cools to 30 ~ 35 DEG C, carry out crystallization filtration treatment, make filtrate circulation crystallization process in cooling crystallizer, the filter cake obtained is biphosphate calcium product, detects the component content in filtrate; At filtrate hydro-oxidation potassium and phosphoric acid solution, when when the pH of solution is 8.5 ~ 9.0, nitrogen component content is 20 ~ 25%, phosphorus composition content is 6 ~ 11%, potassium component content is 13 ~ 17%, stop adding potassium hydroxide and phosphoric acid solution; In filtrate, add formaldehyde solution, and carry out pressurizeing and hyperthermic treatment, obtain suspension emulsion A, and then add trace element in suspension emulsion A, obtain suspension emulsion B, and then maize special fertilizer is made in crystallization, granulation and oven dry.
2. prepare the production method of monocalcium phosphate by-product maize special fertilizer as claimed in claim 1, it is characterized in that: described potassium hydroxide solution concentration is 10 ~ 15%.
3. prepare the production method of monocalcium phosphate by-product maize special fertilizer as claimed in claim 1, it is characterized in that: the concentration of described phosphoric acid solution is 10 ~ 15%.
4. prepare the production method of monocalcium phosphate by-product maize special fertilizer as claimed in claim 1, it is characterized in that: the concentration of described formaldehyde solution is 30 ~ 35%, and the mol ratio of the carboxamide contained in formaldehyde and solution is (0.5 ~ 1.5): 4.
5. prepare the production method of monocalcium phosphate by-product maize special fertilizer as claimed in claim 1, it is characterized in that: described pressurization and the design parameter of hyperthermic treatment are: during large 6 ~ 8 normal atmosphere of solution Quick-pressing, pressure is increased with the speed of 20 ~ 30Pa/min, remain unchanged when reaching 10 ~ 12 normal atmosphere, when being rapidly heated to 80 ~ 100 DEG C, with the ramp of 2 ~ 5 DEG C/min, remaining unchanged when reaching 120 DEG C, keeping 1 ~ 2h when pressure and temperature all arrive maximum.
6. prepare the production method of monocalcium phosphate by-product maize special fertilizer as claimed in claim 1, it is characterized in that: described trace element is one or more in iron, boron, arsenic, manganese, copper, cobalt, molybdenum.
7. prepare the production method of monocalcium phosphate by-product maize special fertilizer as claimed in claim 1, it is characterized in that: suspension emulsion B carries out crystallisation step for cooling pressurized treatment, temperature is down to 30 ~ 35 DEG C, pressure increases to 6 ~ 8 normal atmosphere, obtain crystal, dry finally by granulation and obtain maize special fertilizer.
8. prepare the production method of monocalcium phosphate by-product maize special fertilizer as claimed in claim 1, it is characterized in that: described maize special fertilizer is the Chemical Mixed Fertilizer of chemical combination state, wherein the content of nitrogen component is 18-21%, phosphorus composition content is 5-8%, potassium component content is 9-13%.
9. prepare the production method of monocalcium phosphate by-product maize special fertilizer as claimed in claim 8, it is characterized in that: the Chemical Mixed Fertilizer of described chemical combination state contains in its composition and contains following N P and K chemical combination state structural formula:
wherein, the dotted line between carbon atom and Sauerstoffatom represents to there is coordinate bond between C atom and O atom, and contains
with
the Chemical Mixed Fertilizer of realizing controlled-release.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104016325A (en) * | 2014-05-20 | 2014-09-03 | 贵阳中化开磷化肥有限公司 | Production method for tricalcium phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104016325A (en) * | 2014-05-20 | 2014-09-03 | 贵阳中化开磷化肥有限公司 | Production method for tricalcium phosphate |
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